PDF Book of Abstracts - Queen's University Belfast

Welcome to Belfast!
It is my pleasure on behalf of the Local Organising Committee to welcome you to the 5 th
International Conference on Environmental Catalysis. For many of you this will be your first visit
to the North of Ireland and we hope that you will have a very pleasant time here. In the early
part of the 20 th Century Belfast was at the forefront of industrial development with the largest
rope-works, shipyards and tobacco, linen spinning and tea machinery plants in the world. Of
course in the recent past this region was of more interest to political rather than catalytic
scientists!
Now however, Belfast is undergoing a major transformation into a modern, knowledge-led city
with excellent local facilities and communication links to all parts of Europe and beyond. It is
also one of the fastest-growing tourist destinations in these islands.
Queen’s University which is a member of the Russell Group of universities was founded in 1849
and has a global reputation as reflected in the award of a Queen’s Anniversary Prize in 2006,
the fourth time that the University has been honoured in this way. It is set in fine surroundings
and the main building was designed by Charles Lanyon who was responsible for many other
significant edifices in the city.
The School of Chemistry (now the School of Chemistry and Chemical Engineering) has had
many distinguished academics in its history, not least the first two incumbents of the Chair of
Chemistry.
Thomas Andrews, a scholar of European reputation, was Professor of Chemistry between 1849
and 1879. He was an early pioneer of high pressure research and along with Professor James
Thomson (the elder brother of Lord Kelvin) discovered the triple point at which gases can exist
in the gaseous, liquid and solid phases.
His successor Edmund Letts who studied in Vienna and Berlin had been the first professor of
Chemistry at Bristol University - at the age of 24! His research areas included the chemistry of
organic compounds of sulphur and phosphorus; the determination of carbon dioxide in air and
water (his methods were employed by the first Scott Antarctic Expedition) and the pollution of
rivers and tidal waters, including the river Lagan along which the city of Belfast extends.
We hope that you will enjoy the scientific programme for the 5th ICEC. Because of the very
large number of abstracts that we received, the programme has been planned around three
parallel sessions. However, we have aimed to avoid as far as possible any conflicts of interest
between parallel sessions so that the need to move between lecture locations is minimized. We
are also fortunate that the facilities in Queen’s University allow all the sessions to be held in
traditional lecture rooms in close proximity to each other.
Finally, we would like to thank our sponsors for their generosity, our International Advisory
Board for their support in promoting the meeting and of course you, the participants, for coming
to Belfast. The Local Organising Committee will do all we can do to make your visit enjoyable so
if you need any assistance, advice or information please do not hesitate to ask one of the local
5ICEC members who will be wearing distinctive badges or visit the Registration and Information
Desk which during the conference will be situated in the foyer of the Peter Froggatt Building.
Cead Mille Failte

International Advisory Board
Dr. Paul Anastas
Dr. John Armor
Dr. Martin Atkins
Prof. Jesus Blanco
Prof. Hans Blaser
Prof. Edd Blekkan
Prof. Michele Breysse
Prof. Gabriele Centi
Dr. Paul Davey
Prof. Krijn de Jong
Dr. Stan Golunski
Prof. Eiichi Kikuchi
Prof. Can Li
Prof. In-Sik Nam
Prof. Lars Pettersson
Prof. Kohichi Segawa
Prof. Jerry Spivey
Prof. Hugh Stitt
Dr. Martyn Twigg
Prof. Jens Weitkamp
Prof. Blanka Wichterlova
USA
USA
UK
Spain
Switzerland
Norway
France
Italy
UK
The Netherlands
UK
Japan
China
South Korea
Sweden
Japan
USA
UK
UK
Germany
Czech Republic
Local Organising Committee
Professor Robbie Burch
Dr. David Rooney
Dr. Stuart James
Dr. Quan Gan
Dr. Cristina Lagunas
Professor Peijun Hu
Dr. Alex Goguet
Professor Chris Hardacre
Dr. Andrew Marr
Dr. Farid Aiouche
Dr. Mohammad Ahmad
Professor Roy Douglas
Dr. Sergiy Shekhtman
Dr. Jillian Thompson

MONDAY 1 st WHITLA HALL
08.30 OPENING CEREMONY
08.45 PLENARY LECTURE 1
09.30 PLENARY LECTURE 2
10.15 COFFEE COFFEE COFFEE
GO6, Peter Froggatt GO7, Peter Froggatt Bell Theatre, Physics
11.00 Autocatalysis A-1 Clean Energy CE-1 Renewables R-1
11.30 A-2 CE-2 R-2
12.00 A-3 CE-3 R-3
12.30 LUNCH LUNCH LUNCH
14.00 A-4 CE-4 R-4
14.30 A-5 CE-5 R-5
15.00 A-6 CE-6 R-6
15.30 TEA TEA TEA
16.00 A-7 CE-7 R-7
16.30 A-8 CE-8 R-8
17.00 A-9 CE-9 R-9
17.30 POSTER SESSION WITH FOOD
21.00 END OF POSTER SESSION
TUESDAY 2 nd WHITLA HALL
08.45 PLENARY LECTURE 3
09.30 PLENARY LECTURE 4
10.15 COFFEE COFFEE COFFEE
GO6, Peter Froggatt GO7, Peter Froggatt Bell Theatre, Physics
11.00 A-10 CE-10 Green Chemistry GC-1
11.30 A-11 CE-11 GC-2
12.00 A-12 CE-12 GC-3
12.30 LUNCH LUNCH LUNCH
13.00 POSTER SESSION AND TEA
16.00 A-13 Air and Water AW-1 GC-4
16.30 A-14 AW-2 GC-5
17.00 A-15 AW-3 GC-6
19.00 RECEPTION RECEPTION RECEPTION
19.30 BANQUET OR STUDENT PARTY
WEDNESDAY 3 rd GO6, Peter Froggatt GO7, Peter Froggatt
09.00 A-16 AW-4 GC-7
09.30 A-17 AW-5 GC-8
10.00 A-18 AW-6 GC-9
10.30 COFF EE COFFEE COFFEE
11.00 A-19 AW-7 GC-10
11.30 A-20 AW-8 GC-11
12.00 A-21 AW-9 GC-12
12.30 LUNCH LUNCH LUNCH
14.00 A-22 AW-10
14.30 A-23 AW-11
15.00 A-24 AW-12
15.30 TEA TEA TEA
16.00 A-25 AW-13
16.30 A-26 AW-14
17.00 CLOSING CEREMONY

Monday 1 st September
ORAL PROGRAMME
08.30 Opening Ceremony (Whitla Hall)
Plenary session (Whitla Hall)
08.45 Renewables for chemicals and fuels
P. Gallezot, Institut de recherches sur la catalyse et l’environnement de Lyon
09.30 Future demands on buses and implications for emission control
E. Jobson, Volvo Bus Corporation, Dept 80060, ARHK6N,SE-405 08 Göteborg, Sweden
10.15 Coffee break
Autocatalysis (G06 - Peter Froggatt Centre)
11.00 Role of Ag cluster on Hydrogen Effect of HC-SCR over Ag/alumina A-1
Ken-ichi Shimizu, Junji Shibata, Koyoichi Sawabe, Atsushi Satsuma*
11.30 Selective Catalytic Reduction of NOx by Simulated Diesel Fuel Containing A-2
Oxygenated Hydrocarbon
Mun Kyu Kim, Pyung Soon Kim, Joon Hyun Baik, In-Sik Nam*, Byong K. Cho,
Se H. Oh
12.00 A combination between a low- and a high-temperature catalyst for A-3
the SCR of NOx using second-generation biodiesel in microchannels
J.R. Hernández*, K. Arve, K. Eränen, T. Salmi and D.Yu. Murzin
12.30 Lunch break
14.00 A NO x Reduction System Using Ammonia-Storage Selective A-4
Catalytic Reduction in Rich/Lean Excursions
T. Nakatsuji*, M. Matsubara, J. Rouistenmäki, N, Satoh and H. Ohno
14.30 CO and NH 3 -combined SCR with an internal heat exchanging reactor A-5
A. Obuchi*, J. Uchisawa T. Nanba, A. Ohi, N. Iijima, K. Wada
15.00 Nature and evolution of palladium species on Pd-LaCoO 3 and Pd-Al 2 O 3 A-6
on the course of the reactions NO+H 2 +O 2 followed with Operando EXAFS
J.P. Dacquin, P. Miquel, C. Dujardin*, S. Cristol, S. Nikitenko, W. Bras, P. Granger
15.30 Coffee break
16.00 Detailed and global kinetic modelling of ammonia SCR on copper zeolites A-7
Louise Olsson*, Hanna Sjövall, Richard J. Blint and Ashok Gopinath
16.30 Mechanistic kinetic modelling of the “Fast” NH 3 -SCR reaction over a A-8
Fe-ZSM5 Catalyst
Isabella Nova, Antonio Grossale, Enrico Tronconi*, Daniel Chatterjee and Michel Weibel
17.00 Direct conversion of NO x and soot into N 2 and CO 2 in diesel exhaust A-9
on Fe 2 O 3 catalyst
D. Reichert, H. Bockhorn and S. Kureti*
17.30 Poster session I - in the Great Hall and South Dining Room
20.00 End of Poster session

Monday 1 st September
Clean Energy (GO7 - Peter Froggatt Centre)
11.00 Fuel production by Fischer-Tropsch synthesis with CO/H 2 CE-1
from different feeds
S. Løgdberg, Ø. Borg, D. Tristantini, E.A. Blekkan, B. Gevert, S. Järås,
and A. Holmen*
11.30 Catalyst calcination and glow discharge plasma: Tools to enhance, CE-2
Dispersion reducibility and performance of cobalt catalysts in
Fischer-Tropsch synthesis
A.Y. Khodakov*, W. Chu*, J. Hong, P.A. Chernavskii, J.-S. Girardon and
A. Griboval-Constant
12.00 A new option in CO 2 recycle: conversion to long-chain alcohols CE-3
and hydrocarbons
M. Gangeri, S. Caudo, S. Perathoner*, G. Centi, D. Bégin, C. Pham-Huu,
J.P. Tessonnier and D.S. Su
12.30 Lunch break
14.00 Preparation of ordered mesoporous CuO/CeO 2 and their catalytic CE-4
behavior in CO preferential oxidation and water gas shift reaction
S. Naito*, W. Shen, T. Hasegawa and T. Miyao
14.30 Controlled surface modification of Pt/Al 2 O 3 catalysts for preferential CE-5
oxidation of CO in hydrogen fuel streams
S.K. Jain, E.M. Crabb*, L.E. Smart and D. Thompsett
15.00 Preferential oxidation of CO over Au/Al 2 O 3 catalysts CE-6
for fuel cell applications
E. Quinet, F. Morfin, F. Diehl, P. Avenier, V. Caps* and J.-L. Rousset
15.30 Coffee break
16.00 Stable gold nanoparticles for hydrogen purification reactions: CE-7
a challenging approach for robust catalysts
M. Cargnello, P. Fornasiero*, C. Gentilini, M. Graziani, T. Montini,
L. Pasquato, S. Polizzi
16.30 Reversible changes occurring in the CO chemisorption capability CE-8
of a Au/Ce 0.62 Zr 0.38 O 2 catalyst. Influence of the support redox state.
José M. Cíes, E. del Río, M. López Haro, S.E. Collins, J.J. Calvino, J.J. Delgado,
S. Trasobares, and S. Bernal*
17.00 Kinetics of the water-gas shift reaction over Pt and Au supported CE-9
bifunctional catalysts.
Olivier Thinon, Yves Schuurman*, Fabrice Diehl, Priscilla Avenier
17.30 Poster session I - in the Great Hall and South Dining Room
20.00 End of Poster session

Monday 1 st September
Renewables (Bell Lecture Theatre - Physics Building)
11.00 Liquid phase hydrogenation of biomass-derived lactic acid: R-1
A detailed description of kinetics and mechanism over Ru-based catalysts
at low pressure
Hans Gelten, Barbara Mojet and Leon Lefferts*
11.30 Bio-glycerol conversion under mild conditions through heterogeneous R-2
catalysis
E. D’Hondt, S. Van de Vyver, B. De Vis, B. Sels, and P.A. Jacobs*
12.00 New insight into glycerol etherification over basic oxides R-3
A.M. Ruppert, J.D. Meeldijk, B.W.M. Kuipers, B.H. Erné and B.M. Weckhuysen*
12.30 Lunch break
14.00 Transesterification of vegetable oils on basic large mesoporous alumina R-4
supported alkaline fluorides – evidence of the nature of the active site and
catalytic performances
M. Verziu, S. Simon, P. Filip and V.I. Parvulescu*
14.30 New developments in solid acid and base catalysts for biodiesel synthesis R-5
K. Wilson*, A.F. Lee, J. Montero and K. Narashimharao
15.00 Cellulose conversion to soluble sugars by supported metal catalysts R-6
A. Fukuoka*, P. L. Dhepe, M. Watanabe, K. Kasai, M. Kondo and K. Hara
15.30 Coffee break
16.00 Telomerization of crude glycerol with 1,3-butadiene towards R-7
new surfactant molecules
R. Palkovits, I. Nieddu, C. Kruithof, R. J. M. Klein-Gebbink and B. M. Weckhuysen*
16.30 Catalytic valorization of bioethanol over mixed oxides Cu-Mg-Al catalysts R-8
Nathalie Tanchoux*, Ioan-Cézar Marcu, Didier Tichit and François Fajula
17.00 Hydrogen from Glycerol by Aqueous-Phase Reforming R-9
K. Lehnert and P. Claus*
17.30 Poster session I – in the Great Hall and South Dining Room
20.00 End of Poster session

Tuesday 2 nd September
Plenary session (Whitla Hall)
08.45 Ultra-deep Desulfurization of Fuels by Emulsion Catalysis
Can Li, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, China
09.30 Sustainability through Green Processing –
Novel Process Windows intensify Micro Processing and Applications in Catalysis
V. Hessel, Eindhoven University of Technology (TU/e), Eindhoven, the Netherlands;
Institut für Mikrotechnik Mainz GmbH (IMM), Mainz, Germany
10.15 Coffee break
Autocatalysis (G06 - Peter Froggatt Centre)
11.00 Evaluating Axial Distributions of Species and Temperature on A-10
Monolith-Supported Catalysts via Spatially-Resolved Calorimetry
William Epling*, Alan Shaw, Khurram Aftab, Aleksey Yezerets and
Neal W. Currier
11.30 Intermediate NH 3 Generation and Utilization Inside a Lean NO x A-11
Trap Catalyst
W. P. Partridge*, J-.S. Choi, J.A. Pihl, T.J. Toops and C.S. Daw
12.00 Novel CeO 2 -Al 2 O 3 nano composite for inhibiting Pt sintering of A-12
NSR catalyst
Hiroyuki Matsubara*, Yuichi Sobue, Nobuyuki Takagi, Yasutaka Nagai,
Keisuke Kishita, Nobumoto Ohashi and Shin’ichi Matsumoto
12.30 Lunch break
13.00 Poster Session II - in the Great Hall and South Dining Room
15.30 Coffee break
16.00 Kinetics of Sulfur Removal from a Commercial Lean NOx Trap Catalyst A-13
Aleksey Yezerets*, Neal W. Currier, Junhui Li, Haiying Chen and
Howard S. Hess
16.30 Thermal Aging of Lean NO x Trap Catalysts Using Reactor-Generated A-14
Exotherms and the Resulting Material Effects
T.J. Toops*, B.G. Bunting, K. Nguyen, N.A. Ottinger and H. Kim
17.00 Hydrolysis of Isocyanic Acid over TiO 2 (Anatase): Unraveling the A-15
Reaction Mechanism by a Combination of DFT Calculations,
DRIFT Spectroscopy and Kinetic Studies
O. Kröcher*, I. Czekaj and G. Piazzesi
19.00 Banquet Reception (Great Hall) or start of Student Party (Student’s Union)
19.30 Banquet (Whitla Hall) or continuation of Student Party (Student’s Union)

Tuesday 2 nd September
Clean Energy (G07 - Peter Froggatt Centre)
11.00 Molecular mechanism and intrinsic kinetics of catalytic steam CE-10
reforming of methane over Rh/Ce Zr 1- O 2 as an efficient catalyst
for H 2 production with in situ CO 2 capture
M.H. Halabi, M.H.J.M. de Croon, J. van der Schaaf, P.D. Cobden* and
J.C. Schouten
11.30 Detailed surface mechanism for the catalytic partial oxidation CE-11
of ethanol over rhodium
N. Hebben* and O. Deutschmann
12.00 New Research System for Environmental Catalysis: CE-12
Coupled Instrument Array
John T. Gleaves, Gregory Yablonsky*, Rebecca Fushimi, Xiaolin Zheng,
Steven Buckner and Patrick Mills
12.30 Lunch break
13.00 Poster Session II - in the Great Hall and South Dining Room
15.30 Coffee break
Air and Water (GO7 - Peter Froggatt Centre)
16.00 The utility of cyclodextrins for enhancing the hydrodechlorination of AW-1
carbon tetrachloride in water catalyzed by palladium on charcoal
Anne Ponchel*, Sophie Lamotte-Fourmentin, David Landy and Eric Monflier
16.30 Solvent and particle size effects in the liquid phase hydrodechlorination AW-2
of 2,4-chlorophenol over Pd/Al 2 O 3
S. Gómez-Quero* and M.A. Keane
17.00 Tailoring of Pd-Catalysts for Application under Environmental Conditions AW-3
Katrin Mackenzie, Dalia Angeles-Wedler and Frank-Dieter Kopinke
19.00 Banquet Reception (Great Hall) or start of Student Party (Student’s Union)
19.30 Banquet (Whitla Hall) or continuation of Student Party (Student’s Union)

Tuesday 2 nd September
Green Chemistry (Bell Lecture Theatre - Physics Building)
11.00 Carbon dioxide and methane in chemical synthesis: GC-1
direct catalytic carboxylation of methane and acetylene to vinyl acetate
J.J. Spivey*, E.M. Wilcox and G.W. Roberts
11.30 CO 2 conversion via one-step synthesis of dimethyl ether (DME) GC-2
A. Narvaez-Dinamarca, L. Torrente-Murciano, Y.K. Chan, C.L. Tang and D. Chadwick*
12.00 Green Chemistry with CO 2 : synthesis of carbamates and cyclic carbonates GC-3
Angelica Ion*, Vasile Parvulescu, Pierre Jacobs and Dirk De Vos
12.30 Lunch break
13.00 Poster Session II - in the Great Hall and South Dining Room
15.30 Coffee break
16.00 Green synthesis of DMC by transesterification of ethylene carbonate GC-4
over solid bases
Georgiana Stoica, Sònia Abelló and Javier Pérez-Ramírez*
16.30 Activity and Selectivity Control in the Synthesis of Alicylic Amines. GC-5
K.F. Graham, K.T. Hindle, S.D. Jackson*, D.J.M. Williams and S. Wuttke
17.00 Use of Gold Catalysts to Promote the Ultra-Selective GC-6
Sustainable Production of Aromatic Amines
F. Cárdenas-Lizana* and M.A. Keane
19.00 Banquet Reception (Great Hall) or start of Student Party (Student’s Union)
19.30 Banquet (Whitla Hall) or continuation of Student Party (Student’s Union)

Wednesday 3 rd September
Autocatalysis (G06 - Peter Froggatt Centre)
09.00 Model NO x Storage Catalysts: Reaction Mechanisms and Kinetics A-16
at the Microscopic Level
A. Desikusumastuti, T. Staudt, M. Happel, Z. Qin, S. Shaikhutdinov,
S. Gardonio, S. Lizzit, E. Vesselli, A. Baraldi, H. Grönbeck and J. Libuda*
09.30 NSR catalyst supported on a Al 2 O 3 / ZrO 2 -TiO 2 nano-composite: A-17
Sulphur Resistance
N. Takahashi*, H. Imagawa, T. Tanaka, S. Matsunaga, H. Sobukawa and H. Shinjoh
10.00 Understanding practical catalysts using a surface science approach: A-18
The importance of strong interaction between BaO and Al 2 O 3
Cheol-Woo Yi, Ja Hun Kwak, Charles H.F. Peden, and János Szanyi*
10.30 Coffee break
11.00 Synthetic gas bench study of a 4 way catalytic converter: catalytic A-19
oxidation, NOx storage/reduction and impact of soot loading and regeneration
C.N. Millet*, R. Chedotal and P. Da Costa
11.30 Copper ferrite nanoparticles as microwaves susceptible soot A-20
oxidation catalyst
Vincenzo Palma*, Paola Russo, Giuseppa Matarazzo and Paolo Ciambelli
12.00 An operando 5.8 GHz microwave-heated FT-IR reactor study of the A-21
NO 2 -CH 4 reaction, over a Co/Pd-HFER catalyst
S. Capela, E. Seguin, C. Henriques*, M.F. Ribeiro, F.Thibault-Starzyk,
S. Thomas, P. Da Costa, G. Djéga-Mariadassou, F. Ramôa Ribeiro
12.30 Lunch break
14.00 Model of catalytic carbon black oxidation in the presence of A-22
CeO 2 : 3-D representation of the solid-solid mixture
M. Issa, H. Mahzoul, V. Tschamber*, A. Brillard and J-F. Brilhac
14.30 Correlation between spatiotemporal distribution of reactions and global A-23
performance of a commercial lean NO x trap catalyst at varying sulfation
stages
Jae-Soon Choi*, William P. Partridge, Josh A. Pihl, Todd J. Toops,
Michael J. Lance, Charles A. Finney, Kalyana Chakravarthy and C. Stuart Daw
15.00 Activation of Al 2 O 3 by a long range stabilization mechanism A-24
Anders Hellman and Henrik Grönbeck
15.30 Coffee break
16.00 Advanced solutions for the pollution abatement from the ships A-25
cruising the motorways of the sea
N. Hickey, I. Boscarato and J. Kašpar
16.30 Mechanism of the C 2 H 2 oxidation in the presence of CO on gold A-26
catalyst : a model reaction for Cold Start Engine Oxidation
Yassine Azizi, Corinne Petit and Véronique Pitchon*
17.00 Closing ceremony in GO6 – Peter Froggatt Centre

Wednesday 3 rd September
Air and Water (G07 - Peter Froggatt Centre)
09.00 Unveiling the mechanism of the SO 2 -assisted N 2 O abatement AW-4
over iron zeolites
Miguel A.G. Hevia, Sònia Abelló and J. Pérez-Ramírez*
09.30 The catalytic performance of Cu-zeolites in the N 2 O decomposition: AW-5
an unprecedented positive effect of H 2 O
P.J. Smeets, B.F. Sels, E.J.M. Hensen and R.A. Schoonheydt*
10.00 Mechanistic origins governing catalytic de-N 2 O activity of Fe- AW-6
and Rh-MFI zeolites
Evgenii V. Kondratenko*, Vita A. Kondratenko, Marta Santiago and
Javier Pérez-Ramírez
10.30 Coffee break
11.00 Maintaining the activity of gold catalysts for cleaning water and air AW-7
Richard Holliday, Jason McPherson, Thabang Ntho and David Thompson*
11.30 Ceria-supported gold catalysts for wastewater treatment: AW-8
influence of the pre-treatment conditions.
N. D. Tran, M. Besson, C. Descorme*, K. Fajerwerg, C. Louis and C. Méthivier
12.00 Relevance of oxygen-containing VOC as model molecule for the AW-9
study of dioxin total oxidation on VO x /TiO 2 catalysts.
R. Delaigle, D.P. Debecker and E.M. Gaigneaux*
12.30 Lunch break
14.00 A time-resolved in situ XANES study of transient methane AW-10
oxidation over alumina supported platinum
E. Becker*, P-A. Carlsson, H. Grönbeck and M. Skoglundh
14.30 Activation and oxidation of methanol over ceria and titania-supported AW-11
Au catalysts: an operando IR study of the active site and reaction mechanism
S. Rousseau, P. Bazin, F.C. Meunier, O. Marie*, V. Harlé, S. Verdier and M. Daturi
15.00 Plasma-assisted total catalytic oxidation of methane. AW-12
On the effects of energy deposition, feed composition, and catalytic phase
Rui Marques, Stéphanie Da Costa, Stephane Carpentier, Patrick Da Costa*
15.30 Coffee break
16.00 Efficient removal and detoxification of organic pollutants by AW-13
catalytic wet-air oxidation
A. Pintar*, J. Batista and T. Tišler
16.30 Wet Air Oxidation of Phenol over ceria and doped-ceria supported AW-14
platinum and ruthenium catalysts: Analysis of the Carbonaceous Deposit
and Study of its impact on the catalytic activity
S. Keav, J. Barbier Jr.* and D. Duprez
17.00 Closing ceremony in GO6 – Peter Froggatt Centre

Wednesday 3 rd September
Green Chemistry (Bell Lecture Theatre - Physics Building)
09.00 Molecular biological designed biotemplates for catalysts with GC-7
reduced precious metal content
S. Roos, D. Keck, J. Hofinger, A. Springer and M. Berndt
09.30 Alkylation of benzene with ethane into ethylbenzene over GC-8
PtH-ZSM-5 bifunctional catalyst at low temperatures
K. S. Wong, T. Vazhnova and D. B. Lukyanov*
10.00 An examination of reaction pathways accessible in the manufacture GC-9
of trichloroethene and tetrachloroethene via the oxy-chlorination process
David Lennon*, John. M. Winfield, Iain W. Sutherland, Neil Hamilton,
Christopher C. Dudman and Peter Jones
10.30 Coffee break
11.00 Selective aerobic oxidation of alcohols GC-10
A.F. Lee*, S.F.J. Hackett, A.D. Newman and K. Wilson
11.30 Green Organic Syntheses with Alcohols by Concerto GC-11
Metal Catalysts Using Inorganic Crystallites
Kiyotomi Kaneda*
12.00 Implication of the support in the Au/TiO 2 -catalyzed aerobic GC-12
epoxidation of stilbene
P. Lignier, B. Jouguet, S. Bennici, A. Auroux, J.-L. Rousset and V. Caps*
12.30 Lunch break
17.00 Closing ceremony in GO6 – Peter Froggatt Centre

Great Hall - Poster Session I
Autocatalysis
113 Synthesis, phase stability and catalytic activity of Pd-doped La-based perovskites during
SCR-NO x with C 3 H 6
G.C. Mondragón Rodríguez*, B. Saruhan
122 In situ FT-IR investigation on Pd/SA for the selective catalytic reduction of NO with CH 4
Hongyan Zhang, Aiqin Wang, Lin Li, Xiaodong Wang and Tao Zhang*
127 Catalytic activity for soot combustion of birnesite and criptomelane.
I. Atribak, A. Bueno-López * , A. García-García, P. Navarro, D. Frías and M. Montes
131 Manganese Based Materials for Diesel Exhaust SO 2 Traps
O. Kröcher*, K. Tikhomirov, M. Elsener, M. Widmer and A. Wokaun
132 New Insights into the Reactions between NH 3 , NO and NO 2 over Fe-ZSM5
O. Kröcher* and M. Elsener
133 Chemical Deactivation of V 2 O 5 /WO 3 –TiO 2 SCR Catalysts by Additives and Impurities
from Fuels, Lubrication Oils, and Urea Solution
O. Kröcher*, M. Elsener, D. Nicosia and I. Czekaj
137 Hydrogen Effect on Urea-SCR by Ag/alumina: Practical and Mechanistic Aspects
Ken-ichi Shimizu* and Atsushi Satsuma
140 Kinetics and mechanism of carbon oxidation with NO 2 and O 2 in presence of Ru/Na-Y
catalyst
M. Jeguirim*, V. Tschamber, K. Villani, J.F.Brilhac and J.A. Martens
143 Novel Preparation Method for Ag/Al 2 O 3 HC-SCR Catalysts
Hannes Kannisto*, Hanna Härelind Ingelsten and Magnus Skoglundh
144 CeO 2 and CeO 2 -ZrO 2 mixed oxides as catalysts for the combined removal of NO x
and soot from diesel exhausts.
I. Atribak, A. Bueno-López and A. García-García*
148 Role of enolic species in the selective catalytic reduction of NOx with hydrocarbons
over Ag/Al 2 O 3
H. He*, Y.B. Yu, Q. Wu and X.L. Zhang
154 H 2 –SCR NO x catalytic activity and N 2 -selectivity of Pd-exchanged perovskites
G. C. Mondragón Rodríguez*, B. Saruhan and J. Breen
158 Screening of different MnO x -CeO 2 doped catalysts for low-temperature SCR reaction
Maria Casapu, Oliver Kröcher and Martin Elsener
168 Mercury oxidation and reduction by SCR-DeNOx-catalysts in coal fired power plants -
Micro scale investigations
Raik Stolle*, Heinz Gutberlet, Joachim Tembrink and Heinz Koeser
169 Support Modification to Improve the Sulphur Tolerance of Ag/Al 2 O 3 for SCR of NO x
with Propene under Lean-Burn Conditions
Neelam Jagtap, Shubhangi B. Umbarkar, Pascal Granger and Mohan K. Dongare*
171 The influence of surface area and redox behaviour in soot oxidation over CeO 2 -ZrO 2
Eleonora Aneggi*, Carla de Leitenburg, Giuliano Dolcetti and Alessandro Trovarelli
181 Effect of ceria on the sulfation and desulfation characteristics of lean NO x trap catalysts
Y. Ji, V. Easterling, M. Crocker*, T.J. Toops, J. Theis, J. Ura and R.W. McCabe

182 Carbon nanotube supported catalysts for NO x reduction using hydrocarbon reductants
E. Santillan-Jimenez and M. Crocker*
199 The effect of NOx traps on the combustion of carbonaceous particulate matter.
J.A. Sullivan and P. Dulgheru*
201 On the characterisation of silver species on Ag/Al 2 O 3 catalysts for SCR of NO x with ethanol
A., Musi, P., Massiani, J.M., Trichard, and P. Da Costa*
211 Selective catalytic reduction of nitrogen oxide with propene in the presence of excess
oxygen over gold based catalysts
L. Delannoy*, L. T. Nga Nguyen, P. Lakshmanan, V. Richard, C. Potvin and C. Louis
213 Soot oxidation characteristics as function of diesel fuel composition
Ing. H.Jansma, Dr. R. Uitz and Dr.Ir. M. Makkee*
214 A systematic examination of the effect of preparation variables on the properties
and the SCR-NH 3 and SCR-Urea activities of Fe ZSM-5 catalysts
S. Burnham*, J. A. Sullivan, P. Dulgheru and L. Sherry
221 Influence of sulphur on Pd/Ce-Zr-based catalysts in CO, C 3 H 6 , and C 3 H 8 oxidation
T. Kolli*, M. Huuhtanen, A. Hallikainen, K. Kallinen and R. L. Keiski
227 On the evolution of commercial Natural Gas Vehicle catalysts as function of mileage
M. Salaün, A. Kouakou, S. Da Costa, P. Granger and P. Da Costa*
229 H 2 -SCR: NO x reduction at low temperatures in diesel passenger cars
F.J.P. Schott and S. Kureti*
231 Insights of NOx storage on ceria based NSR-catalyst compounds
M. O. Symalla, A. Drochner, H. Vogel, S. Philipp and S. Eckhoff
232 Influence of the three way catalyst design parameters on its conversion performance
H. Santos and M. Costa*
235 NO reduction by CO over gold catalysts based on doped ceria
L. Ilieva* G. Pantaleo, A. M. Venezia and D. Andreeva
237 Importance of the WO x -ZrO 2 -supported catalyst composition in the C 3 H 6 - and C 3 H 8 -SCR
of NO x
N. El Kolli, C. Potvin and C. Thomas*
238 On the unexpected promoting effect of the PdCl 2 precursor on the CH 4 -SCR of NO x for
WO x -ZrO 2 -supported catalysts
M. Faticanti, X. Carrier, J.-M. Krafft, M. Che and C. Thomas*
239 Unambiguous evidence for the formation of RNO x compounds on WO x -ZrO 2 -based
catalysts: active or spectator species in the C 3 H 6 -SCR of NO x ?
N. El Kolli, C. Potvin and C. Thomas*
242 Effect of physical mixing of metal oxide with Ir-Ba/WO 3 -SiO 2 on CO-SCR activity
T. Nanba*, K. Wada, S. Masukawa, J. Uchisawa and A. Obuchi
246 DeNO x with CO over Pd catalysts under simulated post Euro- diesel exhaust conditions
Li Yinghua, Dae-Won Lee, Young-Chul Ko, Yoon-Ki Hong a , Young-San Yoo c , Hyun-Sik Han c
and Kwan-Young Lee*
247 Reduction of NO by C 3 H 6 over Rh/CeO 2 -ZrO 2
M. Haneda*, K. Shinoda, A. Nagane, O. Houshito, H. Takagi, Y. Nakahara, K. Hiroe,
T. Fujitani and H. Hamada

248 CeO 2 -Y 2 O 3 and CeO 2 -ZrO 2 -Y 2 O 3 mixed oxide catalysts for diesel soot combustion.
I. Atribak, A. Bueno-López and A. García-García*
251 Direct decomposition of NO on Ba catalysts supported on Ce-Fe mixed oxides
W.-J. Hong, S. Iwamoto* and M. Inoue
259 SCR on Fe/BEA zeolite catalysts in diesel exhaust
P. Balle, B. Geiger and S. Kureti*
260 The possibilities of hydrotalcites as NO x Storage/Reduction catalysts
A.E. Palomares*, A.Uzcátegui and A. Corma
264 A comparison of transport models for the simulation of three-way catalysts
N. Mladenov*, J. Koop and O. Deutschmann
265 Investigation and calibration of a global kinetic model of today's 3 way catalytic converters
C.N. Millet*, S. Benramdhane and E. Jeudy
268 Improved detailed reaction mechanisms for three-way catalysts
S. Tischer*, L. Maier and O. Deutschmann
273 PCHs obtained from various cationic layered clays as base of DeNOx catalysts
L. Chmielarz*, P. Kustrowski, Z. Piwowarska, B. Dudek and R. Dziembaj
274 Cu perovskite catalysts for soot combustion: effect of copper loading method
F. E. López-Suárez, A. Bueno-López, M.J. Illán-Gómez*, B. Ura, J. Trawczynski and A. Adamski
275 Characteristics and catalytic reactivity of soot from biodiesel
F. E. López-Suárez, A. Bueno-López, M.J. Illán-Gómez*, C.A.Cardona, O. H. Giraldo and
C. E. Orrego
276 Cu/BaO/La 2 O 3 catalyst for the efficient simultaneous removal of NOx and carbon
particulate
Hiromi Yamashita*, Yoshiro Iwata, Akihiko Miyauchi and Kohsuke Mori
285 Influence of the ageing conditions on the structure of commercial three-way catalysts
H. C. Hahn*, H. Fuess and C. Heinrich
286 Catalytic Properties of Pr 2 O 2 SO 4 Having a Large Oxygen-storage Capacity:
Unsteady-state NO-CO Reactions under Cycled Feed Stream Conditions
D.J. Zhang, M. Eto, F. Yoshioka, K. Ikeue and M. Machida*
287 On the Reason for High Activity of CeO 2 for Catalytic Soot Combustion
Y.Murata, K.Kishikawa, K.Ikeue and M. Machida*
General Topics
114 Characterization and photocatalytic activity of highly active mesoporous TiO 2
prepared in weak acid solutions by assistance of the hydrothermal treatment
Taicheng An*, Jikai Liu, Guiying Li, Xiangying Zeng, Guoying Sheng and Jiamo Fu
161 Zeolite-encapsulated sensitizers for the photocatalytic decomposition of sulfur
containing chemical warfare agents
B. Cojocaru, V. I. Parvulescu*, E. Preda, G. Lepure, V. Somoghi, E. Carbonell, M. Alvaro
and H. García
166 Synthesis and Application of NaTaO 3 Photocatalysts for Water-Splitting to Produce
Hydrogen
Ien-Whei Chen*, Chih-Hao Tan and Guo-Cheng Peng
192 Photodecomposition of H 2 S to Produce H 2 over Cd x Zn 1-x S Composite Photocatalysts
Xuefeng Bai and Dan Wu

197 Investigation of photocatalytic degradation of p-chlorophenol exploiting zinc oxide
Umar Ibrahim Gaya, Abdul Halim Abdullah*, Zhulkarnain Zaina and Mohd Zobir Hussein
207 Reaction Studies of a Combined Plasma Catalyst Reactor
D.T Lundie, J.A. Rees, D.L Seymour and T.D. Whitmore
208 Photocatalytic Mineralization of Organic Acids in Aqueous Medium using Nano-crystalline
Titania Prepared by Sol-Gel Technique
V.G. Gandhi, M K. Mishra, M.S. Rao, A. Kumar, K.R. Krishnamurthy, P.A. Joshi* and
D.O. Shah
216 TiO 2 /vc-SBA-15: Preparation, characterization and photocatalytic reduction of CO 2
Shu-Hua Chien*, Yi-Jhen Feng, Chin-Jung Lin, Wen-Yueh Yu and Kuo-Pin Yu
245 Kinetic Studies for Photocatalytic Degradation of Methyl Orange on Transition Metal
Modified TiO 2
C.-G. Wu*, S.-H. Hong and I-L. Sung
254 Photocatalytic activity of (Fe, Eu) doped TiO 2 nanocrystals synthesized by a hydrothermal
route
L. Diamandescu, F. Vasiliu*, V. Danciu and D. Tarabasanu-Mihaila
261 Design of hydrophobic zeolite and mesoporous materials by the modification using TEFS
and its application as supports of TiO 2 photocatalyst
Y. Kuwahara, K. Maki, K. Mori and H. Yamashita*
279 Metallic monoliths and microreactors coated with carbon nanofiber layer as catalyst
support
E.García-Bordejé, V. Martinez-Hansen, C. Royo, E. Romeo and A. Monzon
294 Different strategies to improve photocatalytic activity of titania-based systems
A. Marinas*, M.A. Aramendía, J.C. Colmenares, J. Hidalgo, S. López-Fernández,
J.M. Marinas and F.J. Urbano
295 Selective photooxidation of 2-propanol to acetone on different titania and vanadia-based
ZSM-5 systems
M.A. Aramendía, J.C. Colmenares, S. López-Fernández, A. Marinas*, J.M. Marinas and
F.J. Urbano
296 Novel nanohybrid basic material L-leucine/Mg-Al layered double hydroxide
R. A. Miranda, A. M. Segarra, F. Medina and J. E. Sueiras
314 Synthesis and Characterization of N-doped Visible Light Response TiO 2 Nanotubes
Aimin Yu, Baocheng Lv, Guoqing Pan, Yong Pi, Fuxiang Zhang, Yali Yang and Naijia Guan*
316 Photocatalytic properties of TiO 2 supported catalyst under sunlight irradiation for air
treatment
T. Lewis, S. Suárez*, J.A. Coronado, R. Portela, P.Avila and B. Sanchez
333 in situ spatially resolved near-infrared imaging for heterogeneous catalytic reactions
F. Aiouache*, M. Nic An tSaoir, K. Kitagawa and C. Hardacre
344 Direct synthesis of H 2 O 2 from H 2 and O 2 over Pd-loaded powdered diamond catalyst
Ryosuke Yamane, Na-oki Ikenaga, Takanori Miyake and Toshimitsu Suzuki

South Dining Room – Poster Session I
Green Chemistry
101 Negative effect of [bmim][PF 6 ] on the catalytic activity of alcohol dehydrogenase:
mechanism and prevention
Xirong Huang
103 Ullmann coupling reaction of chlorobenzene over a novel nanoporous Pd/SiO 2 -C
catalyst in aqueous media
Haiyan Wang and Ying Wan*
104 Periodic Mesoporous Organosilicas: A Kind of Hybrid Supports for Water-Mediated
Reaction
Ying Wan*
105 Cycloaddition of carbon dioxide to allyl glycidyl ether using immobilized ionic liquid
catalyst on hybrid MCM-41
S. Udayakumar, D. W. Park*, M. K. Lee, H. L. Shim and S. W. Park
109 H 3 [PMo 12 O 40 ] immobilized on Ionic liquids: A green and recyclable catalytic system
for synthesis of 2,4,5-triarylimidazoles using microwave irradiation
N. Mobarrez and A. Mirjafari*
110 Molybdenum carbide catalysts for CO hydrogenation to alcohols
M. Xiang, D. Li, H. Xiao, J. Zhang, W. Li and Y. Sun*
115 Synthesis of 2-Cumaranon in the Presence of Lacunary Keggin Structures,
[PW 11 MO 40 ] p- ( M= Co, Ni, Cu, Zn ) as Green Catalysts
A. Gharib, F. F. Bamoharram, M. Roshani and M. Jahangir
116 An eco-friendly catalytic route for Conversion of Alcohols to Nitro and Azido Compounds
by Effect of Ultrasound and Heteropolyacids Catalysts
A. Gharib, F. F. Bamoharram, M. Roshani and M. Jahangir
121 Investigation of CO 2 adsorption on amine-functionalized nanosized MCM-41 support
Linfang Wang, Aiqin Wang , Lei Ma and Tao Zhang*
126 Surface mobility and reactivity of supported copper oxide catalysts:
Isopropanol decomposition.
K. Lanasri, K. Bachari, D. Halliche, Z. Rassoul, O. Cherifi and A. Saadi*
129 Study of the dimerization of 1-pentene catalyzed by ion-exchange resins
M. Cadenas, R. Bringué, J. Tejero, M. Iborra, C. Fité, J.F. Izquierdo and F. Cunill*
134 Microwave-enhanced rapid one-pot deprotection, esterification and silylation of
MOM- and EOM-ethers in [Hmim]HSO 4 as a Brönsted acid ionic liquid
A. Mirjafari*, I. Mohammadpoor-Baltork, M. Moghdam, A. R. Khosropour, V. Mirkhani and
S. Tangestaninejad
138 Preparation, characterisation and activity testing of Gold Catalysts supported on
Single Walled Carbon Nanotubes
Anne E Shanahan*, James A Sullivan, Mary McNamara and Hugh J Byrne
165 Sulfonic acid functionalized mesoporous organosilicas as novel solid acid for catalysis
Jian Liu, Jie Yang, Congming Li and Qihua Yang*
167 Molybdenum carbide catalysts for CO hydrogenation to alcohols
M. Xiang, D. Li, H. Xiao, J. Zhang, W. Li and Y. Sun*
174 Anion-modified Mg-Al mixed oxides as solid base catalysts for the alcoholysis of
propylene oxide
G. Wu, X. Wang, J. Li, F. Xiao, W. Wei * and Y. Sun*

175 Efficient selective oxidation of benzyl alcohol with hydrogen peroxide catalyzed
by chromium Schiff base complexes immobilized on MCM-41
Xiaoli Wang, Gongde Wu, Junping Li, Fukui Xiao, Wei Wei and Yuhan Sun*
176 One-Step Method of Direct Synthesis of Dipropylene Glycol over Efficient Super Basic
Catalyst
Z. Liu, G. Wu, N. Sun, J. Li, N. Zhao, F. Xiao, W. Wei* and Y. Sun*
178 Development of new Ce/La/Zr Super Acid Catalysts
H. Stephenson*, H. Bradshaw, C. J. Butler, D. Harris, R. Brown and H. Williams
180 Ceria supported group IB metal catalysts for oxidation reactions of environmental interest
S. Scirè*, C. Crisafulli and P.M. Riccobene
184 Urea obtaining by and ammonia interaction
A.R. Elman* and A.E. Batov
185 Decarbonylation reaction in the course of Pd-catalyzed olefin hydrocarboxylation
A.R. Elman*, .. Batov, Yu. G. Noskov, V.M. Nosova and A.V. Kisin
209 Oxidation of anisole and 2-methoxyphenol with metal carboxyethylphosphonates
Graça Rocha*, Teresa Santos and Claúdia Bispo
217 Green and eco-friendly heteropolyanion catalysts for the selective oxidation of amine
compounds
F. F. Bamoharram*, M.M. Heravi, M. Roshani and F. Abrishami
218 [NaP 5 W 30 O 110 ] 14- as an efficient and eco-friendly catalyst for synthesis of acylals
F. F. Bamoharram*, M.M. Heravi, M. Roshani and T. Mirghafari
219 Heteropoly anions as eco-friendly catalysts for synthesis of lactones
F. F. Bamoharram*, M.M. Heravi, M. Roshani and A. Gharib
220 A catalytic route for acetylation of phenols and alcohols in the presence of sodium
30-tungstopentaphosphate
M.M. Heravi*, F. F. Bamoharram and F. Behbahani
224 Production of C 3+ olefins from ethanol by second elements-modified Fe/H-ZSM-5 catalysts
M. Inaba*, K. Murata and I. Takahara
241 NMR Determination of the Enrichment Extent in Octanoic Acid during Hydrocarboxylation
of 1-Heptene with labeled 13 CO catalyzed by PdCl 2 (PPh 3 )/PPh 3
V.. Nosova*, .V. Kisin and .R. Elman
282 Acylation of 2-methoxynaphthalene over fly ash supported cerium triflate catalyst
Chitralekha Khatri, Deepti Jain and Ashu Rani*
311 Synthesis of Primary Amides from Aldoximes by Supported Rhodium Hydroxide Catalyst
K. Yamaguchi, H. Fujiwara, Y. Ogasawara, M. Kotani and N. Mizuno*
318 Development of Dendrimer-Encapsulated Pd Catalysts for Organic Synthesis
T. Mizugaki, T. Mitsudome, K. Jitsukawa, and K. Kaneda*
349 A non-phosgene synthesis of MDI intermediate derived from CO 2
Xiaoguang Guo, Jian Li, Jianpeng Shang, Xiaoping Zhang* and Youquan Deng*
358 Alkylation of p-cresol with tert-butyl alcohol using novel Bronsted acidic ionic liquids
Sreedevi Upadhyayula*, P. Elavarasan and Kishore Kondamudi
363 Mesoporous SBA-15 silica-supported nitroxyl radical catalyst for the hypochlorite
oxidation of alcohols
A. Machado, J. E. Castanheiro, E. Godoy, I. M. Fonseca, A. M. Ramos and J. Vital*

Clean Energy
111 Mechanism of remarkable hydrogen occlusion and catalytic reaction over Ir metal clusters
confined in the hollow SiO 2 nanospheres
S. Naito*, H. Yamada, and T. Miyao
118 Catalytic purification process for the upgrading of landfill gas to fuel cell quality
W. Urban*, J. I. Salazar Gómez and H. Lohmann
120 Finely dispersed Au-Cu and Au-Ag alloy particles for CO removal from H 2 fuel
Aiqin Wang, Xiaoyan Liu, Wanjun Li and Tao Zhang*
123 Evaluation of a flexible fuel autothermal reformer using Rh catalyst
X. Karatzas*, M. Nilsson, B. Lindström and L.J. Pettersson
124 New heteropolyacid based catalyst for the removal of mercaptans from kerosene
A. de Angelis*, C. Flego, F. Cavani, A. Frattini, C. Rizzo, P. Pollesel, and W.O. Parker Jr.
125 Effect of chlorine on the catalytic behavior of Ir/CeO 2 for preferential CO oxidation
Yanqiang Huang, Aiqin Wang, Lin Li, Xiaodong Wang and Tao Zhang*
135 Mg-promoted Cu/ZnO/Al 2 O 3 catalysts for water-gas shift reaction
K. Takehira*, K. Nishida, D. Li, T. Shishido, Y. Oumi and T. Sano
136 Development extraction of oil from clay by friendly phase transfer catalyst
A.K. El Morsi* and A.M.A. Omar
150 Understanding and controlling the catalytic hydrolysis of sodium borohydride for the
production of high-purity hydrogen
S. Bennici*, A. Garron, D. wierczyski and A. Auroux
151 Supported hydrotalcites for enhanced and stable CO 2 capture
N.N.A.H. Meis*, J.H. Bitter and K.P. de Jong
157 Methanolysis of frying oil catalyzed by papaya lipase for biodiesel fuel synthesis
P. Porntippa* and P. Jakkrite
159 Comparative Study on the Transesterification of Triolein into Fatty Acid Methyl Ester
(FAME) Using Homogeneous and Heterogeneous Quaternary Ammonium Functional
Group (QN + OH - )
H. W. Yussof and A.P. Harvey*
170 Catalytic pyrolysis of biomass for the production of alternative fuels and chemicals:
Effects of catalyst’s acidity
E.F. Iliopoulou*, K. Papazisi, A.A. Lappas and K.S. Triantafyllidis
179 Granulated Lithium Zirconate for CO 2 Sorption
H. Stephenson*, A. Lapkin and A. Holt
183 Bio-oil upgrading using platinum catalysts
C.A. Fisk, T. Morgan, M. Crocker*, C. Crofcheck and S.A. Lewis
186 Ni 5 P 4 , a Highly HDS Active Phase of Bulk and Silica-Supported Nickel Phosphide Catalysts
G. Berhault*, H. Loboué, T. Cseri, A.Lafond and C. Geantet
190 Experimental Study of Sulphur Impact on Biogas Catalytic Steam Reforming:
Deactivation and Regeneration of Nickel-based Catalysts
M. Ashrafi*, C. Pfeifer, T. Pröll and H. Hofbauer
193 Catalyst developments for ultra-deep hydrodesulfurization of gas oil
Koichi Segawa*, Qiang Gao and Christopher T. Williams

196 Activity and selectivity of PdZn-based catalysts in dimethyl ether autothermal reforming
M. Nilsson*, P. Jozsa and L.J. Pettersson
202 The Water Gas Shift activity of Pt, Pd, and Re on Pr-doped ceria
S. Srikhwanjai, P. Nachai, W. Wongphathanakul and S. Hengrasmee*
203 Deep Hydrodesulfurization of Diesel over Co/Mo Catalysts Supported on Oxides
Containing Vanadium
C.M. Wang and Ikai Wang*
215 Development of catalysts for hydrogen production from dimethyl ether
Kaoru Takeishi
230 Gold catalysts based on ceria doped with lanthanides for pure hydrogen production
D. Andreeva*, I. Ivanov, R. Nedyalkova and L. Ilieva
233 New active and selective Rh-REOx-Al 2 O 3 catalysts for ethanol steam reforming
F. Can, A. le Valant*, N. Bion, F. Epron and D. Duprez
244 Strong effect of CO 2 and H 2 on the rate of water-gas shift reaction
T. Ishikawa, K. Shimada, O. Okada, S. Tsuruya, Y. Ichihashi and S. Nishiyama*
249 High temperature steam reforming of methanol catalyzed over Cu/ZnO/ZrO 2
Yasuyuki Matsumura* and Hideomi Ishibe
256 Effect of structural and acidity/basicity changes of CuO-CeO 2 catalysts on their activity for
water-gas shift reaction
P. Djinovi, J. Batista, J. Levec and A. Pintar*
269 Low temperature two-step process for hydrogen production
N. Ballarini, F. Cavani*, S. Passeri and L. Pesaresi
278 Stability of bimetallic monolithic catalysts in autothermal reforming of isooctane
N. Guilhaume*, L. Villegas and F. Masset
280 Single stage bimetallic water gas shift conversion catalysts for fuel cell applications
K. Seshan, K.G. Azzam, I.B. Babich, and L. Lefferts
288 Low temperature shift reaction catalyst : preparation, spectroscopic study and activity test
Karim H. Hassan
321 Extractive Regeneration of Lipophilic Amine CO 2 Absorbent
Y.H. Tan*, R. Misch and D.W. Agar
329 Hydrogen from biomass derived oxygenates – steam reforming of acetic acid over
supported Nickel-catalysts
B. Matas Güell*, K. Seshan and L. Lefferts
334 Nano-particle metal sulfides for ultra-deep HDS of diesel fuels
Zongxuan Jiang, Lu Wang and Can Li*
335 Ultra-deep desulfurization of fuels by emulsion catalysis
Can Li*, Zongxuan Jiang, Jinbo Gao, Hongying Lu and Yongna Zhang
338 Water gas shift reaction over tungsten carbides for CO removal
Tsutomu Kakinuma and Masatoshi Nagai*
342 Experimental and Numerical Investigation of Catalytic Partial Oxidation of Higher
Hydrocarbons over Rhodium coated Catalysts
M. Hartmann*, L. Maier, H. D. Minh and O. Deutschmann

366 Study of Rh-Doping on Ni-Based Supported Catalysts for CPO of CH 4
V. De Grandi*, V. Dal Santo, P. Benito, A. Vaccari and R. Psaro
374 Catalytic activity in WGS reaction of gold catalysts supported on mixed ceria-titania
oxides: role of the calcining temperature of the support
F. Vindigni*, M. Manzoli, A. Chiorino, T. Tabakova, V. Idakiev and F. Boccuzzi
387 Industrial Development of FCC Catalyst for Increasing Diesel Yield and Reducing
Olefins in Gasoline
Qin Song and Yin Jiudong*
400 Vanadium-molybdenum based catalysts for residue hydrodemetallation
D. Soogund, A. Daudin*, B. Guichard, M. Digne, D. Guillaume, C. Lamonier and
E. Payen
402 Promoting and Support effect in HDO of Guaïacol on CoMoS catalysts
Bui Van-Ngoc, Laurenti Dorothée* and Geantet Christophe
408 Hydrogen production by glycerol steam reforming
V. Dal Santo * , V. De Grandi, A. Gallo, L. Sordelli and R. Psaro
414 Probing hydrocarbonaceous overlayers on doped Ni/Al 2 O 3 autothermal
methane-reforming catalysts
Ian Silverwood, Neil G. Hamilton, R. Mark Ormerod, Hayley Parker, John Staniforth,
David T. Lundie, Stewart F. Parker and David Lennon*
422 Hydrogen production via methanol steam reforming over Ga-promoted copper based
catalysts: in situ DRIFT-MS study
Jamil Toyir*, Pilar Ramirez de la Piscina and Narcis Homs
429 Effective utilization of electrical field/discharges for hydrogen production
Y.Sekine*, M.Matsukata and E.Kikuchi
431 Investigation of two-stage hydrodearomatization of gas oils
G. Nagy*, J. Hancsók, Gy. Pölczmann, Z. Varga and D. Kalló
438 Influence of the ZnO/Al 2 O 3 support composition on the ethanol steam reforming reaction
R. Buitrago, J. Ruiz-Martínez, A. Sepúlveda-Escribano, F. Rodríguez-Reinoso and
J. Silvestre-Albero.
441 Kinetics of CH 4 partial oxidation over Rh/Al 2 O 3 and Rh/ZrO 2 : role of CO 2 reforming
A. Donazzi, A. Beretta*, G. Groppi and P. Forzatti
469 Light Hydrocarbon Reforming over Doped Ceria-Zirconia Catalysts for SOFC Applications
U. Wetwatana and D. Chadwick*
470 Non-parametric determination of distribution of active species on sulfided Mo/Al 2 O 3
catalyst
H. Tominaga, A. Irisawa, M. Kiyoshi and M. Nagai*
473 The relevance of support on the performances of Pt and Pt-Ni catalysts for the low
temperature ethanol steam reforming
P. Ciambelli*, V. Palma and A. Ruggiero

Great Hall – Poster Session II
Autocatalysis
291 Comparative study of natural gas vehicles commercial catalysts in monolithic form:
On the effect of gas composition and catalyst formulation
M. Salaün, A. Kouakou, S. Da Costa and P. Da Costa
292 Inverse Hysteresis during NO Oxidation on Platinum: Experiments and Simulation
W. Hauptmann, A. Drochner, H. Vogel, M. Votsmeier* and J. Gieshoff
293 NH 3 -SCR: From Mechanistic Understanding to an Improved Ammonia Dosing Scheme
M. Votsmeier*, A. Schuler, P. Kiwic, A. Drochner, H. Vogel, C. Onder and J. Gieshoff
304 Nucleation on and stability of -Al 2 O 3 surfaces: the special role of penta-coordinated
Al 3+ sites
Ja Hun Kwak, Jian Zhi Hu, Do Heui Kim, Charles H.F. Peden, and János Szanyi*
305 Detailed kinetic modeling of NO x storage and reduction with hydrogen –
ammonia formation
Anna Lindholm, Neal W. Currier, Junhui Li, Aleksey Yezerets and Louise Olsson*
315 Selective catalytic reduction of NO by hydrogen under lean-burn conditions using
Pt/Ti-Si-MCM-41 catalysts
Peng Wu, Fuxiang Zhang, Shuang Miao, Wenwen Shen, Yali Yang, Xiaohong Sun and
Naijia Guan*
324 Phase Characterisation of Ag/-Al 2 O 3 using NO 2 as probe molecule
Hanna Härelind Ingelsten*, Anders Hellman and Henrik Grönbeck
328 Catalytic oxidation of Carbon Black over Ru/CeO 2
in the presence of propene or toluene
S. Aouad, E. Saab, E. Abi-Aad* and A. Aboukaïs
331 DRIFTS Investigation of Sulfation of Model Lean NO x Trap
J.A. Pihl and T.J. Toops*
337 Enhancement of catalytic activity of Pt-mesoporous silica for HC-SCR through change in
pore structures and addition of cerium
Akiko Koga, Chika Saito and Masakazu Iwamoto*
340 A Reactivity of SOF on Various Oxygen Condition and De-NOx by producted syn-gas
J. W. Kim, H. K. Kim and Y. S. Yoo and S. J. Choung*
346 Engine bench tests for continuous HC-SCR over a Ag/Al 2 O 3 converter under lean
conditions using a 3.3 liters common rail turbo diesel off-road engine
K. Arve*, K. Eränen, J. Perus, M. Lauren, S. Niemi and D. Yu. Murzin
347 Kinetics of the reduction of NO by a model paraffinic second generation bio-diesel
compound over Ag/Al 2 O 3 under excess of oxygen
K. Arve*, J. Hernández, K. Eränen, and D. Yu. Murzin
355 The importance of zeolite synthesis on the stability of Cu-ZSM-5
M. Berggrund*, H Härelind Ingelsten, M Skoglundh and A. Palmqvist
367 Screening of palladium-containing modified ceria-zirconia catalysts for the Selective
Catalytic Reduction (SCR) of NOx by methane
B. Azambre*, L. Zenboury, P. Burg and P. Da Costa

372 Toward Three-way Nanocatalyst with High Performance and Low Noble Metals Loading
Zhimei Li, Xiao Guan, Licheng Liu, Hongxing Dai, Xuehong Zi and Hong He*
381 Synthesis of CeO 2 -ZrO 2 solid solution by glycothermal method and its oxygen release
capacity
S. Hosokawa, S. Imamura, S. Iwamoto and M. Inoue*
382 DRIFTS-SSITKA analysis of H 2 -assisted NH 3 SCR on Ag-alumina
J. Sjöblom*, D. Creaser and J.P. Breen and R. Burch
384 Performance of alumina and silica-supported copper oxide catalysts for simultaneous
removal of NO x and SO 2 from combustion flue gases
M. A. Goula*, O. Bereketidou, C. Economopoulos, H. Latsios and G. Grigoropoulou
389 Metal substrate SCR catalysts for NO x reduction in mobile applications
T. Maunula*, K. Rahkamaa-Tolonen, A. Viitanen, M. Kärkkäinen, A. Lievonen
and T. Kinnunen
390 H-ZSM-5 as promising catalyst for selective catalytic reduction of NO x with dimethyl ether
Stefanie Tamm*, Hanna H. Ingelsten and Anders E.C. Palmqvist
394 Mechanistic aspects of the “Fast” SCR reaction over Fe-ZSM5 catalysts
Isabella Nova*, Antonio Grossale, Enrico Tronconi, Daniel Chatterjee and Michel Weibel
395 The highly active catalysts of nmCeO 2 -supported CoO x for soot combustion
Jian Liu, Zhen Zhao*, Chunming Xu, Aijun Duan and Guiyuan Jiang
398 Mesoporous oxides with ceria for the purification catalysts of automotive emission
V. Parvulescu*, S. Somacescu, I. Sandulescu, I. Popescu, S. Todorova and G. Kadinov
410 Transient effective diffusivity studies on a catalytic converter under non reacting
conditions
S.T. Kolaczkowski*, K.Robinson, S. Awdry and Y.H. Yap
411 Transient heat transfer studies on a catalytic converter under non reacting conditions
S.T. Kolaczkowski*, K. Robinson, S. Awdry and S. Ye
421 Pt-induced distribution of Ba-sites activity towards regeneration stage on NO x
storage-reduction catalysts
U. Elizundia, R. López-Fonseca*, M.A. Gutiérrez-Ortiz and J.R. González-Velasco
423 0D modelling : a promising way for exhaust after-treatment issues in automotive
application
G. Mauviot and F. Le Berr
445 Novel NO x reduction method combining NO x storing materials with electrochemical
reduction of nitrogen oxides
U. Röder*, K. Sahner and R. Moos
450 Continuous monitoring and measurements for N 2 O emissions from NH 3 -SCR DeNO x
reaction on commercial V 2 O 5 /TiO 2 -based catalysts
Ki-Hwan Kim, Young-Hyun Lee, Moon Hyeon Kim*, Sung-Won Ham, Seung Min Lee,
Jeong-Bin Lee
455 Chemical Deactivation of SCR catalysts
P. Kern, M. Klimczak, M. Lucas and P. Claus*
461 New catalysts for reduction of nitric oxides by carbon monoxide
R.B. Akverdiyev and V.L. Baghiyev*
462 Experimental investigation of the reduction mechanisms over Pt-Ba/Al 2 O 3 Lean NO x
trap systems
Isabella Nova*, Luca Lietti, Pio Forzatti, F. Prinetto, F. Frola and G. Ghiotti

463 NO x storage on Pt-K/Al 2 O 3 NSR catalyst
F. Frola, S. Morandi, F. Prinetto, G. Ghiotti*, L. Castoldi, L. Lietti and P. Forzatti
464 Soot combustion: reactivity of alkaline and alkaline-earth metal oxides
Lidia Castoldi, Roberto Matarrese, Luca Lietti* and Pio Forzatti
466 A Novel Method for Automotive NOx depollution : in situ Generation of Ammonia
Sébatien Thomas and Véronique Pitchon*
471 A Novel Cu-V/Al 2 O 3 Catalyst for Selective Reduction of NO by NH 3 at Low Temperature
Chengjun Wang, Yuegang Zuo* and Chen-lu Yang
479 NH 3 production and decomposition during regeneration of NO x storage catalyst
P. Koí * , J. Štpánek, F. Plát, M. Marek, V. Schmeisser, D. Chatterjee and M. Weibel
483 Evidence of WGS activity over precious/transition metal DeNO x catalyst during HC-SCR
J.M. Pigos and C.J. Brooks*
Renewables
107 Catalytic conversion of cellulose over carbon supported tungsten carbide catalysts
Na Ji, Mingyuan Zheng, Aiqin Wang, Xiaodong Wang, Tao Zhang* and Jingguang G. Chen*
198 Effect of carbon-nanotube support on Ru-Mn-based Fischer-Tropsch catalysts for
hydrocarbon productions from biomass-derived synthesis gas
K. Murata*, K. Okabe, I. Takahara, M. Inaba and L. Yanyong
200 Nanocomposite heterogeneous catalysts for biodiesel production
L. Sherry* and J.A. Sullivan
223 Methanolysis of frying oil catalyzed by papaya lipase for biodiesel fuel synthesis
P. Porntippa* and P. Jakkrite
234 Catalytic conversion of glycerol to value-added products
A. Bienholz and P. Claus*
252 Production of Ethers of Glycerol: Side-Product of Biodiesel Production
N. Ozbay, N. Oktar*, G. Dogu and T. Dogu
270 Natural aluminosilicates and synthetic zeolites as the catalysts for energy generation
from biomass via low-temperature catalytic pyrolysis
Yu. Kosivtsov, V. Alfyorov, A. Sidorov*, M. Sulman, V. Matveeva, E. Sulman, O. Misnikov,
A. Afanasjev, N. Kumar and D. Murzin
289 Bio-fuel synthesis in transesterification of castor oil using heteropolyacid-based solid
catalysts
A. Ziba*, T. Kasza, L. Matachowski, A. Pacua, A. Bielaski, E. Serwicka-Bahranowska and
A. Drelinkiewicz
309 Activity and durability of solid acid catalysts for the esterification of free fatty acids with
methanol in vegetable oils.
Frederic C. Meunier*, Jun Ni and David Rooney
322 Performance of a catalytically activated ceramic hot gas filter for catalytic tar removal from
biomass gasification gas
M. Nacken*, L. Ma, S. Heidenreich and G.V. Baron
370 A novel catalyst support for Fischer-Tropsch synthesis Performance of Cobalt-Loaded
Powdered Diamond Catalysis
Toshimitsu Suzuki*, Tetsushi Kitano, Atsuo Nishizawa and Takanori Miyake

392 Gold-mediated catalysis in methanol/DME routes to lower carbon footprint fuels
A. Mpela,* S. Mokoena, G. Gladile, D. Hildebrandt, D. Glasser and M.S. Scurrell
405 Transesterification of triglycerides on heterogeneous polymer supported Lewis acid
catalysts
N.V. Kramareva*, O.P. Tkachenko and L.M. Kustov
424 The hydrogenation of vegetable oil: Low trans formation.
S. Mc Ardle, J.J. Leahy and T. Curtin*
427 Investigation of hydrotreating of vegetable oil-gas oil mixtures
J. Hancsók*, M. Krár, T. Kasza and Cs. Tóth
433 Enzymatic transesterification of used frying oils
M. Krár*, S. Kovács and J. Hancsók
443 Esterification of glycerol with acetic acid over heteropolyacids encaged in USY zeolite
P. Ferreira, I.M. Fonseca, A.M. Ramos, J. Vital, J.E. Castanheiro*
457 Selective oxidation of glycerol to dihydroxyacetone using bimetallic platinum catalysts
A. Brandner, S. Demirel, K. Lehnert and P. Claus*
General Topics
350 CO-TPR-DRIFTS in situ study of CuO/Ce 1-x Tb x O 2- (x = 0, 0.2 and 0.5) catalysts:
Support effects on redox properties and catalysis
Parthasarathi Bera, Aitor Hornés, Daniel Gamarra, Guillermo Munuera and Arturo Martínez-Arias *
357 Effect of TiO 2 particle size on photocatalytic reduction of CO 2
K. Koí * , L. Obalová, L. Matjová, D. Plachá, Z. Lacný and J.C.S. Wu
365 Visible-Light Induced Photocatalytic Activities of N- and Si-codoped Titanias modified
with Fe
S. Iwamoto*, H. Ozaki, K. Fujii and M. Inoue
385 Carbon nanotube-TiO 2 materials for visible-light-driven heterogeneous photocatalysis
C.G. Silva and J.L. Faria*
391 Study of the “anatase / electrolyte solution” Interface: Streaming Potential Measurements
and Potentiometric Titrations
N. Spanos*, A. Tsevis and G. Kamarianakis
432 Simplification method for the fast simulation of catalyst models with surface reactions
R. Möller*, M. Votsmeier, C. H. Onder, L. Guzzella and J. Gieshoff
446 Ba-incorporated mesoporous MCM-41 synthesis and characterization
E. Kaya, N. Oktar*, G. Karakas and K. Murtezaoglu
447 Characterization of Nb 2 O 5 -ZrO 2 mixed oxides synthesized from Nb(V) peroxo precursor
as novel solid acids
M. Kantcheva*, O. Samarskaya, I. Cayirtepe, H. Butunoglu, G. Ivanov and A. Naydenov
448 Photocatalytic Waste Waters Treatment from Pharmaceutical Industries
E. M. Méndez*, M. V. Lemus Salazar and J. E. Zaldaña Gómes
478 Modeling exploration of the relationships between meteorological parameters and
homogeneous nucleation the continental boundary layer over China
Enagnon A. Gbaguidi*, Jinnan Chen*, Zifa Wang and Chao Gao
481 A Characterization Study of CeO 2 and Carbon Supported AgCu and FeNi Bimetalics:
Search for Their Potential as Anode Electrodes in DEFC
N.A. Tapan* and Ö. Yldz

South Dining Room – Poster Session II
Green Chemistry
364 Development of Clay-Palladium(II) Nanocomposite Catalyst for Green Alcohol Oxidation
T. Hara, M. Ishikawa, N. Ichikuni and S. Shimazu*
371 Immobilization studies and biochemical properties of free and immobilized candida
rugosa lipase onto mesocellular silica foams: A comparative study
Reshmi.R, S. Sugunan*
383 Allyl transfer reaction of homoallyl alcohols to aldehydes via cleavage of a C-C bond
on heterogeneous Ru/CeO 2 catalyst
H. Miura, M. Sai, S. Hosokawa, T. Kondo, K. Wada* and M. Inoue
388 Ru/CeO 2 -catalyzed addition of aromatic C-H bonds to alkenes
H. Miura, K. Wada*, S. Hosokawa and M. Inoue
396 Beckmann rearrangement of cyclohexanone oxime to -caprolactam over heteropoly
acid supported on mesoporous silica molecular sieves
N. R. Shiju, M. Bandyopadhyay and D. R. Brown*
403 The Study of Propanal Condensation and Hydrogenation over Bifunctional Metal/Solid
Base Catalysts
S. David Jackson and Meilin Jia
415 The application of alumina-supported palladium catalysts for the hydrogenation of
aromatic nitriles in the liquid phase.
Liam McMillan, Justin Baker, David T. Lundie, Colin Brennan, Alan Hall and David Lennon*
416 The Gas Phase Hydrogenation of 1,3-pentadiene: a FTIR Study.
Neil G. Hamilton, Andrew R. McFarlane, David Siegel, David T. Lundie and David Lennon*
419 Chemical recycling of PET assisted by phase transfer catalysis
R. López-Fonseca*, M.P. González-Marcos, J.R. González-Velasco and J.I. Gutiérrez-Ortiz
430 A polyoxometallate-tethered Ru (II) bifunctional catalyst for alcohol carbonylation and
solvent-free alkyne oligomerisation
Lee Dingwall, Adam F. Lee* Karen Wilson* and Jason M. Lynam*
459 Vapor phase Beckmann rearrangement of cyclohexanone oxime on deboronated B-ZSM-5
M. Matsukata*, K. Nakagawa, Y. Sekine and E. Kikuchi
460 Research of ethanol oxidation over V-Mo-O catalysts
V.L. Baghiyev*, E.H. Alakbarov and A.D. Guliyev
482 A Catalytic Route for Michael Addition of Indole using Tungstophosphoric Acids as Green
Catalysts
M. Mohadeszadeh* and M.H. Alizadeh
485 Side-chain alkylation of toluene with propene over a basic catalyst. A DFT study.
Sawomir Ostrowski and Jan Cz. Dobrowolski
Air and Water
106 Catalytic decomposition of CFC-12 on solid super acid Mo 2 O 3 /ZrO 2
T.-C. Liu, P. Ning*, H.-J. Bart, Y.-M Wang and H. Gao
108 Copper oxidation degree and catalytic activity in CO oxidation
V.Yu. Bychkov*, Yu.P. Tyulenin, A.A. Firsova and V.N. Korchak

119 Destructive adsorption of CF 4 over NaF-Si-MO ternary adsorbents
Jie Fan, Xian-Jun Niu, and Xiu-Feng Xu*
128 Effect of chlorine on the catalytic behavior of Ir/CeO 2 for preferential CO oxidation
Yanqiang Huang, Aiqin Wang, Lin Li, Xiaodong Wang and Tao Zhang*
147 Effects of preparation conditions on gold/13X-type zeolite for CO oxidation
Qing Ye*, Caiwu Luo, Dao Wang and Shuiyuan Cheng
149 Catalytic blocks based on foam metals in some technology of air clearing
A.M. Makarov*, A.A. Makarov, M.A. Makarov and N.P. Makarova
153 An innovative preparation of heterogeneous metal nanoparticles catalysts for VOC
abatement: the onion-type multilamellar vesicles route.
D.P. Debecker, M.-E. Meyre, A. Derré, C. Faure and E.M. Gaigneaux*
156 Electrochemical treatment of Rhodamine 6G by using RuO 2 coated titanium electrode
Rita Farida Yunus, Yu-Ming Zheng, Shuai-Wen Zou and J Paul Chen*
162 Plasma-catalytic decomposition of aromatic VOC
M. Magureanu, D. Piroi, N.B. Mandache, V. Parvulescu and V.I. Parvulescu*
172 Promotion effect of lanthanum in Pd/Al 2 O 3 -La 2 O 3 catalysts prepared by sol-gel
on the catalytic activity in the CH 4 + O 2 reaction
A. Barrera*, G. Díaz, A. Gómez-Cortés, F. Tzompantzi, A. López-Gaona, F.J. Moscoso and
S. Fuentes
173 Metal-substituted hexaaluminates for high-temperature N 2 O abatement
Marta Santiago and J. Pérez-Ramírez*
177 Effect of potassium in calcined Co-Mn-Al layered double hydroxide on catalytic
decomposition of N 2 O
L. Obalová*, K. Jirátová, K. Galejová and F. Kovanda
194 Comparative Analysis of Measurement of Indoor Radon Concentration Using Active and
Passive Measurement Techniques
Rohit Mehra* and Surinder Singh
195 Bimetallic Fe/Me - zeolite catalysts for decomposition of N 2 O
K. Jíša, A. Vondrová, D. Kaucký, J. Nováková and Z. Sobalík
204 The promotion of carbon monoxide oxidation by hydrogen on platinum
S. Salomons, R.E. Hayes* and M. Votsmeier
205 Hybrid catalyst composed of zeolite and Pt/Al 2 O 3 for VOCs combustion
Y. Takamitsu* and W. Kobayashi
222 Feasibility of catalytic wet hydrogen peroxide oxidation process for the treatment of
industrial wastewaters
J.A. Melero, J.A. Botas, F. Martínez and M.I. Pariente*
228 New synthesis for Pt containing porous material for high temperature oxidation of volatile
organic compounds
M. Hutt*, A. Tissler, H.C. Schwarzer and T. Turek
236 Catalysis by phthalocyanines of chlorophenols oxidation
T. M. Fedorova*, E.G. Petrova, S.A. Borisenkova, O.A.Yuszakova, V.M.Negrimovskiy and
O. L. Kaliya
240 EnviNOx ® process for the abatement of nitrous oxide emissions from nitric acid tail gases
M. Schwefer, R. Siefert, H.C. Schwarzer, A. Tissler, C. Perbandt and T. Turek*

250 N 2 O decomposition mechanism on Rh catalyst studied by isotopic gases
S. Parres Esclapez, A. Bueno López*, M.J. Illán Gómez and C. Salinas Martínez de Lecea
253 Activation of hydrotalcite-like materials containing nickel for catalytic decomposition of
nitrous oxide
P. Kutrowski*, L. Chmielarz and R. Dziembaj
257 Rapid elimination of methylene blue dye in wastewater by adsorptive and photocatalytic
activities of structurally modified and supported TiO 2
M.A. Zanjanchi* and H. Golmojdeh
262 CO Oxidation on Pd/Al 2 O 3 : Correlation between Pd- oxidation state and activity
Katrin Zorn*, Suzanne Giorgio, Claude R. Henry and Günther Rupprechter
263 Catalytic oxidation of isopropanol/o-xylene mixture on zeolite catalysts
R. Beauchet*, J. Mijoin and P. Magnoux
271 Ultrasound activated catalytic systems for waste water denitrification
A. Gavrilenko, A. Sidorov*, M. Sulman, V. Matveeva, E. Sulman
272 Novel catalyst on a basis of immobilized oxidoreductases for wastewater purification
from phenols
A. Sidorov*, B. Tikhonov, N. Lakina and E. Sulman
277 Activated carbon and ceria as catalysts for the ozonation of organic compounds in the
aqueous phase
P.C.C. Faria*, J.J.M. Órfão and M.F.R. Pereira
281 Phenol degradation by Fenton system with in-situ generated H 2 O 2 over supported-Pd
catalysts
M. S. Yalfani*, S. Contreras, F. Medina and J. E. Sueiras
284 Catalytic removal of propene in air over Pd oxide catalysts
M. Ousmane, L. Retailleau, A. Giroir-Fendler*, L. F. Liotta, G. Di Carlo, G. Pantaleo and
G. Deganello
298 Performance of SBA-type catalysts in degradation of polypropylene
Z. Obali*, N.A. Sezgi and T. Dogu
299 Activated carbon supported metal catalysts Pd-Cu, Pt-Cu and Rh-Cu for nitrate reduction
in water
O.S.G.P. Soares*, J.J.M. Órfão and M.F.R. Pereira
300 Study of the effect of different pretreatments on Pt/CeO 2 catalysts for the
hydrodechlorination of trichloroethylene (TCE)
N. Barrabés*, A. Dafinov, K. Föttinger, G. Rupprechter, F. Medina and J.E.Sueiras
307 Catalytic oxidation of ethyl acetate over different metal-doped cryptomelane catalysts
V.P. Santos*, M.F.R. Pereira, J.J.M. Órfão and J.L. Figueiredo
310 Fe containing silica gel catalysts for catalytic wet peroxide oxidation processes
H. T. Gomes*, A.C. Barbosa, C.A. Amaro, C.M. Oliveira, R.G. Sousa, J.L. Faria and
B.F. Machado
320 Catalytic oxidation of 1-methylnaphthalene, a PAH representative molecule –
influence of PAH and steam concentrations
S.C. Marie – Rose*, J. Mijoin, P. Magnoux, E. Fiani, M. Taralunga and X. Chaucherie
326 Alkali metal modified Pd-MgAlO x catalyst for hydrodechlorination of chloro-aromatic
pollutants: activity and reactivation study
M. T. Beteley, A. M. Segarra, F. Medina*, J. E. Sueiras , Y. Cesteros and P. Salagre

327 Methane combustion over Pd-doped LaFeO 3 perovskites: where is the palladium?
A. Eyssler*, P. Hug, P. Lienemann, A. Weidenkaff and D. Ferri
332 Catalytic wet peroxide oxidation of phenolic solutions over a LaMeO 3 perovskites
O.P. Pestunova* and L.A. Isupova
336 Effects of preparation conditions on gold/13X-type zeolite for CO oxidation
Qing Ye*, Caiwu Luo, Dao Wang and Shuiyuan Cheng
351 Catalytic reduction of nitrates in water solution over Pt-Ag/AC
A. Aristizábal*, N. Barrabés, S. Contreras and F. Medina
352 Novel electrochemical catalyst for the electrochemical promotion of the deep oxidation
of methane: Pd deposited on YSZ monolith
V. Roche*, T. Pagnier, R. Revel, L. Rodriguez-Perez, E. Comte, A. Lambert and P. Vernoux
353 Wet air oxidation of acetic acid over ruthenium catalysts supported on cerium based
materials – influence of metal and oxide crystallite sizes.
J. Mikulová*, J. Barbier Jr., S. Rossignol, D. Mesnard, D. Duprez and C. Kappenstein
354 Nitrate removal from water by catalytic hydrogenation
J.V. Pande, A. Shukla, V. Kumar, A. Bansiwal, S. Rayalu and R.B. Biniwale*
356 Effect of potassium in layered double hydroxide-related Co-Mn-Al mixed oxide catalyst
on deep oxidation of VOC
K. Jirátová * , J. Mikulová, J. Klempa, T. Grygar, Z. Bastl and F. Kovanda
361 TCE dechlorination over zero-valent iron aerogels
Jihye Ryu, Young-Woong Suh, Young-Kwon Park and Dong Jin Suh*
362 Novel catalytic method for ammonia removal from waste gases
T. Maunula* and M. Härkönen
368 Promoting effect of tin in the preferential oxidation of CO over Pt/TiO 2 catalysts
J. Ruiz-Martínez, Hernán Pablo Bideberripe, G. Sirib, A. Sepúlveda-Escribano*,
J. Silvestre-Albero and F. Rodríguez-Reinoso
375 Ce and Ti as promoters of Au/Al 2 O 3 catalyst in the VOCs oxidation
G. Di Carlo*, L.F. Liotta, G. Pantaleo, A.M. Venezia, G. Deganello, M. Ousmane,
A. Giroir-Fendler and L. Retailleau
376 Development of Zeolite Monoliths by Paste Extrusion for ClVOCs Emissions Control by
Catalytic Oxidation
M. Romero-Sáez, A. Aranzabal*, J.A. González-Marcos and J.R. González-Velasco
378 Decomposition of tristearin by ozonolysis over heterogeneous catalysts under moderate
conditions
Kaori Kunisawa, Kohei Urasaki, Shigeru Kato, Toshinori Kojima and Shigeo Satokawa*
379 Adsorptive removal of tert-butanethiol on Ag and Cu exchanged Y-zeolites under ambient
conditions
Takuro Ohnuki, Tmoki Takahiro, Shigeru Kato, Toshinori Kojima and Shigeo Satokawa*
380 Carbon monoxide (CO) removal using activated carbon (AC) supported oxide catalyst
derived from waste
Snigdha Sushil* and Vidya S. Batra
397 Microwave-assisted adsorptive-catalytic removal of VOC from air
I.M. Sinev*, A.V. Kucherov, L.M. Kustov and M.Yu. Sinev

406 The influence of cooling atmosphere after reduction on the catalytic properties of
Au/Al 2 O 3 and Au/MgO catalysts in CO oxidation
E. Gy. Szabó*, A. Tompos, M. Hegeds and J. L. Margitfalvi
407 Effect of the Au chemical state on the synergistic performance of Au-VO x /TiO 2 catalysts
in the total oxidation of chlorobenzene
R. Delaigle, A. Coget, P. Eloy and E.M. Gaigneaux*
409 The selectivity of the noble metal catalysts on the oxidation of chlorinated hydrocarbons
S. Pitkäaho*, S. Ojala and R. L. Keiski
417 Oxygen Isotopic Exchange from CO 2 over Pd/Al 2 O 3 catalyst
S. Ojala*, N. Bion, D. Duprez and R. Keiski
420 Study of thermal and chemical stability of Ce/Zr mixed oxides for Cl-VOC oxidation
B. de Rivas, R. López-Fonseca, J.I. Gutiérrez-Ortiz* and M.A. Gutiérrez-Ortiz
425 The removal of carbon monoxide over CuO-Fe 2 O 3 /SiO 2 catalysts
M. Zieliski, S.Monteverdi and M.M. Bettahar*
426 Catalytic combustion of toluene on Cu and Pt MFI zeolites supported on cordierite foams
E.R. Silva, J.M. Silva, M.F. Vaz, F.A Costa Oliveira, F.R. Ribeiro and M. F. Ribeiro*
434 Noble metals supported on Cu-hydrotalcites for selective reduction of chlorinated
contaminants
K. Föttinger*, N. Barrabes, D. Cornado, A. Haghofer, F. Medina and G. Rupprechter
442 Degradation of clofibric acid in aqueous medium by heterogeneous catalytic oxidation
L. Fialho, A. Fernandes, A. Dordio, A. Carvalho, D. Teixeira, A. Candeias, C.T. Costa,
A.P. Pinto and J.E. Castanheiro*
444 TiO 2 -ZrO 2 based catalysts for chlorinated organics combustion
S. Albonetti, R. Bonelli*, J. Epoupa Mengou and F. Trifirò
449 Parametric study on the durability of CoO x /TiO 2 catalysts for low-temperature CO
oxidation
Ki-Hwan Kim, Moon Hyeon Kim*, Dong Woo Kim and Sung-Won Ham
452 Effect of acidity in the catalytic destruction of 1,2-dichlorobenzene over V 2 O 5 /TiO 2 based
catalysts.
S. Albonetti*, S. Blasioli, R. Bonelli, J. Epoupa Mengou, S. Scirè and F. Trifirò
453 Total oxidation of toluene over cluster-derived gold/iron catalysts
S. Albonetti*, R. Bonelli, L. Folli Ruani, C. Femoni, C. Tiozzo, S. Zacchini and F. Trifirò
458 Platinum catalysts on activated carbon support for water denitrification. States of oxygen
surface groups and textural properties after impregnation and reduction steps.
P. Gheek, G. Finqueneisel*, T. Zimny and J. Trawczyski
475 Oxidation of benzyl alcohol in aqueous medium by ZrO 2 catalyst at mild conditions
Mohammad Sadiq* and Mohammad Ilyas
476 Sulfur organic compounds oxidation by hydrogen peroxide in the presence of transition
metal peroxo complexes and crown ethers
A.V.Anisimov*, A.V.Tarakanova, M.Kh. Baishev and V.A.Certkov
477 Selective Methanation of CO over Supported Noble Metal Catalysts
P. Panagiotopoulou, D.I. Kondarides and X.E. Verykios*
480 Investigation of total oxidation of toluene over Al 2 O 3 -supported composite metal oxide
catalysts
Saleh M. Saqer, Dimitris I. Kondarides and Xenophon E. Verykios*

484 Commercial Application of Catalytic Combustion Treatment Technology for Waste Gases
from Wastewater Treatment System in Petrochemical Enterprises
Chen Yuxiang, Liu Zhongsheng, Wang Xin and Wang Xuehai
486 Optimal hydrocarbon selection for selective N 2 O reduction over FeZSM-5
Miguel A.G. Hevia and Javier Pérez Ramírez*

ORAL
PRESENTATION
ABSTRACTS
PLENARY
LECTURES

PL-1
Renewables for chemicals and fuels
Pierre Gallezot
Institut de recherches sur la catalyse et l’environnement de Lyon, CNRS/Université de Lyon
2, avenue Albert Einstein, 69626 Villeurbanne cedex, France
pierre.gallezot@ircelyon.univ-lyon1.fr
Various challenges have to be met in the development of biomass conversion to biofuels and bioproducts, e.g., the
design of new catalytic routes and processes adapted to oxygenated molecules to replace value chains from
hydrocarbons. Cost effective processes should be developed to make the quality and price of bioproducts competitive
with respect to products derived from fossil fuels. Recent literature gives a very complete account on the present state of
the research on the catalytic conversion of biomass [1]. However, the extensive use of biomass for industrial
production, particularly for biofuels involving high tonnages, raises environmental and ethical issues that may throw
some doubts on the sustainability of these processes. This lecture is intended to give a survey of the main scientific and
technological challenges and to address the environmental and ethical issues at stake.
Renewables to biofuels
Biodiesel is presently produced from triglycerides either by transesterification to fatty esters or by hydrotreatments to
hydrocarbons carried out in existing petroleum refineries. The sustainability of biodiesel (and bioethanol) production
from agricultural crops is questioned both on environmental ground (impact on biodiversity, land use, doubtful benefits
on green house gas reduction) and ethical ground (competition with food/feed supply). Further development must be
based on non-food crops grown on marginal land or preferably on oleaginous microalgaes grown from aquaculture.
Biofuels of second generation are obtained from lignocellulosic materials present in vegetative biomass (whole plants),
crop residues, or organic wastes. These feedstocks can be processed to hydrocarbons via a combination of high
temperature catalytic treatments mostly similar to those employed for fossil fuel conversion. Aqueous phase catalytic
reforming is a major innovation in this area. Lignocellulosic feedstocks can also be depolymerised to produce
fermentable sugars. The use of chemicals formed as co-products of biofuel production contributes to improves process
economy.
Renewables to bioproducts
Synthesis routes from fossil fuels were improved continuously during more than a century resulting in a very high
degree of technical sophistication and cost optimisation. In contrast, biomass processing to chemicals is comparatively
in infancy. Accordingly, extensive R&D efforts in biotechnology, chemistry and engineering are required to increase
the efficiency of biomass processing, specifically new catalytic routes and value chains adapted to the specific structure
of oxygenated molecules have to be designed. Flexible catalytic processes are needed to cope with variations in
feedstock availability and molecular structure.
Two process options to convert biomass derivatives into valuable bioproducts via innovative catalytic routes will be
discussed, viz.:
(i) Synthesis of chemicals via platform molecules. According to this option, biomass is first converted via
biotechnological processes to well-identified platform molecules that can be employed as building blocks for
chemical synthesis via catalytic routes.
(ii) (ii) Synthesis of mixtures of molecules with the same functionalities, suitable for the formulation of endproducts,
via one-pot conversion.
Process integration in a biorefinery scheme increases the value derived from biomass. Examples of catalytic conversion
of various bioresources to intermediate and fine chemicals will be given.
Industrial production systems starting from biomass to produce biofuels or bioproducts should be subjected to life-cycle
assessment (LCA) to evaluate their environmental and societal impact. They can be used as a tool to decide whether it is
better, environmentally and economically, to prepare a given product from bioresources or from fossil resources.
[1] J.N. Chheda, G.W. Huber, J.A. Dumesic, Angew.Chem. Ind. Ed.,2007, 46, 7164-7183; G.H. Hubert, A. Corma,
Angew. Chem. Int. Ed., 2007, 46, 7184-7201; G.W. Hubert, S. Iborra, A. Corma, Chem.Rev., 2006, 106, 4044-4098; A.
Corma, S. Iborra, A. Velty, Chem. Rev., 2007, 107, 2411-2502; Catalysis for Renewables, G. Centi, R.A. van Santen
Eds., Wiley-VCH, Weinheim, 2007

PL-2
Future demands on buses and implications for emission control
Edward Jobson
Volvo Bus Corporation, Dept 80060, ARHK6N, SE-405 08 Göteborg, Sweden
The rapid global development, not least driven by the climbing oil price, is rapidly changing the requirements on
modern transport. Hazardous emissions with impact on human health, use of fossil fuels and energy efficiency are now
regulated with increasing stringency. A holistic perspective is required to identify the long term sustainable solutions
and the route of how to get there. Today, the trend is towards public transport, by bus for most people, as being the most
cost efficient solution for society to meet the prioritised requirements. Further improvements in emissions and energy
efficiency are about to be realised for buses. US10 and Euro VI emission standards together with hybrid technology,
high capacity buses and new engine technology is about to set new standards.
The traffic pattern for city and intercity buses were analysed in detail by vehicle statistics. It was thereby possible to
simulate the impact of the new technologies on fuel consumption and emissions. The use of diesel buses, hybrid buses
and high capacity buses were analysed. The results were compared with the well-to-wheel environmental impact of
cars, metro, tram and electric buses. The implications for the exhaust conditions were analysed to understand the
challenges for future emission control technology.
On the highest level it was found that bus transport provides superior environmental performance as compared to the
other technologies. The new bus technologies will widen the gap further. The cost for the new technologies are
profitable for the public transport operators with fuel prices above 0.8 € per litre. Buses will thus become the preferred
environmental choice in future public transport. The emission performance of future bus operation depends strongly on
the priorities from society. When given the same priority as metro and rail the average load increases, the efficiency
improves and the exhaust conditions are improved for both NOx and particulate abatement. Based on the new
knowledge about exhaust conditions it is possible speculate about the implications for future emission control systems.

PL-3
Ultra-deep Desulfurization of Fuels by Emulsion Catalysis
Can Li*, Zongxuan Jiang, Jinbo Gao, Hongying Lu, Yongna Zhang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
*Corresponding author. Tel: 86-411-4379070, Fax: 86-411-469444
e-mail: canli@dicp.ac.cn http://www.canli.dicp.ac.cn
Introduction
Much attention has been paid to the deep desulfurization and even ultra-deep desulfurization of fuel oils due to
more stringent environmental regulations for environmental concerns. Although hydrodesulfurization (HDS) is highly
efficient in removing thiols, sulfides, and disulfides, it is difficult to reduce refractory sulfur-containing compounds
such as dibenzothiophene (DBT) and its derivatives, especially 4, 6-dimethydibenzothiophene (4, 6-DMDBT), to an
ultra-low level. Therefore, it is highly desirable to develop non-HDS methods to meet the demands of producing clean
diesel1 with an extremely low concentration of sulfur-containing compounds. Among them, oxidative desulfurization
combined with extraction is considered to be one of the most promising processes. In this lecture, we report that
amphiphilic catalysts assembled in an emulsion in diesel, could selectively oxidize sulfur-containing compounds into
their corresponding sulfones by using an approximately stoichiometric amount of H 2 O 2 as the oxidant. The sulfones can
be readily separated from the diesel using an extractant and ultra-deep desulfurization of diesel can be achieved.
Results and discussion
We have developed a series of emulsion catalysts, which are composed of the quaternary ammonium salt cations
and heteropolymetalate anions, such as Q 3 [PW 12 O 40 ] and Q 4 [H 2 NaPW 10 O 36 ]. The catalysts are assembled at the
interface of two immiscible liquids and form emulsion droplets. These emulsion droplets act as a homogeneous catalyst
to efficiently oxidize the sulfur-containing molecules to sulfones in diesel.
As an example, the catalyst, [C 18 H 37 N(CH 3 ) 3 ] 4 [H 2 NaPW 10 O 36 ], in the W/O emulsion system exhibits very high
catalytic activity such that all sulfur-containing compounds in either model or real diesel can be selectively oxidized
into their corresponding sulfones using hydrogen peroxide as an oxidant. The sulfur level of a prehydrotreated diesel
can be lowered from 500 to 0.1 ppm after oxidation and then extraction, whereas the sulfur level of a straight-run diesel
can be decreased from 6000 to 30 ppm after oxidation and extraction. The catalysts demonstrate high performance, i.e.,
96% efficiency of H 2 O 2 , and ~100% selectivity to sulfones.[1-3]
Conclusion and perspectives
The amphiphilic catalysts assembled at the interface of emulsion droplets, which can be separated easily from
reaction systems, shows high selectivity and activity in the oxidation of sulfur-containing molecules to sulfone. The
sulfur level in diesel is reduced to only a few ppms from several hundred ppms using the oxidation/extraction approach.
This approach is actually an environmentally friendly strategy not only effective for removing the sulfur-containing
compounds from fuels but also potentially useful for the organic synthesis using water as the solvent. Our preliminary
results demonstrated that the emulsion catalysis can significantly enhance the catalytic performance of selective
oxidation of alcohol, epoxidation of olefins and chiral Aldole reactions[4-6].
Related references
[1] Can Li, Zongxuan Jiang, Jinbo Gao, Yongxing Yang, Shaojun Wang, Fuping Tian, Fuxia Sun, Xiuping Sun,
Pinliang Ying, Chongren Han, A European Journal - Chemistry , 2007, 10 (9): 2277-2280.
[2] Hongying Lü, Jinbo Gao, Zongxuan Jiang, Fei Jing, Yongxing Yang, Gang Wang, Can Li,
J. Catal., 2006, 239: 369–375..
[3] Hongying Lü, Jinbo Gao, Zongxuan Jiang, Yongxing Yang, Bo Song, Can Li, Chem. Comun., 2007, 150-152.
[4] Jinbo Gao, Yongna Zhang, Guoqing Jia, Zongxuan Jiang, Shouguo Wang, Hongying Lu, Bo Song and Can Li
Chem. Commun., 2008, 332-334.
[5] Jinbo Gao, Shouguo Wang, Zongxuan Jiang, Hongying Lu, Yongxing Yang, Fei Jing and Can Li,
J. Mol. Catal. A: Chem., 2006, 258: 261-266.
[6] Lin Zhong, Qiang Gao, Jinbo Gao, Jianliang Xiao, and Can Li, J. Catal., 2007, 250: 360-364.

PL-4 Sustainability through Green Processing –
Novel Process Windows intensify Micro Processing and Applications in Catalysis
Volker Hessel 1,2 , G. Kolb 2 , J. Schouten 1 , Dana Kralisch 3
1 Eindhoven University of Technology (TU/e), Eindhoven, the Netherlands; v.hessel@tue.nl
2 Institut für Mikrotechnik Mainz GmbH (IMM), Mainz, Germany
3 Friedrich-Schiller University, Institute for Technical Chemistry and Environmental Chemistry, Jena, Germany.
This presentation tries to cover two aspects relevant to the topics and motto of the Conference 5ICEC.
To show up how micro process technology contributes to green processing and to achieve sustainability in
chemical industry and what role novel process windows have here. This will be done in the field of fine
chemistry (often non-catalytic). However, the major conclusions can be transferred to catalysis.
Catalytic applications of micro process technology will be given in the field of heterogeneous catalysis,
particularly for fuel processing to generate hydrogen for fuel cells.
Sustainability through Green Processing – Process Intensification by Novel Process Windows
Draw on sustainability for chemical production processes demands the integration of sustainability aspects already
during process development, whereas further environmental impacts and production costs become predefined. Micro
and milli process technologies [1,2] can provide novel ways for process intensification combined with ecological [3]
and economic [4] advantages and first assessments were made here [5], mainly by industry. Microstructured reactors
have entered the field of fine chemistry with first pilot and production plants; some examples being reported [6]. To
bring these innovative apparatus to their operational limit and thus to process with maximal cost competitiveness and
environmental sustainability, the idea of “Novel Process Windows” [7] is discussed referring examples of actual
research. A recent case study disclosed the key drivers for ecological and economic optimisation [5] when intensifying
the aqueous Kolbe-Schmitt synthesis in a minicapillary reactor [8] by using microwaves as alternative energy source
and ionic liquids as alternative solvents.
References
[1] Hessel, Hardt, Löwe / Hessel, Löwe, Müller, Kolb, Chemical Micro Process Engineering (2 Volumes), Wiley-VCH, Weinheim,
2004/2005. [2] Jähnisch, V. Hessel, Löwe, Baerns, Angew. Chem. Int. Ed. 2004, 43 (4), 406. [3] Kralisch, Kreisel,
Chem. Eng. Sci., 2007, 62 (4), 1094. [4] Krtschil, Hessel, Kralisch, Kreisel, Küpper, Schenk, Chimia, 2006, 60 (9), 611.
[5] Hessel, Kralisch, Krtschil, Energy Environ. Sci. (submitted). [6] Hessel, Löb, Löwe, Industrial Microreactor Process
Development up to Production, in: Microreactors in Organic Chemistry and Catalysis (ed. T. Wirth), Wiley-VCH, Weinheim,
2008, pp. 211-275. [7] Hessel, Löb, Löwe, Curr. Org. Chem., 2005, 9 (8), 765. [8] Hessel, Löb, Löwe et al., Org. Proc. Res.
Dev., 2005, 9 (4), 479.
Applications in Catalysis – Process System Engineering
For catalysis using microreactors [1], it is essential to have total reaction control at all length scales, ranging from mm
to nm, which includes smart engineering of reactor plates and microchannels as well as proper setting of catalyst
coatings and metal clusters in mesopores. Most essential here is the reliable finding of activated catalysts and proper
introduction of these into the microchannels [2-7]. In continuation, catalytic pilot and production microstructured
reactors [8,9] demand for solutions on scale-out (system assembly) [8,9], control over flow distribution and heat
management at multi-plate architecture [10,11], integration of reaction and heat exchange / separation, process flow
with many coupled reactions and operations (sometimes involving recirculation) [8,9], reduction in expenditure for
energy and apparatus required for work-up [12], and increase in the service life of the catalyst including concepts for
catalyst change, e.g. by replacement of entire modules. This is accompanied by the development of new
microfabrication and joining techniques applicable to large, meter-sized format such as rolling / embossing / etching
and brazing / diffusion bonding [13]. System and process design is widely practised at IMM for applications in fuel
processing for hydrogen production to feed fuel cells [14]. This has led to industrial implementation already, e.g. the
250 W LPG fuel processor-fuel cell VEGA for leisure vehicles and boats (Truma Gerätetechnik) and a 2 kW diesel fuel
processor-fuel cell prototype as auxiliary power unit for trucks (Volvo, DAF; assembled by Tenneco) [14]. Applications
using fossil fuels being reality, the next step is to explore chances of the technology for biofuels with its more complex
processing schemes, different logistics and cost structures.
References
[1] Kolb, Hessel, Chem. Eng. J., 2004, 98 (1-2), 1. [2] Muraza, Rebrov, de Croon, Schouten et al., Chem. Eng. J., 2008, 135S,
S99. [3] Mies, Rebrov, Jansen, de Croon, Schouten, J. Catal., 2007, 247 (2), 328. [4] Rebrov, Kuznetsov, de Croon, Schouten,
Catal. Today, 2007, 125, 88. [5] Pennemann, Hessel, Kolb, Löwe, Zapf, Chem. Eng. J., 2008, 135 (1), S66. [6] Men, Kolb,
Zapf, Hessel, Löwe, Catal. Today 2007, 125 (1-2), 81. [7] Men, Kolb, Zapf, Hessel, Löwe, Trans IChemE, 2007, 85 (B5), 1.
[8] Men, Kolb, Zapf, Tiemann, Wichert, Hessel, Löwe, Int. J. Hydrogen Energy, 2008, 33 (4), 1374. [9] Kolb, Schürer,
Tiemann, Wichert, Zapf, Hessel, Löwe, J. Power Sources, 2007, 171 (1), 198. [10] Rebrov, Ismagilov, Ekatpure, de Croon,
Schouten AIChE J., 2007, 53 (1), 28. [11] Mies, Rebrov, Deutz, Kleijn, de Croon, Schouten, Ind. Eng. Chem. Res., 2007, 46
(12), 3922. [12] Delsman, Uju, de Croon, Schouten, Ptasinski, Energy Int. J., 2006, 31 (15), 3300.
[13] Hessel, Kolb, Brandner, Microfabrication for Energy Generating Devices and Fuel Processors in: Microfabricated Power
Generation Devices (eds.: Mitsos, Barton, ), in print (2008). [14] G. Kolb, Fuel Processing, Wiley-VCH, Weinheim, 2008

ORAL
PRESENTATION
ABSTRACTS
AUTOCATALYSIS

A-1 Role of Ag cluster on Hydrogen Effect of HC-SCR over Ag/alumina
Ken-ichi Shimizu, Junji Shibata, Koyoichi Sawabe, Atsushi Satsuma*
Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
* Corresponding author. Tel. : +81-52-789-4608 FAX : +81-52-789-3193,
e-mail : satsuma@apchem.nagoya-u.ac.jp
Background
Selective catalytic reduction of NO by hydrocarbons (HC-SCR) is one of the promising technologies for removal of NO in the exhausts from diesel and leanburn
gasoline engines. Ag/alumina is thought to be the most promising candidate for practical use, and its HC-SCR activity can be boosted by the addition of H 2 [1].
The important role of Ag cluster on the hydrogen effect was demonstrated by in-situ UV-Vis by our group [2]. The aggregation of Ag into Ag cluster is in harmony
with the introduction of hydrogen into HC-SCR conditions and boosting of NOx conversion. On the other hand, it is reported that the "hydrogen effect" cannot be
directly connected to the formation of Ag cluster as follows; (1) the co-feeding of CO results in the formation of Ag cluster without enhancing effect of HC-SCR
activity [3], and (2) the formation of Ag cluster shows slower response than the increase in NOx conversion [4]. These results demonstrate that the presence of Ag
cluster is not a “sole factor” for the hydrogen effect. In this presentation we will show that the presence of both Ag cluster and dissociated hydrogen are sufficient
and necessary requirements.
Results
The hydrogen effect was not observed on 0.5 wt% Ag/alumina, in which Ag species is fixed as Ag + on alumina surface and hardly aggregated into Ag cluster even
in the presence of hydrogen. This fact demonstrates that Ag cluster is a necessary condition for the hydrogen effect. However, as reported by Burch et al.[3], and
Sazama et al.[4], the formation of Ag cluster is not a sufficient condition for the enhancement of HC-SCR activity. Therefore, a chemical effect should be taken into
account as another condition for the hydrogen effect. Sazama et al. reported that a promotion effect was also observed in decane-SCR with 0.2% of hydrogen
peroxide as well as the hydrogen effect [5]. Their result strongly suggests the important role of hydroperoxy-like species on H 2 -HC-SCR.
In this presentation, we would like to show that Ag cluster is a good “mediator” of the active H 2 O 2 -species, which is the essential for the activation of reactants in
HC-SCR.
(1) The formation of O - 2 species was detected by ESR spectrum of 2wt% Ag/alumina after Ag cluster formation in a flow of H 2 +O 2 followed by addition of O 2 [6].
Since the hydrogen effect is significant on partial oxidation of hydrocarbons, a kind of active oxygen species is essential for the hydrogen effect.
(2) The formation of O - 2 species was not detected in 0.5 wt% Ag/alumina, on which Ag species are not aggregated even after the reduction by H 2 . Formation of Ag
cluster is not a necessary condition.
(3) The formation of O - 2 species was not detected after Ag cluster formation in CO + O 2 followed by addition of O 2 . The presence of hydrogen is essential.
(4) The reaction mechanism was evaluated by DFT calculation using Ag/MFI as a model catalyst. It is reasobale that [HHAg 4 ] cluster activates oxygen to form
HOO[HAg 4 ] cluster, which leads to the formation of H 2 O 2 -species [7].
References
[1] S. Satokawa, Chem. Lett., 2000 (2000) 294.
[2] A. Satsuma, J. Shibata, K. Shimizu, T. Hattori, Catal. Surv. Asia, 9 (2005) 75.
[3] J. P. Breen, R. Burch, C. Hardacre, C. J. Hill, J. Phys. Chem. B, 109 (2005) 4805.
[4] P. Sazama, J. Ddeek, K. Arve, B. Wichterlová, et al., J. Catal., 232 (2005) 302.
[5] P. Sazama, B. Wichterlova, Chem. Commun, 2005 (2005) 4810.
[6] K. Shimizu, A. Satsuma, et al., J. Phys. Chem. C, 111(2007) 950.
[7] K. Sawabe, T. Hiro, Y. Iwata, K. Shimizu, A. Satsuma, to be submitted.
A-2 Selective Catalytic Reduction of NOx by Simulated Diesel Fuel Containing Oxygenated Hydrocarbon
Mun Kyu Kim a , Pyung Soon Kim a , Joon Hyun Baik a , In-Sik Nam a *, Byong K. Cho b , Se H. Oh b
a Department of Chemical Engineering / School of Environmental Science and Engineering, Pohang University of Science and Technology
(POSTECH), Pohang, Korea b General Motors R&D and Planning Center, Warren, MI, USA
*Corresponding author. Tel: +82 54 279 2264, Fax: +82 54 279 8299, e-mail: isnam@postech.ac.kr
Background
Ag/Al 2 O 3 catalyst has been known to be one of the most promising catalysts for HC/SCR under lean exhaust conditions, particularly in the high reaction
temperatures above 350 o C [1]. However, improvement of low temperature activity is critical for its application to lean-burn engine exhausts. Oxygenated
hydrocarbons (OHCs) are widely recognized as efficient NOx reductants for lowering the lightoff temperature as well as preventing catalyst deactivation by coking
[2].
Results
The NOx reduction activity of Ag/Al 2 O 3 catalysts was investigated in a packed-bed reactor using a mixture of simulated diesel fuel and ethanol as the reductant. A
major N-containing byproduct was NH 3 , whose rate of formation increasing with the amount of ethanol in the fuel mixture. To clean up the NH 3 produced over the
Ag/Al 2 O 3 catalyst, dual-bed catalyst systems were investigated; with the CuZSM5 catalyst in the rear bed, the NOx-to-N 2 conversion increased to 90 % over the
temperature range of 350 o C to 450 o C due to the oxidation of NH 3 to N 2 in the rear bed [3]. Further improvement of this dual-bed catalyst system was achieved
through optimization of the catalyst preparation method and operating conditions. Physicochemical characterization of Ag/ Al 2 O 3 using TEM, UV-vis, H 2 -TPR and
XPS has indicated that ionic Ag species are active reaction sites for NOx reduction to N 2 , while metallic Ag sites are for NOx reduction to NH 3 .
Justification for acceptance
This study has demonstrated that there are two reaction pathways in the NOx reduction by (HC+OHC) over Ag/Al 2 O 3 ; NOx reduction to either N 2 or NH 3 , occurring
on ionic or metallic Ag species, respectively. The NH 3 produced over the Ag/Al 2 O 3 can be oxidized to N 2 in a rear bed catalyst such as CuZSM5.
References
[1] T. Furusawa, L. Lefferts, K. Seshan, K. Aika, Appl. Catal. B: Environ. 42 (2003) 25.
[2] K.-I. Shimizu, M. Tsuzuki, A. Satsuma, Appl. Catal. B: Environ. 71 (2007) 80.
[3] R.Q. Long, R.T. Yang, Chem. Commun. (2000) 1651.
Present address of Dr. Joon Hyun Baik: Dept. of Chemical Engineering, MIT, Cambridge, MA, USA

A-3 A combination between a low- and a high-temperature catalyst for the SCR of NOx using second-generation biodiesel in microchannels
J. R. Hernández*, K. Arve, K. Eränen, T. Salmi and D.Yu. Murzin
Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre,
Åbo Akademi University, FI-20500, Turku/Åbo, Finland.
*Corresponding author. Tel: +358 2 2154431, Fax: +358 2 2154479, e-mail: johernan@abo.fi
Background
Growing concern for the environment and the strict legislation regarding mobile source emissions have led to the emergence of the research area of environmental
catalysis. Biofuels are regarded as an alternative for reducing oil dependence in the transport sector. The EU has mandated that biofuels comprise 5.75% of the total
vehicle fuel consumption in the EU by 2010, and the goal for 2020 is 10%. Since biodiesel produces more NOx than petrodiesel when combusted, its use as a fuel
requires the understanding of NOx reduction. Selective catalytic reduction (SCR) with hydrocarbons is an elegant way for addressing this problem.
Results
Micro structured platelets (Ø=460 m and depth 75 m) were successfully coated with an Ag/Al 2 O 3 catalyst by washcoating, as well as with ZSM-5 zeolite ionexchanged
with copper. Ten plates were coated (five with each catalyst) and they were arranged in alternation in a two-piece cubic chamber with two inlets and one
outlet, each with a tube diameter of 900 m 1. The coated microplatelets were tested for the SCR of NOx, using a typical diesel engine exhaust through the
microreactor inlet. Hexadecane, which is regarded as a high-quality diesel fuel, was used as a model compound for second-generation biodiesel [2]. The system
proved to successfully reduce NOx over the temperature range 150-550 C. The maximum NOx reduction was 2% lower compared to the case when only Ag/Al 2 O 3
was used as catalyst. When both catalysts were used, the temperature window for the reduction was broadened towards the low temperature range. A NOx reduction
up to four times higher was achieved at temperatures below 350 C. HC/NO ratio was, in principle, set to 6. However, tuning of this ratio resulted in an improved
NO to N 2 conversion, especially at the lower temperature range (150-350 C), where the enhancement of the activity due to the tuning was up to 7%. Optimal
HC/NO ratios for the Ag/Al 2 O 3 and Cu-ZSM-5 catalysts at different temperatures are presented and discussed.
Justification for acceptance
Low-temperature SCR (

A-5 CO and NH 3 -combined SCR with an internal heat exchanging reactor
A. Obuchi*, J. Uchisawa T. Nanba, A. Ohi, N. Iijima, K. Wada
National Institute of Advanced Industrial Science and Technology (AIST), Research Center for New Fuels and Vehicle Technology, 16-1 Onogawa, Tsukuba 305-8569, Japan
*Corresponding author. Tel: +81-29-861-8685, Fax: +81-29-861-8259, e-mail: a-obuchi@aist.go.jp
Background
Simultaneous achievements of low automotive emissions and high fuel economy are demanded. Newly developed engines with high fuel economy emit exhaust
gases with lower temperatures and this makes catalytic purification reactions more difficult. To resolve this dilemma, an internal heat exchanging reactor, which
integrates heat exchanging function and catalytic reactions together, is being attempted [1-3]. We report here on the performance of a test reactor, which combined a
catalyst active for the selective reduction of NOx with CO (CO-SCR) and that for NH 3 -SCR as well as an internal heat exchanging function.
Results
The reactor was based on the folded sheet design proposed by Jobson and Heed [1]. A thin, strip-shaped (300mm in width) stainless sheet folded back and forth 47
times in an interval of 50mm was installed in a cuboids casing (56x70x390mm) having an inlet and outlet opposing to each other near its center. Corrugated stainless
sheets with 1.2mm in height washcoated with Cu-ion exchanged ZSM-5 were sandwiched at the clearances of folded sheet in the inlet side. The same corrugated
sheets but coated with Ir and Ba supported on WO 3 -SiO 2 and those coated with Pt/Al 2 O 3 were sandwiched at the clearances in the outlet side. These catalysts were
for NH 3 -SCR, CO-SCR [4] and catalytic combustion of CO for assisted heating, respectively. The exhaust gas from the inlet is divided into two flows going to
opposite longitudinal directions till the ends of folded sheet. There, the gas flows turn over and come back to the center in the outlet side. By this counterflow, heat
can be recovered from the downstream to upstream, which will result in a promoted temperature rise near the turning point when exothermic catalytic reactions
occur in this reactor.
Part of the exhaust gas from a diesel vehicle containing ca.100ppm NOx was introduced to the reactor. By artificially raising the CO concentration of 180L/min of
introduced gas to 0.32% and applying totally 55W of electric heating at the ends of the reactor, the temperature near the turning point was raised to 320 o C while that
of the introduced gas was 100 o C, and 25% of NOx was reduced. The temperature rise corresponded to 80% of heat recovery. By further adding 90ppm NH 3 , the
NOx conversion was increased to 77%. It is evident that deNOx becomes possible at the lowest exhaust gas temperatures by applying this kind of reactor.
Justification for acceptance
Although with a small scale reactor, we suppose this will be the first report on experimental results on the application of an internal heat exchanging reactor to SCR
processes. Because there are many practical difficulties in realizing this reactor, our presentation will give a lot of useful information to researchers and engineers
engaging or interested in the development of this advanced emission control technology.
References
[1] E. Jobson, B. Heed, European Patent Application, EP 1016777 A2 (2000).
[2] G. Kolios et al., Appl. Catal. B 70 (2007) 16.
[3] A. Obuchi, J. Uchisawa, A. Ohi, T. Nanba, N. Nakayama, Topics in Catal. 42 (2007) 267.
[4] A. Takahashi et al. Chem. Lett. 35 (2006) 420.
A-6 Nature and evolution of palladium species on Pd-LaCoO 3 and Pd-Al 2 O 3 on the course of the reactions NO+H 2 +O 2
followed with Operando EXAFS
J.P. Dacquin 1 , P. Miquel 1 , C. Dujardin 1* , S. Cristol 1 , S. Nikitenko 2 , W. Bras 2 , P. Granger 1
1 Unité de Catalyse et de Chimie du Solide, USTL-CNRS, UMR 8181, Bât. C3, 59655 Villeneuve d’Ascq, France
2 DUBBLE, ESRF Grenoble, 6 rue Jules Horowitz, BP220, 38043 Grenoble, France
*Corresponding author. Tel : +44 328 77 85 29, Fax : +44 320 43 65 61, e-mail : christophe.dujardin@univ-lille1.fr
Background - The use of reducible supports has been largely applied on deNOx 3-way catalysis. Perovskite could be envisaged as alternative to ceria zirconia
supports since interesting activities were reported from literature for the selective reduction for NO into nitrogen for mobile sources and stationary sources [1,2].
Previous studies evidenced surface and structural changes on Pd-LaCoO 3 systems in the course of the NO+H 2 +O 2 reaction with the stabilisation of oxidic palladium
species characterised by XPS with an unusual binding energy of 337.5eV after stabilisation at high temperature in lean conditions [3]. The insertion of palladium
inside the framework of the perovskite like LaFe 0.95 Pd 0.05 O 3 proposed by Uenishi et al. [4] is still under debate.
Results - Operando EXAFS (Palladium K-edge energy) and in situ XPS experiments were used to follow the chemical environment of palladium and its evolution
during the 0.15%NO+0.5%H 2 +3%O 2 reaction on 1%Pd-LaCoO 3 and 1%Pd-Al 2 O 3 catalysts. The effluents were analysed on-line using a μGC chromatograph.
The stabilising effect of perovskite support has been examined and compared to a non-reducible support Al 2 O 3 . First, the reduction of Pd particles occurs
significantly at higher temperature on LaCoO 3 support than on alumina support. During the temperature programmed reaction, the oxidation of Pd particles arises at
90°C and 210°C on Al 2 O 3 and LaCoO 3 respectively as illustrated on XANES spectra (Fig 1). The different behaviour of Pd species depending on the support has
been also examined in EXAFS in terms of coordination of Palladium atoms.
After 2h steady state at 300°C, the EXAFS spectra become similar with PdO spectra with
A
B
characteristic coordination of Pd. At higher temperature and as previously observed on
30°C
XPS experiments, the chemical environment of Pd seems to be perturbed after stabilisation
60°C
30°C
90°C
90°C
at 500°C under NO+H 2 +O 2 reaction mixture. Those results will be discussed and related to
120°C
120°C
150°C
changes in activity and selectivity in the presentation.
180°C
Figure 1 : XANES spectra of K-edge energy of palladium for Pd/Al 2 O 3 (A) and Pd/LaCoO 3 (B) catalysts during the
operando temperature programmed reaction under 0.15%NO+0.5%H 2 +3%O 2 (20-300°C)
References
[1] C.N. Costa, V.N. Stathopoulos, V.C. Belessi, A.M. Efstathiou, J. Catal. 197 (2001) 350.
[2] M. Engelmann-Pirez, P. Granger, L. Leclercq, G. Leclercq, Topics in Catal. 30/31 (2004) 59.
[3] I. Twagirashema, M. Frere, L. Gengembre, C. Dujardin, P. Granger, Topics in Catal.
42/43 (2007) 171
[4] M. Uenishi, M. Taniguchi, H. Tanaka, M. Kimura, Y. Nishihata, J. Mizuki, T.
Kobayashi, Appl. Catal. B 57 (2005) 267.
Intensity /a.u.
180°C
210°C
240°C
270°C
300°C
300°C
24.3 24.35 24.4 24.45 24.5
Energy /keV
Intensity /a.u.
210°C
240°C
270°C
300°C
24.3 24.35 24.4 24.45 24.5
Energy /keV

A-7 Detailed and global kinetic modelling of ammonia SCR on copper zeolites
Louise Olsson a,* , Hanna Sjövall a , Richard J. Blint b and Ashok Gopinath c
a Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Göteborg, SWEDEN
b General Motors R&D Center, CES Laboratory, 30500 Mound Rd, Warren, MI 48090-9055, USA
c General Motors R&D, India Science Lab, Creator Bldg, ITPB, Whitefield Rd, Bangalore 560 066, INDIA
*Corresponding author. Tel: +46 31 772 4390, Fax : +46 31 772 3035, e-mail: louise.olsson@chalmers.se
Background
The exhaust gas from diesel and lean burn gasoline engines contains oxygen in concentrations from 3%-12% or more by volume. However the conventional three
way catalyst does not effectively reduce NO x at oxygen concentrations greater than 0.5 % by volume. NH 3 selective catalytic reduction (SCR) is a method for
reducing NO x in oxygen rich (lean) combustion exhaust by injecting aqueous urea into the hot automotive exhaust to produce NH 3 as the operable reductant for the
catalyst.
Results
We have developed both global [1] and detailed [2-4] kinetic models for NH 3 SCR over copper zeolites to increase the fundamental knowledge of these
heterogeneous reaction mechanisms and to apply them to predicting NO x emissions from urea-SCR automotive catalytic converters. The kinetics were developed
using experimental data from coated monoliths in flow reactor experiments, FTIR and temperature programmed desorption (TPD) experiments. In addition two
monolith samples (11 wt.% and 23 wt.% washcoat) were used to evaluate the mass-transfer limitations in the washcoat. The same conversions were obtained when
decreasing the total flow by 50 % for the sample with 11 wt.% washcoat, which indicates that there are no significant mass-transfer limitations in the washcoat layer.
Ammonia TPD experiments were used to investigate the adsorption and desorption kinetics of ammonia from the catalyst, which is crucial for simulating transient
behaviour of the reaction mechanisms. Further, the NO oxidation and NH 3 oxidation submodels were examined separately. The global kinetic model also contains
three steps for NH 3 SCR: standard SCR (NO + O 2 + NH 3 ), rapid SCR (NO + NO 2 + NH 3 ) and NO 2 SCR (NO 2 + NH 3 ) and one additional step for the N 2 O formation.
Both models predicted validation experiments adequately. The global model was validated using long steady state and short transient measurements. The NH 3 and
NO concentrations, and NO-to-NO 2 ratio were varied and the model successfully predicted the validation runs.
Justification for acceptance
The unique kinetic models developed here for NH 3 SCR over copper zeolites capture the effects of both flow/concentration transients and NO/NO 2 ratios which are
crucial for the prediction of NOx reduction. The detailed kinetic models represent a fundamental contribution to the knowledge of the reaction mechanisms that are
necessary to develop the global model which is presently in use for automotive applications.
References
[1] L. Olsson, H. Sjövall and R. J. Blint, Applied Catalysis B: Environmental, In press, 2008.
[2] H. Sjövall, R. J. Blint and L. Olsson, submitted, 2008.
[3] H. Sjövall, R. J. Blint and L. Olsson, submitted, 2008.
[4] L. Olsson, H. Sjövall, R. J. Blint, submitted, 2008.
A-8 Mechanistic kinetic modelling of the “Fast” NH 3 -SCR reaction over a Fe-ZSM5 catalyst
Isabella Nova a , Antonio Grossale a , Enrico Tronconi a* , Daniel Chatterjee b , Michel Weibel b
a
Dipartimento di Energia, Politecnico di Milano, I-20133 Milano, Italy
b Daimler AG, HPC: E220, 70546 Stuttgart, Germany
*Corresponding author: Tel: +39 0223993264, Fax: +390223993318, e-mail: enrico.tronconi@polimi.it
Background
The design of aftertreatment systems for vehicle exhausts is a complex process involving the optimization of several different parameters. In such a context,
numerical simulations are nowadays mandatory for time- and cost-effective development. In this paper a transient kinetic model of the ammonia-based SCR process
on a commercial Fe-ZSM-5 catalyst is presented, urea SCR being considered one of the most promising technologies to comply with the forthcoming EU and US
regulations for Diesel NOx emissions. The model is derived in close agreement with recent findings on the “Fast SCR” catalytic chemistry [1,2].
Results
A micro-kinetic scheme for the “Fast” SCR reaction was developed, based on: 1) NH 3 adsorption–desorption; 2) NO 2 disproportion and heterolytic chemisorption in
the form of surface nitrites and nitrates; 3) reversible reduction of nitrates by NO to form nitrites and NO 2 ; 5) reaction of nitrites with NH 3 to form N 2 via
decomposition of unstable ammonium nitrite. Transient kinetic experiments of various nature (step-response, temperature-programmed) were performed over a
powdered Fe-ZSM-5 catalyst in representative T-ranges to analyse the individual reaction steps of the complete NO/NO 2 + NH 3 + O 2 reacting system. The kinetic
model successfully reproduced not only steady-state results, but also peculiar dynamic features, which are critical for the correct design of SCR automotive
converters. The adequacy of the modelling approach was confirmed by transient validation runs on the same SCR catalyst in the shape of honeycomb monoliths, at
the lab scale as well as in test-bench runs using real engine exhausts and full-scale catalysts.
Justification for acceptance
The identification of SCR kinetics is the preliminary step for model-based development of SCR integrated aftertreatment systems, in relation e.g. to the definition of
the urea dosing strategy, or of position, size and cell density of the honeycomb SCR catalyst. Herein we show that a chemically consistent model affords significant
advantages for the accurate simulation of the complex transients resulting from engine load variations in the operation of automotive SCR converters.
References
[1] O. Krocher, M. Devadas, M. Elsener, A. Wokaun, N. Söger, M. Pfeifer, Y. Demel, L. Mussmann, Appl. Catal. B: Environ. 66 (2006) 208.
[2] I.Nova, C. Ciardelli, E. Tronconi, D. Chatterjee and B. Bandl-Konrad, Catal. Today 114 (2006) 3.

A-9 Direct conversion of NO x and soot into N 2 and CO 2 in diesel exhaust on Fe 2 O 3 catalyst
D. Reichert, H. Bockhorn, S. Kureti*
University of Karlsruhe, Institute of Technical Chemistry and Polymer Chemistry, Germany
*Corresponding author. Tel: +49 721 608 8090, Fax : +49 721 608 2816, e-mail: Kureti@ict.uni-karlsruhe.de
Background
Diesel engines with direct fuel injection exhibit the highest efficiency for automotive applications. However, a constraint is the emission of NO x and soot. In the past
much attention has been concentrated on the removal of these pollutants mainly dealing with the diminution of either soot or NO x . However, the direct catalytic
conversion of soot and NO x into N 2 and CO 2 has hardly been considered. Present contribution deals with the fundamentals of the catalytic soot/NO x /O 2 reaction
including mechanism, kinetics and kinetic modelling, whereas Fe 2 O 3 is used as model catalyst.
Results
To elucidate the mechanism of the soot/NO x /O 2 reaction and particularly the role of the Fe 2 O 3 catalyst a series of examinations is performed including TPO, transient
experiments, carbothermal reaction, DRIFTS, HRTEM and isotopic labelling. TPO and transient studies in which the soot/O 2 and soot/NO reaction are temporally
separated show that the NO reduction occurs on the soot surface without direct participation of the Fe 2 O 3 catalyst. The first reaction step is the formation of CC(O)
groups that is mainly associated with the attack of oxygen on the soot surface. The decomposition of these complexes leads to active carbon sites on which NO is
adsorbed. Furthermore, the oxidation of soot by oxygen provides a specific configuration of active carbon sites with suitable atomic orbital orientation that enables
the chemisorption and dissociation of NO as well as the recombination of two adjacent N atoms to evolve N 2 . Moreover, carbothermal reaction, DRIFTS, HRTEM
and isotopic studies show that the Fe 2 O 3 catalyst acts as an “oxygen pump” leading to a higher number of actice carbon sites thus resulting in enhanced NO reduction.
Pumping of oxygen includes dissociative O 2 adsorption on the catalyst, surface migration of oxygen to the contact points of soot and Fe 2 O 3 and then final transfer of
O to the soot. Moreover, the contact between both solids is maintained up to high conversion thus resulting in continuous oxygen transfer from catalyst to soot.
Based on the above described mechanism a kinetic model is constructed. This model represents a global approach in which the NO reduction and soot oxidation are
coupled. To obtain independent kinetic parameters additional kinetic studies are performed by using a gradient free loop reactor. The comparison of the measured
and calculated data shows that the experimental results of catalytic soot/NO x /O 2 reaction are well described by the kinetic model. In accordance with our mechanism
postulated the kinetic model involves same E A,app for catalytic and non-catalytic NO reduction (56 kJ/mol), but different apparent activation energies for catalytic (85
kJ/mol) and non-catalytic soot/O 2 reaction (115 kJ/mol).
Justification for acceptance
The removal of NO x and soot from diesel exhaust is actually a big challenge as both pollutants reveal high environmental impact and their emission limits will be
drastically tightened. Present contribution deals with the fundamentals of the direct conversion of soot and NO x representing a highly interesting alternative for
future diesel applications. Our basic study provides a detailed understanding of this complex reaction which enables the targeted development of novel catalysts with
advanced activity.
References
[1] S. Kureti, W. Weisweiler, K. Hizbullah, Appl. Catal. B 43 (2003) 281.
[2] H. Bockhorn, S. Kureti, D. Reichert, Top. Catal. 42-43 (2007) 283.
[3] D. Reichert, H. Bockhorn, S. Kureti, Appl. Catal. B 80 (2008) 248.
A-10 Evaluating Axial Distributions of Species and Temperature on Monolith-Supported Catalysts via Spatially-Resolved Calorimetry
William Epling* a , Alan Shaw a , Khurram Aftab a , Aleksey Yezerets b and Neal W. Currier b
a Dept of Chemical Engineering, University of Waterloo, Waterloo, ON, N2L 3G1 (Canada)
b Cummins, Inc., 1900 McKinley Ave, Columbus, IN 47201
*Corresponding author. Tel: 519 888 4567, Fax: 519 746 4979, email: wepling@uwaterloo.ca
Background
In emissions catalyst applications, axial distributions of reaction rates, surface chemistry, and temperature all exist along the catalyst surface. To develop physically
relevant models of such systems, understanding these distributions is required. IR thermography can be used to measure the temperature distributions on a monolithsupported
catalyst, but can also be used to indirectly measure surface concentrations of sorbed species. This indirect method consists of measuring the temperature
rise associated with an exothermic or endothermic reaction, with the target surface species as a reactant in such a reaction.
Results
IR thermography was used to measure the distribution of nitrate species on model and commercial diesel NO X adsorber catalysts. Axial distributions of the nitrate
species as a function of lean-phase time, temperature and using NO 2 and NO as NO X source were evaluated by measuring temperatures along the catalyst surface
during the regeneration phase. With increasing lean-phase time, more NO X was trapped, and larger temperature rises were observed. This was also true of increasing
rich-phase times since more NO X could be trapped with the more fully regenerated surface. The data indicate that with shorter trapping times, NO X is trapped near
the front of the catalyst and the surface concentration of trapped NO X moves from back-to-front, as expected. The data also demonstrate quantitatively, the relative
amounts as a function of axial position. With longer trapping times, more surface NO X species were still found at the front half of the catalyst, however within the
front half, more NO X was trapped slightly downstream relative to the amounts at the very inlet. This indicates that there was not a smooth saturation wave that
propagates simply from front-to-back as more NO X is trapped on the catalyst.
The effect of oxygen-storage and its exothermic reaction with reductants during the rich phase were also studied and the extent of the exotherm evaluated.
Temperature as well as performance data clearly demonstrate that consuming the surface oxygen species, those not associated with nitrites or nitrates, leads to
significant temperature rises, which travel with the gas front down the length of sample. The reactions during the regeneration phase also contribute to a slow
moving conduction wave along the solid, which can influence the subsequent trapping phase at high-temperature operating conditions.
Justification for acceptance
The described technique provides a method of evaluating reaction gradients in emissions control catalysts. It has been used successfully in characterizing oxidation
catalysts and now for NO X trap catalysts. Such results provide critical data for model validation and catalyst design.

A-11 Intermediate NH 3 Generation and Utilization Inside a Lean NO x Trap Catalyst
W. P. Partridge*, J-.S. Choi, J.A. Pihl, T.J. Toops, C.S. Daw
Fuels, Engines, and Emissions Research Center, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6472, USA
*Corresponding author. Tel: +1-865-946-1234, Fax: +1-865-946-1354, e-mail: partridgewp@ornl.gov
Background
Ammonia (NH 3 ) is recognized as important to Lean NO x Trap (LNT) catalyst regeneration, and conceptual models of how and where NH 3 is generated and used
inside LNT catalyst have been proposed. However, understanding of intra-LNT NH 3 function is primarily based on catalyst effluent measurements. Direct intracatalyst
measurements may provide an improved foundation for assessing the validity of this understanding.
Results
We have enabled the SpaciMS [1] to measure transient intra-catalyst NH 3 distributions by addressing the various measurement challenges including interference
with abundant species, wall and chromatography effects. We have used SpaciMS to measure transient species distributions inside a 300-cpsi channelized monolith
model Pt/Ba/Al 2 O 3 washcoated catalyst at three operation temperatures and during lean-rich (60s-5s) cycling. Transient H 2 , NO x , N 2 and NH 3 distributions were
monitored in light of clarifying NH 3 formation and utilization roles. This allowed species timing or phase to be determined along the catalyst channel, as well as the
selectivity and species distributions. Distinct differences in species phase and selectivity were observed along the catalyst channel. The behavior at different
operation temperatures supports the dominant role of H 2 :NO x stoichiometry in NH 3 formation during LNT cycling. The temporal shape of the NH 3 transient
suggests parallel-consecutive pathways for NH 3 formation/utilization. Some intra-catalyst behavior is in stark contrast to effluent measurements upon which our
foundational NH 3 understanding is based, and suggests that certain theories are incomplete. The results clearly demonstrate the complex role NH 3 plays in LNT
regeneration and provides the detailed data necessary to support modeling to begin unraveling the component details of this complex role.
Justification for acceptance
Ammonia is relevant to LNT, Selective Catalytic Reduction (SCR) and hybrid LNT-SCR methodologies for NO x aftertreatment of lean-burn gasoline and diesel
exhaust. Detailed understanding of the NH 3 formation and utilization roles is needed to develop efficient catalyst systems. The SpaciMS measurements provide
unprecedented insights into this important and complex process.
References
[1] J-.S. Choi, W.P. Partridge, C.S. Daw, Applied Catalysis B: Environmental 77 (2007) 145.
A-12 Novel CeO 2 -Al 2 O 3 nano composite for inhibiting Pt sintering of NSR catalyst
Hiroyuki Matsubara a *, Yuichi Sobue b , Nobuyuki Takagi c , Yasutaka Nagai d ,Keisuke Kishita e ,
Nobumoto Ohashi b , and Shin’ichi Matsumoto c
a Material Engineering Div. 3, Toyota Motor Corporation, Susono, Shizuoka, 410-1193, Japan
b
Power Train Engineering Div. 2, Toyota Motor Corporation, Susono, Shizuoka, 410-1193, Japan
c
Material Engineering Div. 1, Toyota Motor Corporation, Toyota, Aichi, 471-8572, Japan
d
Toyota Central R & D labs., inc., Nagakute, Aichi, 480-1192, Japan
e
Material Engineering Div. 2, Toyota Motor Corporation, Toyota, Aichi, 471-8572, Japan
*Corresponding author. Tel:+81-55-997-7824, Fax:+81-55-997-7879 e-mail: hiroyuki@matsubara.tec.toyota.co.jp
Background
Both clean exhaust and low fuel consumption are required for automobiles because of environmental protection. Lean-Burn engines are effective to improve fuel
consumption and NO x Storage-Reduction (NSR) catalysts have been developed for these engines to solve these two problems [1]. There have been many efforts to
tolerate sulfur poisoning [2], however Pt sintering by thermal aging should cause the deterioration of NO x storage capability. In this paper, Pt sintering inhibition
mechanism was investigated, and then a novel material, which is effective to inhibit Pt sintering, was developed.
Results
The interaction between Pt and the catalytic support was investigated by XAFS analysis. It was
found that CeO 2 had a strong interaction with Pt by making the Pt-O-Ce bond, though Al 2 O 3 had
weak interaction with Pt [3]. This suggests that Pt on CeO 2 should not sinter since the interaction of
Pt-O-Ce plays as an anchor to inhibit migration of Pt. A support with high surface area (ex. Al 2 O 3 )
is necessary for the high dispersion of Pt and NO x storage compound. Based on this knowledge, we
made a new concept as shown in Fig. 1: a CeO 2 -Al 2 O 3 nano composite to suppress the sintering
both of Pt and CeO 2 . The concept hypotheses: 1) Smaller size of the primary CeO 2 particle should
have more contact point with Pt. 2) Al 2 O 3 should work as the barrier for CeO 2 grain growth. 3)
Even if Pt on Al 2 O 3 migrates at higher temperatures, it should be grasped on CeO 2 . We succeeded
in developing the catalyst shown inFig. 2. The Pt sintering was suppressed in the developed
Al2O3
60 nm
Fig.2 TEM image of developed
catalyst after aging
catalyst compared with the conventional catalyst. Consequently, the NO x storage amount was improved especially at low temperatures less than 300 °C. In NSR
catalyst, NO x is trapped through the oxidation of NO to NO 2 on Pt. Then, the inhibition of Pt sintering affects the improvement of NO x storage performance.
Justification for acceptance
We developed a new NSR catalyst with a novel CeO 2 -Al 2 O 3 nano composite, which could inhibit sintering both of CeO 2 and Pt. The developed NSR catalyst has
twice the NO x storage performance of the conventional catalysts.
Reference
[1] N. Miyoshi, S. Matsumoto, K. Katoh, T. Tanaka, J. Harada, T. Nakanishi, K. Yokota, M. Sugiura, K. Kasahara, SAE Technical Paper 950809 (1995).
[2] S. Matsumoto, Y. Ikeda, H. Suzuki, M. Ogai, and N. Miyoshi, Applied Catalysis B: Environmental, 25 (2000) 115.
[3] Y. Nagai, T. Hirabayashi, K. Dohmae, N. Takagi, T. Minami, H. Shinjoh, S. Matsumoto, Journal of Catalysis, 242 (2006) 103.
CeO2
Al2O3
Fig.1 CeO2-Al2O3 nano
composite Concept
CeO2

A-13 Kinetics of Sulfur Removal from a Commercial Lean NOx Trap Catalyst
Aleksey Yezerets* a , Neal W. Currier a , Junhui Li a , Haiying Chen b and Howard S. Hess b
a Cummins Inc., 1900 McKinley Ave, Columbus, IN 47201
b Johnson Matthey, Emission Control Technologies, 436 Devon Park Drive, Wayne PA 19087
*Corresponding author. Tel: 812 377 9587, email: aleksey.yezerets@cummins.com
Background
Lean NOx Traps represent one of the key technologies for reducing emissions of NOx under the net oxidizing (lean) conditions typical of diesel operation.
LNTs are poisoned by sulfur present in diesel fuel and require periodic on-board regeneration. This process, often referred to as desulfation, requires high
temperatures and net-reducing (rich conditions). Detailed, quantitative understanding of the desulfation process has proved to be critical for practical application of
LNT systems. Achieving high degree of sulfur removal without excessive thermal damage to the catalyst and with minimal impact on the engine operation is a key
to durability.
Results
In this work, the effect of sulfur on the NOx operation of a commercial LNT catalyst developed by Johnson Matthey has been studied, along with the
mechanism and kinetics of sulfur removal process. In particular, different forms of sulfur have been identified on the catalyst surface, having different impact on the
NOx operation, and different kinetics of removal.
The form of sulfur most relevant to the practical operation of LNT proved to be removable at lower temperatures, and is arguably attributable to surface
sulfate species. The kinetics of its removal was studied via a detailed parametric study encompassing various levels of initial sulfur loading, desulfation
temperatures, as well as type and concentration of reductants. Ths study was based on a laboratory experimental setup developed at Cummins, allowing for accurate,
speciated measurement of the evolved sulfur products with excellent material balance. The results of the kinetic study were reduced to a single, mathematically
uncomplicated kinetic expression. In the presentation we will share this set of kinetic information, along with some additional effects related to the integral nature of
the practical LNT devices, such as spatial distribution of sulfur species on the catalyst surface.
Acknowledgements
This work was supported in part by the US Department of Energy under the Freedom Car program.
Justification for acceptance
This work represents the results which underpinned the development by Cummins in partnership with Johnson Matthey of the first commercial NOx
emissions reduction system compliant with US EPA 2010 NOx standards for diesel engines, implemented in the 2007 Dodge Ram diesel powered vehicles.
A-14 Thermal Aging of Lean NO x Trap Catalysts Using Reactor-Generated Exotherms and the Resulting Material Effects
Background
T.J. Toops 1, *, B.G. Bunting 1 , K. Nguyen 2 , N.A. Ottinger 2 , H. Kim 2
1 Fuels, Engines and Emissions Research Center, Oak Ridge National Laboratory, Knoxville, TN 37932, USA
2 Mechanical, Aeronautical and Biomedical Engineering Dept., University of Tennessee, Knoxville, TN 37996 USA
*Corresponding author. Tel:+1 865 946 1207, Fax: +1 865 946 1354, e-mail: toopstj@ornl.gov
Lean NOx Traps (LNTs) are possible emissions control devices to address the upcoming diesel exhaust regulations; however, its cost-effective implementation is
currently limited by the durability of materials from high temperature desulfation. The onboard desulfation process will be a quick, high temperature excursion with
the catalyst exposed to both lean and rich conditions. This project describes a technique to achieve controlled high temperature exotherms repeatedly and the
systematic materials effects that are incurred. Four aging temperatures were employed over the course of several hundred aging cycles.
Results
The monolithic cores used in this study were removed from a commercial-quality LNT containing Ba, K, Ceria-Zirconia, Pt, Pd, Rh and alumina in the washcoat.
The 22 mm OD cores were aged in a bench-scale reactor using simulated diesel exhaust that includes H 2 O and CO 2 and is capable of both lean and rich operation.
The controlled and repeatable high temperature exotherms were achieved be flowing both H 2 and CO in conjunction with enough O 2 to achieve the desired mid-bed
temperature. In conjunction with aging at 700, 800, 900, and 1000°C, NOx conversiobn measurements were systematically measured throughout the aging.
Periodic materials characterization was also performed during the aging process. Ba agglomeration and possible aluminate formation were qualitatively observed,
while surface area losses, Pt group metals (PGM) sintering, and K migration were quantitatively measured and related to losses on a temperature- and cycle-basis.
The primary benefit from being able to quantify these material effects is to then draw correlations to which material change is having the most significant impact on
performance losses. In this study and in our previous studies the losses in performance can be most closely correlated to total surface area losses [1-2]. This is
primarily a function of alumina sintering, but the storage material supported on the alumina is impacted similarly. For instance, NOx capacity measurements are also
highly correlated to surface area losses, so simply measuring the overall surface area can give insight into storage material effects. The K migration also shows a
good correlation to losses. The temperature that is most critical for acceleration of materials effects and the performance loss is ~850°C. This relates to the surface
area correlation since the transition of alumina from gamma to delta is expected to begin around 860°C.
Justification for acceptance
Durability of LNTs is limiting their cost-effective application in diesel engines. The ability to correlate materials effects to catalyst performance allows catalyst
manufacturers to focus on the most important material improvements; furthermore, the new formulations can be evaluated for durability using the techniques
described in this study.
[1] K. Nguyen, H. Kim, B.G. Bunting, T.J. Toops, C.S. Yoon, SAE 2007-01-0470.
[2] T.J. Toops, B.G. Bunting, K. Nguyen, A. Gopinath, Catalysis Today 123 (2007) 285.

A-15 Hydrolysis of Isocyanic Acid over TiO 2 (Anatase): Unraveling the Reaction
Mechanism by a Combination of DFT Calculations, DRIFT Spectroscopy and Kinetic Studies
O. Kröcher * , I. Czekaj, G. Piazzesi
Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
*Corresponding author. Tel: +41 56 310 20 66, Fax : +41 56 310 23 23, e-mail: oliver.kroecher@psi.ch
Background
Decreasing NO x emissions limits for diesel vehicles impel the further development of the existing DeNOx technologies, particularly the selective catalytic reduction
of nitrogen oxides with urea (urea-SCR). In this process a urea solution is injected into the exhaust gas, where it thermolyses to ammonia and isocyanic acid
(HNCO) [1]. HNCO itself hydrolyses to ammonia and carbon dioxide. This reaction step was found to proceed rapidly on TiO 2 in the anatase modification, which is,
therefore, used as hydrolysis catalyst in the urea-SCR process.
Results
The co-adsorption of isocyanic acid (HNCO) and water (H 2 O) and their reaction to ammonia and carbon dioxide on the anatase TiO 2 (101) surface were studied with
ab initio density functional theory (DFT) calculations using a cluster model as well as with in situ DRIFTS investigations and kinetic experiments. Two mechanistic
pathways have been identified to be feasible. In one mechanism HNCO is molecularly adsorbed and an intermediate surface complex is formed by NCO skeleton
modification [2]. In the second pathway, a water molecule attacks the –NCO group at an early stage, thereby forming carbamic acid at the surface. In a further step
this compound is transformed to a carbamate complex, which leads to CO 2 desorption and consequently NH 3 formation [3]. Since water is always present in diesel
exhaust gas, only the second mechanism is relevant under practical conditions. The comparison between the sum of the theoretical vibrational spectra of the reaction
intermediates with the in situ DRIFT spectra also strongly supports the accuracy of the second reaction pathway. The experimental investigation of the kinetics of the
HNCO hydrolysis on TiO 2 anatase revealed a second order reaction – first order with respect to HNCO and first order with respect to water, which can only be
reconciled with the second mechanism.
Justification for acceptance
TiO 2 is used as catalyst for the decomposition of the reducing agent in urea-SCR systems in trucks from MAN. It is crucial to understand the functionality of the
catalyst for a proper reaction design and further material developments with the objective to develop smaller exhaust cleanup systems with optimum efficiency.
References
[1] G. Piazzesi, O. Kröcher, M. Elsener, A. Wokaun, Appl. Catal. B 65 (2006) 55-61.
[2] I. Czekaj, G. Piazzesi, O. Kröcher, A. Wokaun, Surf. Sci. 600 (2006) 5158-5167.
[3] I. Czekaj, O. Kröcher, G. Piazzesi, J. Mol. Catal. A 280 (2008) 68-80.
A-16 Model NO x Storage Catalysts: Reaction Mechanisms and Kinetics at the Microscopic Level
A. Desikusumastuti a , T. Staudt a , M. Happel a , Z. Qin b , S. Shaikhutdinov b ,
S. Gardonio c , S. Lizzit c , E. Vesselli d , A. Baraldi d , H. Grönbeck e , J. Libuda a, *
a Erlangen Catalysis Resource Center and Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Egerlandstr. 3, 91058 Erlangen, Germany.
b Chemical Physics Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, 14195 Berlin, Germany.
c Sincrotrone Trieste S.C.p.A., S.S. 14 Km 163.5, I-34012 Trieste, Italy.
d Physics Department and Center of Excellence for Nanostructured Materials, Trieste University, 34127 Trieste, Italy.
e
Competence Centre for Catalysis, Chalmers University of Technology, SE-41296 Göteborg, Sweden.
*Corresponding author. Tel: +49 9131 8527308, Fax : +49 9131 8528867, e-mail: libuda@chemie.uni-erlangen.de
Background
Among the catalytic routes towards NO x reduction in lean exhaust gas streams, the concept of nitrogen storage and reduction catalysts (NSR) has attracted much
attention in terms of fundamental research. Still, the underlying processes remain poorly understood at the microscopic level.
Results
In order to obtain microscopic-level insights into the mechanism and kinetics of NO x storage and release, we have developed novel well-defined NSR model
catalysts. These models are based on ordered, single-crystal-supported Al 2 O 3 films, on which BaO and Pd nanoparticles are co-deposited under ultrahigh-vacuum
conditions. Detailed correlations between structure and reactivity are obtained using a unique multiple-method approach: We combine scanning tunneling
microscopy, high-resolution photoelectron spectroscopy using synchrotron radiation, time-resolved IR reflection absorption spectroscopy, multi molecular beam
methods, and combined reactor/TR-IRAS experiments up to ambient pressure conditions. Combining experimental data with density functional theory, the nature of
nitrite and nitrate species on BaO nanoparticles is identified in detail. Surface nitrates and nitrites show a complex formation and interconversion behavior, strongly
depending on particle size, temperature and coverage. Mutual stabilization of surface and ionic nitrates decisively affects their stability. Intermixing of Al 3+ and Ba 2+
ions occurs even at low temperature and critically controls the kinetics of NO x uptake. Doubly nanostructured model systems combining BaO and Pd nanoparticles
on Al 2 O 3 provide unique possibilities to control the degree of contact between BaO and Pd. While the presence of Pd nanoparticles strongly modifies surface nitrate
formation, the adsorption properties of the Pd particles sensitively depend on the degree of surface oxidation, which changes as a function of particle size and
reaction conditions.
Justfication for acceptance
The present results show that all elementary steps occurring on NSR catalysts can be reproduced on suitable NSR model systems. The reduced complexity of these
models and their accessibility to surface science experiments provides insights into mechanistic aspects of the corresponding processes at an unprecedented level of
detail.
References
[1] J. Libuda, H.-J. Freund, Surf. Sci. Rep. 57 (2005) 157.
[2] A. Desikusumastuti, M. Laurin, M. Happel, Z. Qin, S. Shaikhutdinov, J. Libuda, Catal. Lett., in press.
[3] A. Desikusumastuti, T. Staudt, H. Grönbeck, J. Libuda, J. Catal., in press.

A-17 NSR catalyst supported on a Al 2 O 3 / ZrO 2 -TiO 2 nano-composite: Sulphur Resistance
N. Takahashi , *, H. Imagawa, T. Tanaka, S. Matsunaga, H. Sobukawa and H. Shinjoh
TOYOTA Central Research and Development Labs., Inc., Nagakute, Aichi 480-1192, Japan.
*Corresponding author. Tel: +81 561 71 7598 , Fax : +81 561 63 6150, e-mail: e0790@mosk.tytlabs.co.jp
Background
The reduction of CO 2 emissions from automobiles is an important issue to prevent the global warming. The lean-burn engine with NO x storage-reduction (NSR)
catalysts system is one of the most feasible solutions to this technical challenge [1]; however, sulphur poisoning and thermal aging deteriorate the catalytic activity of
the NSR catalyst. We previously reported that a ZrO 2 -TiO 2 solid solution (ZT) instead of pure TiO 2 improved the NSR catalyst durability against thermal aging [2].
In this time, we synthesized a novel Al 2 O 3 / ZT (AZT) nano-composite and used it as a NSR catalyst support to improve its durability against sulphur poisoning and
enhance catalytic performance without hampering thermal stability.
Results
The co-precipitation method was employed to obtain the AZT from a solution. The final AZT material consisted of 50 wt% Al 2 O 3 , 35 wt% ZrO 2 and 15 wt% TiO 2 .
XRD pattern indicated that the AZT contained -Al 2 O 3 and tetragonal ZT phases, and TEM image elucidated that the primary particles of Al 2 O 3 and ZT formed a
nano-composite structure. The NSR catalyst, Ba-K/Pt-Rh/AZT, was prepared by impregnating precious metals and NO x storage materials on the AZT support. A
comparative catalyst, noted Ba-K/Pt-Rh/Al 2 O 3 -ZT, was obtained in the same way, except that-Al 2 O 3 and ZT powders were physically mixed. The catalysts
loadings in Pt, Rh, BaO and K 2 O were 1.3, 0.3, 19.4 and 3.0 wt%, respectively. In a first experiment, both catalysts were exposed to a SO 2 -containing oxidizing
atmosphere at 873 K for 30 min and cooled to 373 K under flowing N 2 . Afterwards, the gas flow was switched to reducing conditions and heated to 1073 K at a rate
of 15 K/min (TPR). It was found that the total sulphur desorption from the Ba-K/Pt-Rh/AZT catalyst was 1.25 times larger than for the Ba-K/Pt-Rh/Al 2 O 3 -ZT
catalyst. This is in agreement with the work of Hachisuka et al., who reported that the decomposition of sulphates was accelerated at the interface between Al 2 O 3 and
TiO 2 [3]. The AZT nano-composite material indeed exhibited a larger contact surface between Al 2 O 3 and ZT than the physically mixed Al 2 O 3 and ZT powders.
Therefore, the nano-composite structure of AZT promoted the decomposition of K and Ba sulphates under reducing conditions. We then studied the NO x storage
capacity (NSC) after sulphur aging of the Ba-K/Pt-Rh/AZT and Ba-K/Pt-Rh/Al 2 O 3 -ZT catalysts. This aging was performed under fluctuating oxidizing and reducing
atmospheres at 873 K for 110 min with switches every 30 s. We observed that the NSC following a 3 s rich-spike was approximately 1.5 times larger for the Ba-
K/Pt-Rh/AZT catalyst than for the Ba-K/Pt-Rh/Al 2 O 3 -ZT catalyst between 673 and 873 K. We assume that this is due to the higher sulphur tolerance of the AZT
support.
Justification for acceptance
Automobile emission control is one of the main topics in this conference and the NSR catalyst system helps reducing both NO x pollutant and CO 2 emissions. As the
developed AZT support has a good potential to improve the sulphur durability of NSR catalysts, we believe this work is very relevant to this conference.
References
[1] N. Takahashi et al., Catal. Today 27 (1996) 63.
[2] N. Takahashi et al., Appl. Catal. B: Environ. 72 (2007) 187.
[3] I. Hachisuka et al., SAE Tech. Paper 2000-01-1196 (2000).
A-18 Understanding practical catalysts using a surface science approach:
The importance of strong interaction between BaO and Al 2 O 3
Cheol-Woo Yi, Ja Hun Kwak, Charles H.F. Peden, and János Szanyi *
Institute for Interfacial Catalysis, Pacific Northwest National Laboratory, Richland, WA 99352, USA
* Corresponding author: Tel: 1-509-371-6524; Fax: 1-509-371- e-mail: janos.szanyi@pnl.gov
Background
NO x storage materials (NS) (e.g. BaO/-Al 2 O 3 ) are the critical components of a new class of catalyst materials considered for use in lean NO x emission technologies.
Fundamental studies on these systems are rare [1-3]. In our initial studies on BaO/Al 2 O 3 /NiAl(110) ( BaO >10 ML) model NO x storage systems we have, for the first
time, given experimental confirmation of the formation of nitrite/nitrate ion pairs during the initial stages of NO 2 uptake on pure BaO surfaces. In this study we have
focused on the NO 2 uptake properties of these model systems at BaO coverages relevant to those of practical catalysts, and the strong effect the support (in this case
Al 2 O 3 ) may play on the properties of the active storage material.
Results
BaO/Al 2 O 3 /NiAl(110) model NS materials were prepared by reactive layer (NO 2 ) assisted Ba deposition onto an ultrathin alumina film with Ba < 1 ML and
characterized by XPS. The NO 2 chemistry of the thus prepared systems was studied by XPS and RAIRS. The results from these systems were compared and
correlated with those obtained from both pure BaO and high surface area practical NS systems containing comparable amounts of BaO active NO x storage phase.
Initial NO 2 adsorption was found to be completely different from that observed for pure BaO; at these low BaO coverages initially nitrite species form that is
converted to nitrates at high NO 2 exposures. BaO which interacts with the alumina support so strongly that it forms a Ba-aluminate surface layer is pulled out by its
reaction with NO 2 and forms bulk-like Ba(NO 3 ) 2 . This phenomenon is identical to that we observed for high surface area BaO/-Al 2 O 3 materials: a. TEM image of
the activated BaO/-Al 2 O 3 is identical to that of the -Al 2 O 3 support, while the nanosized, monodispersed Ba(NO 3 ) 2 particles form upon exposure of this samples to
NO 2 , and b. the formation of nanosized Ba(NO 3 ) 2 crystallites were observed by XRD on high temperature-annealed BaO/-Al 2 O 3 samples after prolonged NO 2
exposure without any change in the initially present Ba-aluminate phase [4].
Justification for acceptance
The results of this study clearly show the consequence of the very strong interaction between BaO and -Al 2 O 3 on the NO x chemistry in both model and practical NS
systems. The work clearly demonstrates the utility of well-designed surface science studies in aiding to understand real catalytic systems.
References
[1] P. J. Schmitz, R. J. Baird, J. Phys. Chem. B 106 (2002) 4172.
[2] A. Tsami, F. Grillo, M. Bowker, R. Nix, M. Surf. Sci. 600 (2006) 3403.
[3] E. Ozensoy, C.H.F. Peden, J.Szanyi, J.Catal. 243 (2006) 149.
[4] C.W. Yi, J.H. Kwak, C.H.F. Peden. C. Wang, J. Szanyi, J.Phys.Chem. C 111 (2007) 14942.

A-19 Synthetic gas bench study of a 4 way catalytic converter : catalytic oxidation, NOx storage/reduction
and impact of soot loading and regeneration
C.N. Millet *a , R. Chedotal a , P. Da Costa b
a IFP-Lyon, BP3, 69360 Solaize, France, b UPMC Paris 6, Laboratoire de Réactivité de Surface, 4 place Jussieu, 75252 Paris cedex 05, France
Corresponding author. Tel: +33 (0) 478022187, Fax : +33 (0) 478022014, e-mail: c-noelle.millet@ifp.fr
Background
The so-called four way catalyst converts CO, HC, NOx and particulate matter on a single monolith. It allows diesel vehicles to obey to the increasingly stringent
emissions regulations to reach EURO 5 while at the same time decreasing the space needed by the exhaust aftertreatment system. The Diesel Particulate NOx
Reduction catalyst (DPNR) developed by Toyota is the first commercialised example of such a technology 1 . It is combined with fine engine control strategies so as
to ensure optimal conversion of all pollutants. It is hence associated with a large number of catalytic reactions which interact with each other and compete for active
sites.
Results
The behaviour of 24.5 ml DPNR carrots was characterized on a synthetic gas bench. This global kinetic study allowed to highlight the complex reaction mechanism
that occurs on a Pt/Ba/ZrO 2 /Al 2 O 3 4 way catalytic converter. Oxidation reactions were dominant in a lean environment: CO oxidation by NO 2 at low temperature 2
followed by H 2 , CO, NO and hydrocarbons (HC) oxidation by O 2 . Moreover, some N 2 O formation was observed simultaneously with HC oxidation light-off. NOx
were stored on barium storage sites. In rich conditions H 2 , CO and HC were used to reduce NOx. NH 3 production from H 2 was also observed. This created ammonia
could be a supplementary reducing agent in the deNOx process. A further conversion of HC was obtained at high temperature (above 500 °C) due to steam
reforming reaction. Interactions and inhibitions were also found. NOx storage appeared to be inhibited by CO oxidation with NO 2 at low temperatures and also by
HC, maybe through competition for storage sites with CO 2 produced during HC oxidation. Catalytic reactions were affected by the soot deposit. Continuous
oxidation of soot by NO 2 also induced a slower NOx storage rate.
Justification for acceptance
Unlike for other aftertreatment systems 3,4 , few studies deal with the complex reaction mechanism occurring in a 4 way catalytic converter. In addition this work
involves experimental conditions close to real engine operation and catalyst samples were loaded with soot on an engine bench device.
References
[ 1 ] T. Tanaka, 22 nd International Vienna Motor Symposium (2001) 216
[ 2 ] S. Erkfeldt, E. Jobson, M. Larsson, Top. Catal. 16/17 (2001) 127
[ 3 ] W.S. Epling, L.E. Campbell, A. Yezerets, N.W. Currier, J.E. Parks II, Catal. Rev. 46 (2004) 163
[ 4 ] J.P. Breen, R. Burch, C. Fontaine-Gautrelet, C. Hardacre, C. Rioche, Appl. Catal. B 81 (2008) 150
A-20 Copper ferrite nanoparticles as microwaves susceptible soot oxidation catalyst
Vincenzo Palma*, Paola Russo, Giuseppa Matarazzo, Paolo Ciambelli
Department of Chemical and Food Engineering, University of Salerno, 84084 Fisciano (SA), Italy.
*Corresponding author: Tel. +39 089 964147–FAX +39 089 964057 e-mail: vpalma@unisa.it
Background
Regeneration of Diesel Particulate Filters (DPF) is actually the critical step in the diesel exhaust after treatment. Continuous DPF regeneration mode is very
attractive, but is still not feasible. Therefore, periodic regeneration of the filter is required. The biggest challenge is to control the heat release resulting from soot
oxidation: filters without adequate regeneration control may easily accumulate soot loads in excess and experience very high temperatures. The application of
microwaves permits to overcome these technical hitches allowing to instantaneously and selectively heat materials in dependence of their dielectric properties.
Results
Spinel ferrites have been investigated in recent years for their useful electrical and magnetic properties arising from their ability to distribute the cations amongst the
available tetrahedral and octahedral sites. In this work they were investigated as microwaves sensitive catalysts for soot oxidation.
Copper ferrites CuFe 2 O 4 were prepared by solid state reaction of CuO and Fe 2 O 3 , by sintering at different temperatures (850-1000°C) and cooling down at different
rates. The ferrites prepared were characterized by XRD diffraction and by microwave absorption properties measurements.
We found that the preparation procedure plays a very important role in determining the chemical structure of spinel ferrites: i) increasing the sintering temperature
the formation of single phase ferrite instead of mixed phases (containing also CuO and Fe 2 O 3 ) was observed; ii) increasing the cooling rate the cubic instead of the
tetragonal structure occurs. In any case, the crystallite size (20-40 nm) prove the formation of nanoparticles. The synthesis conditions influence also the microwave
absorbing properties of the ferrites and consequently their activity towards soot oxidation in the presence of microwaves, as indicated by catalytic activity tests
carried out on soot-catalyst mixtures at controlled heating rate or at constant power in a specifically designed microwave heated laboratory reactor. Results showed a
higher catalytic activity of cubic with respect to tetragonal structure towards soot oxidation, in terms of ignition temperature (260°C against 380°C) and maximum
oxidation rate temperature (480°C against 560°C). In particular, the energy required to reach a given soot conversion for cubic ferrite (6 KJ/mg soot at 50% soot
conversion) is about half of that for tetragonal ferrite, in agreement with the observed superior microwave absorption properties of cubic ferrite with respect to
tetragonal one.
Justification for acceptance
Suitable systems for diesel exhaust catalytic filter regeneration based on microwave heating are not actually available. The present work provides advantages and
alternatives over the known art by providing a catalytic system suitable for high efficient soot-filter regeneration.

A-21 An operando 5.8 GHz microwave-heated FT-IR reactor study of the NO 2 -CH 4 reaction, over a Co/Pd-HFER catalyst
S. Capela a,b , E. Seguin c , C. Henriques a* , M.F. Ribeiro a , F.Thibault-Starzyk c , S. Thomas c ,
P. Da Costa b , G. Djéga-Mariadassou b , F. Ramôa Ribeiro a
a IBB/CEBQ, Instituto Superior Técnico, Lisboa, Portugal
b Laboratoire de Réactivité de Surface, UMR CNRS 7609, Université Pierre et Marie Curie, Paris, France
c Laboratoire Catalyse et Spectrochimie, UMR 6506, ENSICaen & UCBN, Caen, France
*Corresponding author: Tel.: +351 218417325; fax: +351 218419198, e-mail: carlos.henriques@ist.utl.pt
Background
The CH 4 -SCR of NO mechanism has been deeply studied [1, 2]. Nevertheless, the detailed reaction pathway remains a matter of debate among the catalysis
community. The main objective of the present study is to investigate the type of adsorbed species formed during the NO 2 /CH 4 reaction over a Co/Pd-HFER catalyst,
using FT-IR operando techniques that permit the detection of short lived reaction intermediates.
Results
Two different tests, followed by operando FT-IR, were performed over a Co/Pd-HFER catalyst. In the first one, consisting on a TPSR, a reaction mixture (500 ppm
NO 2 and 5000 ppm CH 4 in Ar) was supplied to an IR cell-reactor, where the temperature was increased at 5ºC min -1 from 110ºC until 420ºC. At about 180ºC, the
formation of a band at 1745 cm -1 , characteristic of the vibration C=O on formaldehyde, is observed, accordingly with previous results obtained during catalytic tests
[3]. Moreover, -NCO species were also detected at about 250ºC.
In the second test, the same reaction mixture is supplied to a 5.8 GHz microwave-heated IR reactor-cell, previously stabilised at (i) 80ºC and (ii) 200ºC by
conventional means. The application of a microwave field (60 seconds, 250W) leads to a very quickly cell heating [4]. During this phase, rapid-scan FTIR spectra
were collected (time resolution of 200ms, resolution 4cm -1 ). In both cases formaldehyde formation was detected, as a primary product of the reaction between NO 2
and CH 4 , more markedly than with the conventional operando cell. Furthermore, the formation of CO (2050cm -1 ) was also detected at the catalyst surface, probably
due to the partial oxidation of CH 4 assisted by nitrate-like species.
Justification for acceptance
This work focuses an operando FT-IR spectroscopy study, obtained with a new 5.8 GHz microwave heated cell-reactor, that combines fast heating and time-resolved
IR spectroscopy. The results obtained under these conditions can provide new insight into the detailed mechanism of the CH 4 -SCR of NO.
References
[1] R. Burch, J.P. Breen, F.C. Meunier, Appl. Catal. B 39 (2002) 283.
[2] O. Gorce, F. Baudin, C. Thomas, P. da Costa, G. Djéga-Mariadassou, Appl Catal B 54 (2004) 69.
[3] S. Capela, R. Catalão, M.F. Ribeiro, P. Da Costa, G. Djéga-Mariadassou, F. Ramôa Ribeiro, C. Henriques, Catal. Today, online
(doi:10.1016/j.cattod.2007.11.048).
[4] E. Seguin, S. Thomas, C. Henriques, P. Bazin, G. Bond, F. Thibault-Starzyk, unpublished results.
A-22 Model of catalytic carbon black oxidation in the presence of CeO 2 :
3-D representation of the solid-solid mixture
M. Issa, H. Mahzoul, V. Tschamber, A. Brillard, J-F. Brilhac
Laboratoire Gestion des Risques et Environnement, Université de Haute- Alsace, 25 rue de Chemnitz, 68200 Mulhouse, France.
Phone : +33 3 89 32 76 66, e-mail : jean-francois.brilhac@uha.fr
Background
The enhancement of soot oxidation during catalytic DPF regeneration requires a good understanding of the phenomena involved in this process. Among the
parameters acting on this reaction, the contact between soot and catalyst is a key one. The aim of this work is to propose a 3-D representation of the mixture between
carbon black and CeO 2 particles to simulate catalytic carbon black oxidation in a fixed bed reactor. This representation leads to a realistic sight of the media
investigated (various CB/CeO 2 mixtures). The model is used to extract kinetic parameters of catalyzed carbon oxidation.
Results
The catalytic combustion of carbon black (CB) used as a model of Diesel soot in tight contact with a commercial ceria (CeO 2 ) was investigated. Different CB/CeO 2
mixtures were tested in a fixed bed reactor (mass ratio ranging from 5/95 to 95/5 with a total mass of the sample equal to 10 mg) in order to gain a better
understanding of the effect of CeO 2 /CB ratio on catalysed carbon oxidation. The experimental data are used to propose a model of CB oxidation in the presence of
CeO 2 . The model considers CB/CeO 2 mixtures as 3-D systems. It allows the representation of the mixtures by considering the particles of carbon black and catalyst
as spheres. The particles are located and oriented randomly in a simple cubic system. The model accounts for the fraction and the diameter of catalyst introduced in
the mixture, mass of CB in the sample and the contact area between CB and CeO 2 . This contact area is defined as the surface developed by CeO 2 particles per mass
of catalyst. The model accounts for two fractions of CB :
- carbon sites in tight contact with CeO 2 which are burnt away in the catalyzed reaction at low temperature :
(-C) +2 CeO 2 CO 2 + 2 Ce 2 O 3
- carbon sites for which CB oxidation does not depend on the catalyst (reaction between CB and molecular oxygen)
2 (-C) + 3/2 O 2 CO 2 + CO
This model enables to predict the experimental combustion rate of carbon black in the tested mixtures and kinetic parameters were proposed.
Justification for acceptance
The 3-D model developed in this work enables to model CB combustion in the presence of a catalyst in a fixed bed reactor. Such a model could be used to simulate
catalysed DPF regeneration.

A-23 Correlation between spatiotemporal distribution of reactions and global performance
of a commercial lean NO x trap catalyst at varying sulfation stages
Jae-Soon Choi a *, William P. Partridge a , Josh A. Pihl a , Todd J. Toops a , Michael J. Lance b , Charles A. Finney a ,
Kalyana Chakravarthy a , C. Stuart Daw a
a
Fuels, Engines, and Emissions Research Center, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6472, USA
b
High Temperature Materials Laboratory, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6068, USA
*Corresponding author. Tel: +1-865-946-1368, Fax: +1-865-946-1354, e-mail: choijs@ornl.gov
Background
The intrinsically transient and integral nature, and the complex interplay between various chemical reactions, make fundamental understanding of LNTs, especially
that of commercially relevant formulations, difficult with conventional reactor-outlet measurements alone. In this work, we attempted to provide new insights into
the functioning of LNTs by integrating results from various techniques with different scales. A particular emphasis was given on understanding how sulfation
impacts both local and global LNT structure, chemistry and performance: information relevant to real LNT systems.
Results
A commercial LNT was evaluated in a bench flow reactor as 2.1-cm diameter and 7.4-cm long cores under realistic cyclic conditions: 60-s lean/5-s rich with H 2 O
and CO 2 present. The gas composition was analyzed by a Spatially Resolved Capillary Inlet Mass Spectrometer (SpaciMS) at different axial locations inside the
catalyst [1]. Spatiotemporal species profiles clearly showed how a specific reaction such as sulfation developed along the catalyst and interacted with other
reactions such as NO x storage, O 2 storage, and reductant consumption. The performance evaluation was complemented by postmortem characterization using
elemental analysis, XPS, EPMA, DRIFTS, and TPR revealing the nature and axial distribution of sulfur species. In this presentation, we will discuss how local
sulfation, NO x storage, O 2 storage, and reductant consumption chemistry are interrelated to determine global LNT performance. For example, the increasing global
NH 3 selectivity with sulfation will be rationalized by a plug-like downstream shift of the NH 3 -forming NO x storage/reduction (NSR) zone and the resultant
shortening of the NH 3 -consuming oxygen-storage-capacity-only zone downstream of the NSR zone.
Justification for acceptance
This work led to a conceptual model describing commercial LNTs under a broad range of operating conditions. In particular, the correlation between the nature and
spatial distribution of different sulfur species, and their impact on local and global LNT performance, is a useful addition to the field of automotive catalysis where
little information of this kind is available to model and implement real LNTs.
Reference
1. J.-S. Choi, W.P. Partridge, C.S. Daw, Appl. Catal. B 77 (2007) 145.
A-24 Activation of Al 2 O 3 by a long range stabilization mechanism
Anders Hellman,*, and Henrik Grönbeck
Department of Applied Physics and Competence Centre for Catalysis,
Chalmers University of Technology, SE-412 96, Göteborg, Sweden
*corresponding author. Tel: +46 31 7725611, Fax: +46 31 160062, e-mail: ahell@fy.chalmers.se
Background
Hydrocarbon (HC) assisted selective catalytic reduction (SCR) can be used to reduce NO x in an excess of oxygen. Especially a catalyst with silver supported on
alumina (Ag/Al 2 O 3 ) has been measured to have high activity for this reaction [1,2]. Although numerous experimental studies have clarified many issues concerning
the Ag/Al 2 O 3 catalyst, the nature of the active phase is still an open discussion [1,2]. Relevant for the discussion are recent results from surface science experiments
and theory, which show that combined metal-oxide systems behave very different as compared to its separate components [3].
Results
Recently, we demonstrated the existence of a long-ranged stabilization mechanism for NO 2 adsorption on
Al 2 O 3 in contact with silver [4]. The activation is present both when Al 2 O 3 is supported by Ag(111) and when
it is in contact with small Ag clusters. A crucial component of the stabilization mechanism is a charge transfer
to NO 2 . Another component is the change in the chemical bond between Al 2 O 3 and NO 2 on one hand and
Al 2 O 3 and the metal on the other. It is clear that Al 2 O 3 supported on Ag is vastly different as compared to the
separated systems. The character of the proposed stabilization mechanism may have implications for how
oxide supports should be regarded in heterogeneous catalysis. For instance, spill-over effects or even change of
the active site from the metal phase to the surrounding oxide are possible scenarios. The fact that the longranged
stabilization mechanism is active also for small Ag clusters suggests an interesting interpretation of the
recent suggestion that the active phase in HC-SCR consists of a small number of Ag atoms. Given the present
mechanism, one possibility is that the Ag clusters are not centers for the catalytic reactions but merely act as
dopants for Al 2 O 3 .
Justification for acceptance
The general nature of the long-range stabilization mechanism will have consequences for our understanding of metal-oxide systems within heterogeneous catalysis.
References
[1] R. Burch, Cat. Rev. 46 (2004) 271.
[2] K. Shimizu and A. Satsuma, PCCP 8 (2006) 2677.
[3] H.J. Freund, Surf. Sci. 601 (2007) 1438 and references therein.
[4] A. Hellman and H. Grönbeck, Phys. Rev. Lett. (accepted)

A-25 Advanced solutions for the pollution abatement from the ships cruising the motorways of the sea
N.Hickey, I.Boscarato and J.Kašpar
Dipartimento di Scienze Chimiche, Università di Trieste,Via Giorgieri, 1, 34127-Trieste, Italy and also INCA – Interuniversity Consortium Chemistry
for the Environment. Fax +39-040 5583903, e-mail: kaspar@units.it.
Background
In 2004, the EU provided a legal framework for funding the “motorways of the sea” with the aim of increasing the intermodality of the transport
network and to favour a shift towards transport of goods over the sea. (see: http://ec.europa.eu/transport/intermodality/motorways_sea/index_en.htm)
However, regulations on marine-emissions and on the quality of the fuel are quite relaxed. For example, the International Marine Organisation limits
NO x emissions to 13 g/kWh compared to the Euro V limit of 2 g/kWh set for heavy-duty diesel engines. Similarly, sulphur content of 2.5-1.5 % is
normally found in the marine fuel (bunker) compared to the value of 10-50 ppm which is present in the fuels used for the surface transport. As a result
of this, it is estimated that in EU25, the emissions due to sea transport will overtake those from land transport by 2017 and 2020 for, respectively, SO 2
and NO x . Under such premises, the Italian Ministery of University and Research has recently supported a 6 billion € project (ECOMOS [1]), which
joins the Fincantieri S.p.A., a major cruising ship builder (45% of world market), CETENA (Fincantieri’s research centre), University of Genoa, CNR
– “Istituto Motori” Naples and INCA aimed at the development of advanced strategies for the integrated control of marine emissions.
Results
An overview of the world situation on the impact of the emissions from marine engines will be given. We will focus the specific strategies and the
problems in the field of the control of the emissions from ships, which arise mainly from the poor quality of the fuel compared to surface transport, as
well as the different engine characteristics. A scenario of the different technologies, in terms of engine modifications, scrubber-type of technologies
and catalytic solutions will be presented and the efficiency of the different solution compared. Preliminary results will be reported, obtained on a minipilot
plant specifically designed for the abatement of marine diesel emissions using a real high sulphur marine fuel.
Justification for the acceptance
The global impact of the emissions from the ships is extremely high and strongly increasing all over the world. For example, it has been estimated that
world marine SO 2 emissions in 2001 were three-times those from surface transport. Rapid development of cost-effective, compact and efficient
catalytic technologies capable of solving the specific problems and the real difficulties found in this sector is therefore mandatory. Unfortunately, this
sector has received scarce attention from the scientific community so far. In addition to the presentation of our results, the aim of this presentation is
also to heighten the awareness of the specific problems found in the field.
References
[1] http://www.ecomos-cetena.it/.
A-26 Mechanism of the C 2 H 2 oxidation in the presence of CO on gold catalyst : a model reaction for Cold Start Engine Oxidation
Yassine Azizi, Corinne Petit, Véronique Pitchon *
LMSPC, UMR 7515 du CNRS 25 rue de Becquerel, 67087 Strasbourg, France, pitchon@chimie.u-strasbg.fr
Background
Cold-start emissions are responsible for 90% of the pollution emitted by cars operated with a TWC, since this latter is not efficient below 200°C. To solve this
problem, an introduction of a catalyst able to oxidise the unburned hydrocarbons and CO at low temperature is required. In a previous work we have demonstrated a
remarkable resistance to thermal ageing at 600°C of gold catalysts in the absence or presence of water which opens up the perspectives for an application of gold
catalysis in automotive industry.
Therefore, the main objectives of the work presented in this contribution, is the preparation of gold catalyst various supports with high oxidation activity and strong
resistance to both presence of water and thermal deactivation. Being the most difficult HC to be burned in an exhaust gas, this study was focussed on the reaction of
C 2 H 2 oxidation in the presence of CO. A comparison of the mechanism of C 2 H 2 oxidation with O 2 or C 2 H 2 reduction with H 2 gives very good indication on the
nature of the active sites.
Results
The catalysts were prepared by Direct Anionic Exchange which consists in a controlled exchange between an HAuCl 4 solution and a support, in this caseCeO 2 , ZrO 2
and TiO 2 . The preparation includes a careful control of each parameter (concentration, pH, time of exchange) and a washing procedure with concentrated ammonia
at 70°C in order to ensure complete removal of chloride ions.
The conversion of CO alone occurs at low temperature (below 75°C) in the following order Au/CeO 2 > Au/TiO 2 > Au/ZrO 2 . The reaction of oxidation of CO is
inhibited in the presence of alkynes but not in the presence of alkenes. This gives indications over the mechanism of oxidation – the adsorption of acetylene and CO
most probably occurs on the same active site. The adsorption is competitive in favour of acetylene according to CO. The acetylene is strongly adsorbed to the surface
at room temperature and occupy all adsorption sites which does not allow an adsorption of CO. However, it provokes an increase in the temperature of acetylene
conversion of c.a. 50°C in whole range of temperatures compared to the conversion of acetylene alone. Once the oxidation of acetylene is complete the oxidation of
CO begins. The delayed oxidation of CO indicates that CO could adsorb and react only on the sites totally liberated from acetylene or its products of oxidation.
On the contrary, for the reduction of C 2 H 2 , CO does not affect the C 2 H 2 conversion nor the selectivity, proving that either hydrogen or carbon monoxide adsorbs on
different sites or the competition for the adsorption site is strongly in favour of H 2 . This complete difference of affinity for C 2 H 2 whether in oxidative or reducing gas
atmosphere and its implication on the nature of the active sites in gold catalysts will be discussed during the presentation.

ORAL
PRESENTATION
ABSTRACTS
CLEAN ENERGY

CE-1
Fuel production by Fischer-Tropsch synthesis with CO/H 2 from different feeds
S. Løgdberg b , Ø. Borg d , D. Tristantini c , E.A. Blekkan a , B. Gevert c , S. Järås b , A. Holmen a,x
a Norwegian University of Science and Technology, Dept. Chem. Eng., N-7491 Trondheim, Norway.
b Royal Institute of Technology, Chemical Technology, S-10044 Stockholm, Sweden.
c Chalmers University of Technology, Dept. Chem. & Biological Eng. S-41296 Gothenburg, Sweden.
d StatoilHydro Reseach Centre, Postuttak, N-7005 Trondheim, Norway.
x Corresponding author. Tel: +47 73594151, Fax: +47 73595047, e-mail: holmen@chemeng.ntnu.no
Background
Syngas precursors such as natural gas and biomass (and coal) can be converted into a high-value, clean-burning fuel via the Fischer-Tropsch synthesis. The fuel
consists mainly of linear alkanes giving a high cetane number. The fuel is colourless, odourless and virtually free of aromatics, sulphur and nitrogen compounds.
Syngas from natural gas has a higher H 2 /CO ratio than syngas derived from coal or biomass. Cobalt is considered the most favourable catalyst for the synthesis of
long-chain hydrocarbons from natural gas-based syngas [1]. In this paper we explore the differences between natural gas-based syngas (H 2 /CO ratio close to 2)
and syngas with a lower H 2 /CO ratio over Co catalysts as well as new systems where the idea is to introduce water-gas shift (WGS) activity through adding Fe.
Results
Fischer-Tropsch synthesis was performed in a fixed-bed reactor (10 mm i.d.) at 483 K and 20 bar using 1 g catalyst diluted with inert particles. The catalysts
contained 12 or 20 wt% Co and Re was added to some of the catalysts as a promoter. Supported catalysts containing 12 wt% Co + Fe with different ratios
between Co and Fe were also prepared by the incipient wetness technique. Care was taken in order to achieve good temperature control and a reliable mass
balance. Details of the experimental set-up and the procedures are given elsewhere [1]. The SSITKA studies (Steady-State Transient Isotope Kinetic Analysis)
were done at 1 bar and with a large excess of H 2 (methanation conditions) [2]. The catalysts were characterized by BET, chemisorption, TPR, XRD and TEM.
SSITKA studies show that for most Co catalysts the turnover frequency is constant provided that the particle size is larger than 6-7 nm. For smaller particle sizes
the turnover frequency decreases [3]. The selectivity, however, depends on catalyst characteristics. Over Co-based catalysts the selectivity also depends on the
conversion, mainly due the partial pressure of water [4]. Comparisons must therefore be performed at the same conversion level. Pore structure and the shape and
size of the Co particles determine the C 5 + selectivity. CO 2 and N 2 are inert in the Co-based FT synthesis and the influence on the kinetics is therefore through
dilution alone. In order to simulate syngas made from biomass, experiments have been performed with H 2 /CO ratios lower than 2. The same trends in terms of
activity and selectivity are evident also with lower H 2 /CO ratios. The usage ratio varied only very little with the H 2 /CO ratio. To avoid H 2 depletion in the gas it is
therefore necessary to design WGS activity into the catalysat or by using a separate WGS reactor. We will report results on mixed metal CoFe catalysts, showing
detrimental effects on activity and selectivity from adding Fe to the Co system.
Justification for acceptance
Fischer-Tropsch synthesis is an interesting technology for converting different C-containg materials to transportation fuels. Modern FT synthesis is mostly
studied with natural gas as the feedstock and it is therefore important to investigate what differences are imposed when biomass is used as the feed.
References
[1] Ø.Borg, S.Eri, E.A.Blekkan, S.Storsæter, H.Wigum, E.Rytter, A.Holmen, J. Catal.248 (2007) 89
[2] V.Frøseth, S.Storsæter, Ø. Borg; E.A.Blekkan, M.Rønning, A.Holmen, Appl.Catal.A 289 (2005)10
[3] P.B.Radstake, J.P.denBreejen, G.L.Bezemer, J.H.Bitter, K.P.deJong, V.Frøseth, A. Holmen, Stud. Surf. Sci. Catal. 167 (2007) 85
[4] E.A.Blekkan, Ø.Borg, V.Frøseth, A.Holmen, Catalysis (RSC, London) 20(2007) 13
CE-2
Catalyst calcination and glow discharge plasma: Tools to enhance dispersion, reducibility and performance of cobalt
catalysts in Fischer-Tropsch synthesis
A.Y. Khodakov a , * W. Chu b ,* J. Hong a,b , P.A. Chernavskii c , J.-S. Girardon a , A. Griboval-Constant a
a Unité de catalyse et de chimie du solide, UMR 8181 CNRS, USTL-ENSCL-EC Lille, Bât. C3 , Cité scientifique, 59655 Villeneuve d’Ascq, France
b Department of Chemical Engineering, Sichuan University, Chengdu 610065, China
c Department of Chemistry, Moscow State University, 119992 Moscow, Russia
*Corresponding authors. Tel: +33 3 20 33 54 37, Fax : +33 3 20 43 65 61, e-mail: andrei.khodakov@univ-lille1.fr (A.Y. Khodakov), chuwei.scu.cn@163.com (W.Chu)
Background
Fischer-Tropsch (FT) synthesis over cobalt catalysts produces clean fuels from syngas which is generated from natural gas, biomass or coal. Control of cobalt
dispersion, reducibility and stability is a key issue in the catalyst design [1]. Decomposition of cobalt precursor is an important step in the catalyst preparation.
Cobalt precursor in FT catalysts can be decomposed using either calcination in oxidizing atmosphere or glow discharge plasma [1, 2]. The paper focuses on the
effect of calcination and pretreatment with plasma on the structure and catalytic performance of cobalt FT catalysts.
Results
The catalysts were prepared using impregnation of alumina and silica with aqueous solutions of cobalt nitrate. The catalysts were characterized by XRD, XPS,
TPR, in situ XANES/EXAFS, in situ magnetic method, propene and CO chemisorption. It was found that both calcination and treatment with glow discharge
plasma led to decomposition of cobalt nitrate and formation of small cobalt oxide nanopaprticles. In silica catalysts, cobalt particle sizes were smaller, when the
catalysts have been calcined at lower temperature (423-473 K). In the alumina supported catalysts, temperature of catalyst calcination produced a much smaller
effect on cobalt dispersion. Calcination at temperatures higher than 673 K resulted in mixed non-stoichiometric compounds of cobalt oxide with the supports.
Decomposition of cobalt nitrate in glow discharge plasma at ambient temperatures (293-323 K) led to much smaller cobalt oxide particles than catalyst
calcination. These oxide particles produced very small cobalt metal superparamagnetic particles after reduction. The size of cobalt particles depended on the
conditions of plasma generation. In all catalysts, FT catalytic performance was a function of cobalt surface metal sites. The plasma assisted cobalt catalysts
exhibited FT reaction rates higher to their counterparts prepared using conventional calcinations
Justification for acceptance
The paper presents novel techniques to control the structure and catalytic performance of cobalt FT catalysts for synthesis of clean fuels. Optimization of catalyst
structure has led to a more than 10-fold increase in the catalytic activity.
References
[1] A.Y. Khodakov, W. Chu, P. Fongarland, Chem. Rev. 107 (2007) 1692.
[2] W. Chu, L.-N. Wang, P. A. Chernavskii and A. Y. Khodakov, Angewandte Chemie Int. Ed., submitted.

CE-3
A new option in CO 2 recycle: conversion to long-chain alcohols and hydrocarbons
M. Gangeri a , S. Caudo a , S. Perathoner a* , G. Centi a , D. Bégin b , C. Pham-Huu b , J. P. Tessonnier c , D. S. Su c
1 Dept. of Industrial Chemistry and Materials Engineering, University of Messina, Italy.
2 Lab. Des Matériaux, Surface at Procédés pour la Catalyse, CNRS &ULP, Strasbourg, France.
3 Fritz Haber Institut der M.P.G., Berlin, Germany
*Corresponding author. Tel: +39 90 6765609, Fax : +39 90 391518, e-mail: perathon@unime.it
Background and Justification for Acceptance
Effective recycle of CO 2 , a necessary option alternative to storage, is still a challenge, notwithstanding the increasing number of studies. We proposed a novel
concept based on a gas-phase photoelectrocatalytic devices [1,2], e.g. different from the conventional liquid phase PEC systems and closer to PEM fuel cells. In
this device, one side is composed from a nanostructure TiO 2 -based thin film where gaseous water is splitted using solar light to produce O 2 , protons and electrons,
while the anode side is based on novel nanostructured carbon-based electrode also operating in gas phase. On the anode side, CO 2 is converted using protons
passing through a Nafion membrane and electrons (a wire connects the two sides of the cell). The characteristics of the electrode are a critical aspect and we
showed that at room temperature and pressure, using Pt nanoparticles confined in conductive carbon nanopores, it is possible to form long-chain hydrocarbons
[2]. We report here new results, using Fe or Pt nanoparticles on carbon nanotubes (CNT) and operations at slightly higher temperature (60°C), where we show
that one order of magnitude higher productivities are possible, with a selective synthesis of alcohols (particularly isopropanol).
Results
Electrocatalytic activity tests are carried out in a continuous flow electrocatalytic reactor at room temperature and T=60 °C where the working electrode operates
in contact with CO 2 , fed continuosly, and protons, provided by an electrolyte (KHCO 3 , 0.5 M), diffuse to the catalyst through a Nafion ® membrane. Experiments
are conducted galvanostatically with modulations in current to improve desorption of the products from the working electrode (± 20 mA). Fe or Pt /CNT (10%
wt) on gas diffusion electrodes assembled with Nafion ® 112 membranes were tested in the CO 2 electrocatalytic conversion. Reaction products are mainly
alcohols and (>C5) hydrocarbons. Distribution of products depends on the nature of the metal ion and reaction temperature. At room temperature mainly C5-C8
hydrocarbons are formed, whereas at higher temperatures preferentially oxygenates prevails. Fe catalysts show a higher selectivity in to isopropanol, whereas Pt
elctrocatalysts are more selective towards C1-C2 oxygenate products. TEM characterizations of the electrocatalysts support structure-activity relationships.
References
[1] (a) G. Centi, S. Perathoner, Studies in Surface Science and Catalysis, 153 (2004) 1. (b) G. Centi, S. Perathoner, Z. Rak, Studies in Surface Science and
Catalysis, 145 (2003) 283-286.
[2] G. Centi, S. Perathoner, G. Winé, M. Gangeri, Green Chem., 9 (2007) 671.
CE-4
Preparation of ordered mesoporous CuO/CeO 2 and their catalytic behavior in CO preferential oxidation
and water gas shift reaction
S. Naito*, W. Shen, T. Hasegawa, and T. Miyao
Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University,
3-27-1, Rokkakubashi, Kanawa-ku, Yokohama, 221-8686, Japan.
*Corresponding author. Tel.+81-45-481-5661, Fax.+81-45-413-89770, e-mail:naitos01@kanagawa-u.ac.jp
Background
The oxygen storage capacity of CeO 2 and its cooperative effect with copper lead Cu/CeO 2 catalyst to be highly active for CO PROX and WGSR [1]. It is
generally accepted that its optimum catalytic activity is achieved in the presence of well-dispersed copper oxide clusters over CeO 2 [2]. Accordingly, higher
surface area CeO 2 as a carrier is preffered to obtain highly dispersed copper species with relatively high Cu loading amount. In the present study, we have
succeeded in the preparation of well ordered high surface area mesoporous CeO 2 by the hard template method, and employed it as a support for Cu loading.
Formed mesoporous Cu/CeO 2 catalysts exhibited an excellent activity for CO PROX and WGSR.
Results
Ordered mesoporous CeO 2 was synthesized for the first time by using the ordered mesoporous silica KIT-6 as a hard template, followed by the removal of
silica with NaOH solution. The CuO/CeO 2 catalysts were prepared by two methods; (1)impregnation of EtOH solution of Cu(NO 3 ) 2·3H 2 O into the ordered
mesopore of CeO 2 followed by calcination at 500 o C (designated as CuCeO-I); (2) heat decomposition(80 o C) of the pressed mixture of Ce(NO 3 ) 4 xH 2 O and
Cu(NO 3 ) 2 xH 2 O inside the pore of silica KIT-6 followed by calcination at 500 o C, and then by removal of silica with NaOH solution (designated as CuCeO-D).
The catalysts were characterized by N 2 sorption, SEM, TEM, and XRD. The CO PROX reaction and WGSR were carried out in a fixed-bed flow system
(W/F=0.36g.min.mL -1 ). The input gas composition for PROX reaction was H 2 /CO/O 2 /N 2 = 70%/0.7%/1.4%/28 %, and the O 2 /CO ratio was 2.0.
Formed mesoporous ceria showed the characteristic small-angle XRD diffraction peaks same as the silica template. The TEM images of both CuCeO-I and -
D catalysts exhibited a well ordered framework with the array of tiny CeO 2 crystallites. The BET specific surface area of mesoporous CeO 2 was more than 180
m 2 /g with the pore volume of 0.20 cm 3 /g. In the case of CuCeO-I, these values decreased considerably with the increase of Cu loading, indicating the presence of
impregnated Cu species inside the pore of CeO 2 . On the other hand, in the case of CuCeO-D, they remained unchanged indicating the presence of Cu species
inside the lattice framework of CeO 2 .
In the Prox reaction over CuCeO-I, 100% CO conversion was obtained at 80 o C with 100% selectivity. However, both activity and selectivity decreased
considerably at higher temperatures by the prevalence of H 2 -O 2 reaction. On the other hand, the Prox activity of CuCeO-D catalysts was rather low and 100%
CO conversion was obtained at 140 o C with 100% selectivity. However, they remained unchanged up to 200 o C, indicating the parallel suppression of H 2 -O 2
reaction over CuCeO-D catalysts. In-situ EXAFS, XPS and FT-IR spectroscopies indicated that CuO clusters were the catalytically active species in the case of
CuCeO-I, whereas isolated Cu x+ cations in the case of CuCeO-D. In the WGSR over CuCeO-I, more than 80% CO conversion was obtained at temperatures
higher than 250 o C, which was comparable to the activity of practically employed CuO-ZnO-Al 2 O 3 catalysts.
References
[1] M.Flytzani-Stephenopoulos et al. J.Catal.153 (1995) 304. [2] M. Luo et al., J.P.C.(B) 111 (2007) 12686.
[3] M. Fernandez-Garcia et al. J.P.C.(B) 110 (2006) 428.

CE-5
Controlled surface modification of Pt/Al 2 O 3 catalysts for preferential oxidation of CO in hydrogen fuel streams
S.K. Jain, E.M. Crabb* a , L.E. Smart a , and D. Thompsett b
a Department of Chemistry, The Open University, Walton Hall, Milton Keynes, MK7 6AA, UK
b Johnson Matthey technology centre, Sonning Common, Reading, RG4 9NH, UK
*Corresponding author. Tel: +44 (0) 1908 659894, email: e.m.crabb@open.ac.uk
Background
Hydrogen fuel cells have been studied extensively in recent years as they show considerable promise for both stationary and automotive power supply. The
hydrogen fuel can be supplied by reforming of hydrocarbons, however the reformate also contains CO, a poison for the Pt electrocatalysts in the fuel cell. The
majority of the CO can be removed using the water gas shift reaction, followed by preferential oxidation (PROX). A number of catalysts have been studied for
the PROX reaction and some of the most interesting systems combine a noble metal and a reducible metal oxide, such as CoO x , FeO x , MnO x or CeO x .
Results
The catalytic performance of a series of Pt/Al 2 O 3 catalysts, modified with Cr, Mn, Fe, Co, Ni, Cu and Sn, has been tested for the preferential oxidation of CO in
hydrogen. The promoters were deposited onto the surface of a 5wt% monometallic Pt/Al 2 O 3 catalyst using a controlled surface approach, to give a nominal
surface promoter:Pt atomic ratio of 1:2 (corresponding to typically 0.15–0.25 wt.% of the promoting metal). The aim of this approach was to build the Pt -
promoter oxide interfacial sites believed to be important for the non-competitive dual site mechanism proposed for these catalysts[1]. The catalysts were
characterised using TEM, EDX, ICP-AES and CO chemisorption and results suggest that the promoter was successfully deposited on to the Pt surface creating
these Pt-promoter metal oxide interfacial sites. Even at these low loadings, significant enhancement was observed in the catalytic performance for the Fe-, Coand
Sn- promoted catalysts, highlighting the successful preparation of these sites. Further studies at a lower O 2 :CO ratio, showed significant enhancement for the
Co- promoted system, attributed to the non-competitive dual-site mechanism, with the promoting oxide acting as an active oxygen provider, providing oxygen for
the oxidation of the CO on the Pt. The Fe-promoted catalysts, however demonstrated an unusual minimum in CO conversion with increasing temperature,
between 100 – 150 o C. We account for the differences observed between the two systems to a difference in reducibility of FeO x and CoO x and possible
enhancement of H 2 spillover and oxidation on the FeO x (:Pt) species.
Justification for acceptance
Our work has shown significant enhancement of the Pt/Al 2 O 3 catalyst for the PROX reaction with just low loadings of a promoting oxide, emphasising the
importance of Pt-promoter metal oxide interfacial sites. The work is especially relevant to the session on “Catalysis for the production of clean fuels” but would
be of general interest in terms of catalyst design.
References
Y.J. Mergler, A. van Aalst, J. van Delft, B.E. Niewenhuys, Appl. Catal. B, 10 (1996) 245.
CE-6
Preferential oxidation of CO over Au/Al 2 O 3 catalysts for fuel cell applications
E. Quinet a , F. Morfin a , F. Diehl b , P. Avenier b , V. Caps a ,*, J.-L. Rousset a
a Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON, CNRS / University of Lyon), 2 avenue Albert Einstein, Villeurbanne Cedex, F-69626, France
b IFP-Lyon, Direction Catalyse & Séparation, BP 3, Vernaison, F-69390, France
*Corresponding author. Tel : +33 472 445 331, Fax : +33 472 445 399, e-mail : valerie.caps@ircelyon.univ-lyon1.fr
Background
The preferential oxidation of CO in the presence of hydrogen (PrOx) is of interest for the purification of the gas feeding proton-exchange membrane fuel cells
(PEM-FC). The key-challenge is to achieve high conversion of CO at low temperature (80-120°C) without oxidizing the hydrogen fuel. Alumina-supported gold
catalysts turned out to be highly active for the PrOx reaction, despite their poor activity in pure CO oxidation [1]. This makes them industrially attractive for the
PEM-FC technology, due to the extensive know-how available on alumina. Here, we show how the CO oxidation rate is promoted by the concentration of
hydrogen in the feed and how this promotion is affected by the gold particle size.
Results
0.92wt.%Au/Al 2 O 3 is synthesized by direct anionic exchange [2] using -Al 2 O 3 (AXENS, 140 m 2 g -1 ). The
average gold particle diameter, initially at 1.8 ± 0.7 nm, is grown up to 5.8 ± 2.2 nm (TEM). A detailed
study (fixed-bed flow reactor, reactant feed 2%CO/4%O 2 /x%H 2 /He, 0 < x < 75%, 0.25 mg Au, total flow
rate of 50 cm 3 min -1 , GHSV ~ 2100 h -1 ) of CO (Fig.1) and H 2 oxidation rates, CO 2 selectivity, activation
energies and hydrogen partial orders in the PrOx reaction allows us to show that the key-role of hydrogen
in the CO oxidation rate enhancement is different from a promotion with water. For the same alumina
support, the H 2 -promotion effect increases with decreasing particle of gold. A mechanism for O 2 activation
in the Au/Al 2 O 3 -catalyzed low temperature PrOx reaction will be proposed.
Justification for acceptance
We believe that these new results are suitable for the « Catalysis for the production of clean fuels »
session. We hope to stimulate discussion on the development of alumina-supported catalysts for the PrOx
reaction and, more generally, open up new perspectives for the application and understanding of gold
catalysts.
References
[1] C. Rossignol, S. Arrii, F. Morfin, L. Piccolo, V. Caps, J.-L. Rousset, J. Catal. 230 (2005) 476.
[2] S. Ivanova, C. Petit, V. Pitchon, Appl. Catal. A 267 (2004) 191.
[3] M. Daté, M. Okumura, S. Tsubota, M. Haruta, Angew. Chem. Int. Ed. 43 (2004) 2129.
[4] D.G. Barton, S.G. Podkolzin, J. Phys. Chem. B 109 (2005) 2262.
CO oxidation rate (mol CO.gAu
-1 .s
-1 )
3.0E-03
2.5E-03
2.0E-03
1.5E-03
1.0E-03
5.0E-04
0.0E+00
0 50 100 150 200 250 300
Temperature (°C)
Fig 1. CO oxidation rate vs. temperature in the PrOx reaction over
5.8 nm Au/-Al2O3 using (-) 0%, (×) 0.25%, () 0.50%, () 1%,
() 5%, () 10%, () 20%, () 48%, () 75%.of H2 in the feed

CE-7 Stable gold nanoparticles for hydrogen purification reactions: a challenging approach for robust catalysts
M. Cargnello a , P. Fornasiero, a *, C. Gentilini a , M. Graziani a , T. Montini a , L. Pasquato a , S. Polizzi b
a Department of Chemical Sciences, Center of Excellence for Nanostructured Materials and INSTM-Trieste Research Unit, University of Trieste, Via L. Giorgieri 1, 34127,
Trieste, Italy
b Department of Chemical Physics, University of Venice, Calle Larga S.Marta 2137, 30123 Venezia.
* Corresponding author. Tel: +39 040 558 3973, Fax : +39 040 558 3903, e-mail: pfornasiero@units.it
Background:
The use of H 2 in combination with fuel cells has been indicated as promising solution to attenuate climate changes. Efficient and stable Water Gas Shift (WGSR)
and PReferential OXidation (PROX) catalyst must be designed in order to purify the H 2 produced by reforming reactions. Au-CeO 2 is one of the most promising
systems.[1] However, no general consensus exists on the oxidation state of the gold atoms at the active site. Recently we showed that the advantage of using
preformed gold nanoparticles for the preparation of active and selective PROX catalysts.[2]
Results
Here we report a simple and effective preparation methodology to obtain stable and active embedded Au@CeO 2 catalysts for WGSR and PROX. The synthesis
involves the preparation of Au nanoparticles protected by thiols, the subsequent growth of a porous layer of Ce(OH) 4 around the metal nanoparticles and a final
calcination step. The reported preparation methodology is highly flexible since it offers the possibility to (i) tune the nanoparticle dimensions, (ii) to nicely
control the coverage of the metal particles by the inorganic matrix, (iii) modulate the porous protecting oxides. The catalytic activity of these systems (Au loading
from 1 to 3wt %) indicates excellent activity and a significant superior thermal stability with respect to traditional impregnated catalyst.
Justification for acceptance
The present communication contributes to the development of suitable strategies for enhancing the thermal stability of heterogeneous catalysts. This is
particularly relevant in the case of Au based system where even a mild aging leads to significant metal sintering with dramatic catalyst deactivation. The results
obtained can be widely extended.
References
[1] R. Burch, Phys. Chem. Chem. Phys., 8 (2006) 5483.
[2] N. Hickey, P. Arneodo Larochette, C. Gentilini, L. Sordelli, L. Olivi, S. Polizzi, T. Montini, P. Fornasiero, L. Pasquato and M. Graziani, Chem. Mater. 19
(2007) 650.
CE-8
Reversible changes occurring in the CO chemisorption capability of a Au/Ce 0.62 Zr 0.38 O 2 catalyst.
Influence of the support redox state.
José M. Cíes, E. del Río, M. López Haro, S.E. Collins, J.J. Calvino, J.J. Delgado, S. Trasobares, and S. Bernal*
Departamento de Ciencia de los Materiales, Ingeniería Metalúrgica y Química Inorgánica. Facultad de Ciencias. Universidad de Cádiz. Campus Río San Pedro. E-11510
Puerto Real (Cádiz). Spain
*Corresponding author. E-mail: serafín.bernal@uca.es
Background
The influence of the support redox state on the CO-Au interaction occurring in a 3%Au/Ce 0.62 Zr 0.38 O 2 catalyst in investigated by means of STEM-HAADF, FTIR
and volumetric adsorption techniques.
Results
The table below summarises the results of our study. According to (1), the amount of CO chemisorbed on gold was determined from the second of two
consecutive isotherms recorded at 303 K for each of the Au/CZ samples, after correction of the CO adsorbed in the second isotherm on the bare support.
Sample
Pre-treatment
(A) Au/CZ
5%O 2 /He at 523 K (1h) + Evac at 523 K (1h)
(B) Au/CZ
5%O 2 /He at 523 K (1h) + Evac at 523 K (1h) +
+ 5%H 2 /Ar at 673 K (1h) + Evac at 673 K (1h)
(C) Au/CZ
5%H 2 /Ar at 673 K (1h) + Evac at 673 K (1h) + Reoxn/Evac
at 523 K
(D) CZ
5%O 2 /He at 523 K (1h) + Evacn at 523 K (1h)
(E) CZ
5%H 2 /Ar at 773 K (1h) + Evacn. At 773 K (1h)
Au dispersión
STEEM-HAADF
CO Volum Adsorption
at 303 K (2 nd isotherm)
P (CO)
(Torr)
53 % 40.46
62 % 40.36
54 % 40.33
Q ads (Q ads-Au =
Q ads – Q ads-CZ )
mole CO/g cat
22.02
(19.48)
10.43
(9.11)
18.53
(15.99)
--- 40.50 2.54
--- 42.74 1.32
FTIR Integrated
Absorptn. (CO)
(IA/Q ads-Au )
If sample B is further re-oxidised, sample C, the reported volumetric and integrated absorption data clearly show the reversible nature of this effect. Likewise, the
(CO) band in sample C is shifted back to higher wave-numbers (2107 cm -1 ). Also remarkable, the experimental approach followed in this work allows us to
estimate the extinction coefficients for the (CO)-Au band (IA/Q ads-Au ). We may conclude, accordingly that this parameter is also modified by the Au-CZ
interaction, being slightly higher for the catalyst reduced at 673 K.
Acknowledgements: Financial support from MEC/FEDER-EU (MAT2005-00333) and the Junta de Andalucía (FQM-110 and FQM-334) is acknowledged. The
CZ sample was donated by Grace-Davison.
References
[1] S.E. Collins, J.M. Cíes, E.del Río, M. López-Haro, S. Trasobares, J. J. Calvino, J.M. Pintado, S. Bernal, J. Phys. Chem. C 111 (2007) 14371.
20.22
(1.04)
12.68
(1.39)
16.79
(1.05)
0.66
(0.26)
0.27
(0.20)
As deduced from the volumetric study, the amount
of CO chemisorbed on Au (Q ads-Au ) in sample B is
less than one half than that determined for catalyst
A. Significant changes in the FTIR spectra for CO
(P CO = 40 Torr) chemisorbed on Au are also
observed. In good agreement with earlier studies,
the (CO) band is shifted from 2110 cm -1 in
sample A to 2092 cm -1 in sample B. The integrated
absorption data for this band are also different,
being much higher for sample A. We should
conclude accordingly that pre-reduction at 673 K
induces a significant perturbation on the Au-CO
interaction. As revealed by the STEM-HAADF
study, this deactivation effect cannot be attributed
to metal sintering.

CE-9
Kinetics of the water-gas shift reaction over Pt and Au supported bifunctional catalysts.
Olivier Thinon a , Yves Schuurman a, *, Fabrice Diehl b , Priscilla Avenier b
a Institut de Recherche sur la Catalyse et l’Environnement de Lyon, Villeurbanne, 69626, France
*Corresponding author. Tel: +33 472445482, e-mail: yves.schuurman@ircelyon.univ-lyon1.fr
b IFP-Lyon, Solaize, 69360, France
Background: The WGS reaction has attracted a renewed interest for a few years because of its potential application to the CO removal from H 2 -rich feed gases
for fuel cells. Several mechanisms are reported in the literature but no quantitative model taking into account both the metal and the support has been presented
yet. A microkinetic model has been developed based on a dual-site mechanism that describes the WGS over Pt and Au supported on two reducible oxides.
Results: Initial power law rate model yielded the apparent activation energies of catalysts and showed CO and H 2 adsorb stronger on Pt. CO 2 has an inhibiting
effect on ceria-supported catalysts. These observations are in good agreement with a bifunctional mechanism initially proposed over Pt supported catalysts 1 :
CO + * CO* (1) Table 1. Estimated kinetic parameters
Microkinetics
H 2 O + S-O HO-S-OH (2)
Sample H ads (kJ/mol) E a (3)
CO* + HO-S-OH COOH* + S-OH (3a)
CO H 2 H 2 O CO 2
(kJ/mol)
COOH* + S-OH + * 2H* + S-O-CO 2 (3b) Pt/TiO 2 96 65 12 5 74
2H* H 2 + 2* (4) Au/TiO 2 32 33 12 5 56
S-O-CO 2 CO 2 + S-O (5)
Pt/CeO 2 96 65 30 66 115
Au/CeO 2 32 33 30 66 80
In this mechanism CO and H 2 chemisorb on the metal whereas CO 2 and H 2 O are adsorbed on the support. The reaction between “CO-derived” and “H 2 O-
derived” adsorbed species takes place at the metal support interface (step 3a and 3b). In order to verify if this model can be applied in a general way to
bifunctional WGS catalysts the above reaction sequence was further simplified by combining steps 3a and 3b into one step. Furthermore it was assumed that the
sorption steps on the metal and support are independent and thus consistent sorption parameters are required for the 4 samples. The corresponding rate is
calculated by numerically integrating the balances for both the gas and surface species (“microkinetic approach”). The data corresponding to each catalyst was
regressed in an iterative way until similar sorption parameters were obtained for the two metals and the two supports (Table 1). Both CO and H 2 adsorb stronger
on Pt than on Au. Both CO 2 and H 2 O adsorb stronger on CeO 2 than on TiO 2 . The microkinetic model describes the data adequately over all 4 samples thus
capturing the wide variation in reaction orders. Although the reaction between the adsorbed species has to be further detailed, consistent sorption parameters
supports a universal mechanism for bifunctional WGS catalysts.
Justification: A universal reaction mechanism based on a single reaction route, but by taking explicitly the different functions (metal, support) into account can
describe the WGS reaction over very different catalysts. This approach will allow a more rational design of improved bifunctional WGS catalysts.
References
[1] G. Germani and Y. Schuurman, AIChE Journal 2006, 52, 1806-1813.
CE-10 Molecular mechanism and intrinsic kinetics of catalytic steam reforming of methane over Rh/Ce Zr 1- O 2
as an efficient catalyst for H 2 production with in situ CO 2 capture
M.H. Halabi, M.H.J.M. de Croon, J. van der Schaaf, P.D. Cobden * , J.C. Schouten
Laboratory of Chemical Reactor Engineering, Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The
Netherlands
* Energy Research Center of the Netherlands, P.O.Box 1, 1755 ZG Petten, The Netherlands
Corresponding author: M.H. Halabi, m.h.halabi@tue.nl, Tel.:+31402474953, Fax:+31402446653
Introduction
Steam reforming of methane is the most vital reaction route to convert methane into hydrogen as a pollution-free primary energy carrier. An advanced
technique for hydrogen production with in situ carbon dioxide capture is under development in our department using an efficient catalyst-sorbent system. In this
paper, the intrinsic characteristics of the molecular reaction mechanism and of the kinetics of methane steam reforming are experimentally investigated over a
Rh/Ce 0.6 (Zr 0.4 O 2 ) catalyst in a laboratory-scale fixed-bed tubular reactor in the temperature range of 475 to 800 o C and at a total pressure of 1.5 bar. The overall
reaction orders of methane and steam are determined. Also, the catalyst activity and deactivation are investigated at different temperatures and feed compositions.
The effects of the hydrogen, carbon monoxide, and carbon dioxide concentrations on the methane reforming rate are demonstrated. A molecular reaction
mechanism and a LHHW kinetic model are derived for temperatures below 700 o C.
Experimental results
The kinetic experiments show a positive overall reaction order for methane of 0.59 and 0.69 at 475 and 575 o C, respectively. The methane reaction rates show
a non-monotonic dependency on the steam partial pressure. The reaction order for steam depends on temperature and composition. At 475 o C, it is 0.43 at a steam
partial pressure lower than 11.2 kPa and reduces to 0.28 above this pressure. The same is observed at 575 o C, the order reduces from 0.59 to 0.19. At
temperatures higher than 700 o C, the overall rate of reaction has a positive order less than 1.0 at a steam/carbon ratio below 2 and a negative order at higher
steam/carbon ratios. The addition of hydrogen to the feed gas at temperatures of 700 o C and above reduces the negative reaction order of steam due to the
reduction in the catalyst oxidization state. The water-gas shift reaction is suppressed at high temperatures above 575 o C and at low steam partial pressures at a
steam/carbon ratio below 1.5. Hydrogen and carbon dioxide inhibit methane reforming at all investigated conditions of partial pressure and temperature.
Hydrogen reduces the oxidization state of ceria, while carbon dioxide competes with steam on oxidizing the reduced ceria sites at temperatures below 700 o C.
The stronger inhibition of methane reforming at high hydrogen and carbon dioxide partial pressures (5 to 15 kPa) is due to the promotion of methanation and
reverse water-gas shift. The negative contribution of hydrogen to methane conversion and reaction rate is suppressed at temperatures above 700 o C due to its
weakened adsorption on the catalyst surface. The catalyst shows a stable activity at 63% methane at a steam/carbon ratio of 4 at 550 o C and a space time of
0.76 kg.min/mol methane over 65 hours of time on stream with insignificant total deactivation of less than 2.0%.
Reaction mechanism and kinetic model
No competitive adsorption between steam and methane was found at temperatures below 700 o C. Steam is most likely to compete with methane in adsorbing
on the rhodium active sites at temperatures above 700 o C and at low methane coverage. Kinetic experiments of the temperature programmed steam reforming
reaction on ceria–zirconia with false impregnation of 0% rhodium proved that there is insignificant methane adsorption on the support in the temperature range
from 550 to 700 o C. At 725 o C and higher, the steam reforming reaction starts as methane adsorption becomes significant on the support surface. Thus, two
distinct sites are thought to be responsible for the dissociative adsorption of methane and steam on the catalyst surface. Methane is dissociatively adsorbed on the
rhodium sites. Steam is dissociatively adsorbed on the ceria support with insignificant dissociative adsorption on rhodium at temperatures below 700 o C.
However, steam dissociative adsorption on rhodium becomes more influential at higher temperatures. A reaction mechanism and a corresponding kinetic model
are formulated to describe the steam reforming reaction on the studied catalyst from 475 to 575 o C. Redox surface reactions leading to CO and CO 2 production
are assumed to be the rate determining steps.

CE-11
Detailed surface mechanism for the catalytic partial oxidation of ethanol over rhodium
N. Hebben a *, O. Deutschmann
a Institute for Chemical Technology and Polymer Chemistry, University of Karlsruhe, Karlsruhe, 76131, Germany
*Corresponding author: Tel.: +49 721 608 8783, Fax: +49 721 608 4805, e-mail: hebben@ict.uni-karlsruhe.de
Background
There is a strong demand for hydrogen as an alternative energy source. However, the problems of hydrogen transport and storage argue for a local
production from liquid sources, for instance ethanol. Ethanol itself, as a renewable fuel, can easily be obtained in large amounts by fermentation of
biomass waste. Consequently, an increasing interest in the catalytic partial oxidation (CPOX) of ethanol over noble metal catalysts to synthesize
hydrogen can be observed in the last few years.
Results
Here we present the results of a modelling study of the catalytic partial oxidation (CPOX) of ethanol over rhodium based catalyst at short contact times. The
model is based on a detailed gas-phase [1] and surface reaction mechanism coupled with a two-dimensional description on the flow field in a single channel of a
monolithic catalyst [2] that is commonly applied in CPOX reactors.
The newly developed surface reaction mechanism is able to reproduce the experimental results of the group of L. D. Schmidt [3] in terms of product selectivity
and reactant conversion.
Furthermore, the model provides a detailed insight into the on-going reactions inside the reactor. The simulated concentration profiles show that H 2 O, CO, and
CH 4 are formed initially. Steam-reforming of CH 4 and the water-gas shift reaction follow. Further downstream, the concentrations of CO 2 and H 2 increase while
those of CO and H 2 O decrease. The Rh surface is mainly covered by carbon and CO, with vacancies of uncovered Rh sites being sufficiently high to keep the
catalytic cycle active.
A comparison of conversions in uncoated and catalytic active monoliths leads to the following conclusion: Even though, gas-phase reactions in a blank monolith
lead to significant conversion, they do not play an important role in the presence of the very active catalyst, because the catalytic conversion has almost
completed before gas-phase chemistry is initiated (ignition delay time).
Justification for acceptance
The new mechanism proposed and evaluated can be used to explore further operating conditions to optimise hydrogen production. Based on the simulation
results, new experiments with straight channels and varying external conditions are currently under investigation.
References
[1] N. M. Marinov, International Journal of Chemical Kinetics, 31 (1999), 183-220.
[2] O. Deutschmann et al., DETCHEM software package, Version 2.1., www.detchem.com (2007).
[3] J. R. Salge, G. A. Deluga, L. D. Schmidt, Journal of Catalysis, 235 (2005), 69-78.
[4] R. Schwiedernoch, S. Tischer, C. Correa, O. Deutschmann, Chemical Engineering Science, 58 (2003), 633-642.
CE-12
New Research System for Environmental Catalysis: Coupled Instrument Array
John T. Gleaves a,c , Gregory Yablonsky b,a, * , Rebecca Fushimi c , Xiaolin Zheng a , Steven Buckner b , Patrick Mills d
a Department of Energy, Environmental and Chemical Engineering, Washington University, One Brookings Drive, St. Louis MO 63130-4899, USA
b
Parks College, Department of Chemistry, Saint Louis University, 3450 Lindell Boulevard, St. Louis, MO 63103, USA
c Mithra Technologies, Inc., 99 Whippoorwill Ridge, Foley MO 63347, USA
d Department of Chemical and Natural Gas Engineering, Texas A&M University-Kingsville, 700 University Blvd MSC 193 Kingsville, TX 78363, USA
* 1-314-935-4367; gy@seas.wustl.edu
Background A new research system combining catalyst fabrication, kinetic testing, structural
characterization, and process reactor experiments, called a Coupled Instrument Array is proposed.
The system is comprised of 1) a TAP-3 reactor system, 2) a fluid bed reactor array for process
simulation , 3) a micro-reactor array for lifetime studies, CVD preparation, and pretreatment
experiments, 4) a multi-source deposition system for preparing and modifying catalyst samples, 5)
spectroscopy cells for structural characterization and in-situ spectroscopic experiments, 6) a
particle transport system for moving catalyst samples from one experiment to another, and 7) a
distributed computer system for automatic control, and control from a distant site. The system
will be used to study catalytic processes using C1-C4 feedstocks.
Results The system is designed to perform reactions on practical catalysts at atmospheric
pressures and vacuum conditions using a TAP-3 reactor system. We report a new experiment
using a single micron-sized catalyst particle surrounded by 100,000 non-active quartz particles
(“catalyst needle in quartz haystack”) [1]. The catalyst particle occupies less than 1% of the crosssectional
area of the microreactor, so that the reaction zone can be considered a point source. This
configuration eliminates non-uniformity in reactant concentration and catalyst composition even
in the domain of high conversions.
Justification The results allow direct comparison between transient response experiments
performed at vacuum conditions and steady flow experiments performed at atmospheric pressures
- bridging the "pressure gap". We also discuss using remote control to perform catalyst
preparation, kinetic testing, and structural characterization from a distant location by
pneumatically transferring catalyst particles from experiment to another. The proposed system
provides a powerful new integrated approach for preparing, testing and characterizing
environmental catalysts.
5
1
7
6
4
QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
3
2
References
[1] Xiaolin Zheng, J.T. Gleaves, G.S. Yablonsky, R. Fushimi, T. Brownscombe, A. Gaffney, M.
Clark, S. Han, A Needle in a Haystock Catalysis, Applied Catalysis, 2008 (accepted for
publication)
Figure 1. Coupled Instrument Array - 1) TAP-3 kinetic characterization
system, 2) fluid bed reactor array, 3) microreactor array, 4) multi-source
deposition system, 5) spectroscopy cells, 6) particle transport system, 7)

ORAL
PRESENTATION
ABSTRACTS
RENEWABLES

R-1 Liquid phase hydrogenation of biomass-derived lactic acid: A detailed description of kinetics and mechanism over
Ru-based catalysts at low pressure
Hans Gelten, Barbara Mojet, Leon Lefferts *
Catalytic Processes and Materials, University of Twente, Postbus 217, 7500AE Enschede
* Corresponding author: Tel: 003153-4892858, Fax: 003153-4894683, e-mail: l.lefferts@utwente.nl
Background
The exhaustion of fossil carbon compounds reserves leads to a growing interest in the use of renewable raw materials (biomass) as future energy supply. The
objective of the current research is to develop new, in situ spectroscopic tools. These tools are suitable for liquid phase reactions, for instance to explore new
routes to convert flash pyrolysis oil to bulk chemicals. For this purpose, lactic acid, as a model compound of flash pyrolysis oil, is chosen for detailed
investigation in liquid phase hydrogenation.
A detailed description of the kinetics under mild conditions will be presented, combined with mechanistic insight from in situ ATR-IR, which is a relatively new
technique, combining IR with liquid phase reactions. The catalyst (Ru/C or Ru/Al 2 O 3 ) is located on top of the ATR crystal to enable detection of surface species
next to dissolved species.
Results
A remarkable difference between hydrogenation at high versus low pressure is the inhibition effect of 1,2-propanediol on the reaction rate at low pressure. This
inhibition effect influences the activation energy and surface coverage, because of competitive adsorption of lactic acid, hydrogen and 1,2-propanediol.
Using in situ NMR, the intermediate of the reaction is determined. This contributes to a clear, mechanistic view of the reaction steps to hydrogenate lactic acid. In
situ ATR-IR results provide valuable information on adsorption of reactants and/or products and the typical involved surface-species.
Combining in situ NMR and ATR-IR with kinetic results, elucidates a detailed description of the mechanism of lactic acid hydrogenation at low pressure.
Justification for acceptance
This detailed description of the kinetics at mild conditions can, together with the in situ spectroscopic data, give valuable mechanistic information on the target
reaction, providing a knowledge base for catalytic hydrogenation acids and aldehydes, e.g. for hydrogenation of biomass-derived building blocks for bulk
chemicals. This is the first occasion in which in situ spectroscopy is applied to shed light upon the mechanism of this reaction in liquid phase.
R-2 Bio-glycerol conversion under mild conditions through heterogeneous catalysis
E. D’Hondt a , S. Van de Vyver, B. De Vis, B. Sels a , and P.A. Jacobs a ,*
a Centre for Surface Chemistry and Catalysis (COK), Department M 2 S, Catholic University Leuven, 3001 Heverlee, Belgium
* Corresponding author. Tel: +32 16 32 1595, Fax: +32 16 32 1998, e-mail: pierre.jacobs@biw.kuleuven.be
Background
Glycerol offers an alternative as a low cost renewable resource in the production of chemicals. Because of the augmented use of bio-fuels and as a side product of
oleo chemistry, the availability has increased and therefore the price of this compound has declined. In this project a high value chemical bulk intermediate, 1,2-
propanediol, is produced from glycerol through a heterogeneously catalyzed economically and ecologically feasible process.
Results
For the defunctionalisation of glycerol into 1,2-propanediol (1,2-PDO) a heterogeneously catalysed process has been developed to operate under mild conditions.
The bifunctional catalyst facilitates the conversion of a 20 wt% aqueous solution of glycerol into 1,2-PDO under inert atmosphere in a batch reactor. At 230 °C
and after 15 h the reaction yields 55 % of 1,2-PDO at a conversion of 86 %. To provide the second reagent, H 2 is produced in situ as a result of aqueous phase
reforming of glycerol followed by the water gas shift reaction (WGS). Theoretically, this parallel pathway converts glycerol into 3 molecules of CO 2 and 7
molecules of biogenic H 2 giving a maximum 1,2-PDO yield of 87,5 %. However, obtaining such a high yield is not recommended because a reducing
environment prevents cokes formation. Thermo-gravimetric analysis of a used catalyst doesn’t detect cokes and reusing the catalysts two or three times gives
similar results. This implies that the catalyst does not deactivate.
Through a mechanistic and kinetic study, a bifunctional mechanism for dehydroxylation of glycerol is confirmed. Dehydration to hydroxy-acetone on an acid site
followed by fast hydrogenation on a redox site leads to 1,2-PDO witch is quit stable under the applied conditions. Based on experimental findings, a mechanism
for reforming, dehydrogenation and C-CO cracking on a redox site, is suggested. Another feature of the catalyst is the ability to isomerise secondary hydroxyls
into primary hydroxyls and to isomerise double bonds converting several side products into suitable substrates for reforming. This provides more hydrogen
compared to other catalysts that catalyse the same reactions but with a lower performance. Not only isomerisation, but other characteristics of the carrier are
responsible for a better performance. Overall, six reactions –dehydration, (de)hydrogenation, C-CO cracking, WGS, and isomerisation- take place in one pot to
yield 80 % of lower alcohols including 55 % 1,2-PDO.
Justification for acceptance
This project fully implements the definition of green chemistry through the use of a renewable resource, water as a solvent, a heterogeneous catalyst and biogenic,
in situ produced H 2 as second reagent. On the other hand, the economy of bio-diesel benefits from up-grading their waste product into a bulk intermediate.

R-3 New insight into glycerol etherification over basic oxides
A.M. Ruppert a,b , J.D. Meeldijk a,c , B.W.M. Kuipers d , B.H. Erné d , B.M. Weckhuysen a,*
a Inorganic Chemistry and Catalysis, Faculty of Science, Utrecht University, Sorbonnelaan 16, Utrecht, 3584 CA, The Netherlands; b Electron Microscopy Utrecht, Department of
Biology, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands. c Van’t Hoff Laboratory for Physical and Colloid Chemistry, Faculty of
Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.* Bert Weckhuysen: b.m.weckhuysen@uu.nl
Background
Due to the growing production of biodiesel, the availability of glycerol, its by-product, is rapidly increasing. Consequently, new applications for glycerol are
currently being actively researched. One of them is its etherification to di- and triglycerols, used e.g. in cosmetic and pharmaceutical industries. It is predicted that
the market for polyglycerols will significantly develop in the near future. This reaction is known to be catalyzed by acidic or basic catalysts. We explored the
catalytic potential of a series of basic oxides, focusing on CaO as a cheap, environmentally friendly and efficient catalytic material for the etherification of
glycerol.[1]
Results
Our initial screening studies showed that the glycerol conversion gradually increases with increasing basic strength of the catalyst material, i.e. BaO > SrO > CaO
> MgO. In the current work, we show that within the group of CaO-based catalysts basicity is not the only factor determining the catalytic properties. The highest
conversion was observed for materials possessing high basicity, high surface area and the highest Lewis acidity. The activity of such prepared CaO is in the same
range as for the alkaline earth oxides with a much higher basicity; i.e. BaO. This explanation allows us to postulate an alternative reaction mechanism in which
the Lewis acid sites facilitate the leaving of the OH group that follows the nucleophilic attack of the alkoxide anion. However, in order to explain in more detail
the behavior of these catalyst systems we investigated the catalytic materials in connection with the reaction environment in which they work. We have to be
aware of the partial hydration of the catalytic materials during the process. This leads to the potential formation of Ca(OH) 2 , which is to some extent ‘soluble’ in
glycerol. For this purpose, the nature of the glycerol phase was investigated by light scattering (SLS) measurements and cryo-TEM. The presence of in-situ
generated colloids was proven by these techniques. Separate catalytic experiments showed a very high activity for the isolated CaO-based colloidal particles.
Justification for acceptance
Etherification of glycerol provides the application for this widely available bio-feedstock material. Specially prepared CaO is at least as active as BaO and SrO in
this reaction, at the same time being more environmentally friendly.
Reference
[1] A.M. Ruppert, J.D. Meeldijk, B.W.M. Kuipers, B.H. Erné, B.M. Weckhuysen Chem. Eur. J. 2008, 14, 2016
Acknowledgements: Financial support of the ASPECT program is gratefully acknowledged.
R-4 Transesterification of vegetable oils on basic large mesoporous alumina supported alkaline fluorides –
evidences of the nature of the active site and catalytic performances
M. Verziu a , S. Simon a , P. Filip b and V.I. Parvulescu a ,*
a University of Bucharest, Department of Chemical Technology and Catalysis, Bucharest 030016, Romania
b Institute of Organic Chemistry of the Romanian Academy of Sciences, Bucharest 030124, Romania
*Corresponding author. Tel. +4021 4100241, Fax. +4021 4100241, e-mail: v_parvulescu@yahoo.com
Background
The valorification of biomass with the aim to obtain biofuels already entered in the common philosophy and found industrial applications. These refer to the
transesterification of vegetable oils with methanol in the presence of homogeneous basic catalysts. However, from both the green and the environmental point of
view replacing the homogeneous catalysts with heterogeneous stable systems represents an important target. In this study we provide evidences about the
catalytic performances of a heterogeneous system that might be prepared and manipulated in a very simple mode. Evidences about the nature of the active site in
these catalysts are provided as well.
Results
KF and Cs/Al 2 O 3 catalysts with different loadings from 1 till 20 wt% were prepared by wetness impregnation of basic mesoporous alumina synthesized according
to literature data [1,2]. Activation of the catalysts was carried out in nitrogen and followed by in situ XRD measurements. The increase of the temperature over
250 o C corresponded to the diminution of the intensity of the reflexion planes of the AlO(OH) phase and to the formation of K 3 AlF 6 or Cs 3 AlF 6 phases,
respectively. At 500 o C this process is completed. This process was also confirmed by 27 Al MAS NMR for samples calcined at different temperatures, and by insitu
DR-UV-Vis measurements. From the interaction of the alkaline fluorides with the support it is also resulting MOH, which remains strongly chemisorbed onto
the alumina surface. DRIFTS investigation of the catalysts using NH 3 and CD 3 Cl confirmed the presence of the basic sites. Futhermore, calcination in air is
leading to the formation of carbonate species that can be hardly removed. XPS and textural analysis completed the characterization of the catalysts.
Transesterification of different vegetable oils (sunflower, soybean, rapeseed) was carried out using three different experimental procedures, ie autoclave heating,
microwave irradiation or sonication. The catalytic performances were evaluated by comparison with tests carried out using sodium methoxide. The experiments
were carried out at 70 o C, under microwave, at room temperature, under sonication, and at 150 O C, in autoclave. In addition to the product analysis, leaching was
checked in details for each experiment. After less than 90 min, the reaction carried out under microvawe led to a near total conversion of the vegetable oils, with a
near total selectivity in monoesters, irrespective of the vegetable source. The molar ratio methanol: vegetable oil was of 4:1, namely, very small. Under autoclave
and sonication conditions the conversion was about 80%, with a selectivity to monoesters of about 90%. The reactions carried out under the microvawe and
autoclave led to a leaching less than 10 ppm of alkaline species, while under the sonication the leaching was about 5 wt% from the initial content. Under
autoclave and microwave conditions the catalysts showed also a good recyclability.
Justification for acceptance
Alternative energy technologies are becoming increasingly important due to diminishing petroleum reserves and the environmental consequences of exhaust
gases from petroleum- fuelled engines. Alkali-catalyzed transesterification is most often used commercially. However, some alkali remains in the biodiesel
produced and this fact has already generated concern from the automotive producers.
References
[1] Z. Zhang, R.W. Hicks, T.R. Pauly, T.J. Pinnavaia, J. Am. Chem. Soc. 124 (2002) 1592.
[2] Z. Zhang, T.J. Pinnavaia, J. Am. Chem. Soc. 124 (2002) 12294.

y
z
x
c
a
R-5 New developments in solid acid and base catalysts for biodiesel synthesis
K.Wilson, * A.F. Lee, J. Montero and K. Narashimharao
a Department of Chemistry, University of York, Heslington, York, YO10 5DD
*Corresponding author. Tel: +44 1904 432586, Fax : +44 1904 432516, e-mail: kw13@york.ac.uk
Background
Biodiesel is synthesised from plant oils via a two step process in which free fatty acids (FFAs) are first removed by esterification with H 2 SO 4 , then C 14 -C 20
triglycerides (TAGs) are transesterified to their respective fatty acid methyl esters (FAMEs) by a base catalyst. These soluble catalysts are problematic as their
removal necessitates an energy intensive separation to purify biodiesel. Here we report on the development of tuneable solid acid and bases for biodiesel
synthesis, which offer several process advantages by eliminating of the quenching step (and associated waste water), and operate in a continuous reactor.
Results
We have systematically studied a series of solid bases including Li/CaO[1] and [Mg (1-x) Al x (OH) 2 ] x+ (CO 3 ) x/n
hydrotalcites[2], for the transesterification of TAGs. We find that in both cases the electronic state of the Li + or
Mg 2+ surface promoter is found to regulate base strength and control the catalyst activity[2,3]. Application of a
‘Na-free’ route to prepare hydrotalcites also avoids saponification and associated biodiesel contamination.
Solid bases are inactive towards FFA esterification and require oils to be pretreated with an acid catalyst. In our
quest to develop a catalyst system for both FFA esterification and TAG transesterification a series of insoluble
Cs x H 3-x PW 12 O 40 catalysts (x = 0.9-3) were also investigated[3]. Cs x H 3-x PW 12 O 40 is active towards both the
esterification of palmitic acid and transesterification of tributyrin, with optimum catalytic performance observed
for Cs loadings between x = 2.0-2.3 (Figure 1), correlating with the accessible surface acid site density.
Justification for acceptance
The production of biodiesel using more energy efficient processes will have a significant environmental impact.
This presentation will report on catalyst design factors for the conversion of oil feedstocks to fuels and would fit
ideally into the session on ‘Catalysis for the production of clean fuels, including from renewables.’
() TOF esterification (mmol h -1 g -1 )
180
160
80
60
40
H PW O
2
20
1
0 Cs +
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Cs per Keggin
Figure 1. Performance of Cs doped H 3 PW 12 O 40 in
TAG transesterification and FFA esterification.
14
12
7
6
5
4
3
() TOF transesterification (mmol h -1 g -1 )
References
[1] R.S Watkins, A.F Lee and K. Wilson, Green Chemistry 6 (2004) 335.
[2] D.G. Cantrell, L.J. Gillie, A.F. Lee and K. Wilson, Applied Catalysis A 287 (2005) 183.
[3] K.N. Rao, A.F. Lee, S.J. Tavener, D.R. Brown, P. Siril and K. Wilson, J.Catal. 248 (2007) 226.
R-6 Cellulose conversion to soluble sugars by supported metal catalysts
A. Fukuoka a, *, P. L. Dhepe a,b , M. Watanabe a,b , K. Kasai a , M. Kondo a and K. Hara a
a Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan.
b Japan Science and Technology Agency, Kawaguchi, 332-0012, Japan.
*Corresponding author. Tel: +81 11 706 9140, FAX: +81 11 706 9139, e-mail: fukuoka@cat.hokudai.ac.jp
Background
Cellulose is the most abundant organic compound in nature as the main component of plants. However, the use of cellulose is limited, because cellulose is
resistant to degradation due to its robust crystal structure with extensive hydrogen bonding. In our study of the conversion of sugars by heterogeneous catalysis
[1], we found that cellulose is converted into soluble sorbitol by supported Pt or Ru catalysts under the hydrogenolysis conditions [2] (Fig. 1).
Results
Catalytic reactions were performed in a stainless-steel high-pressure reactor, in which cellulose (Avicel),
catalyst (metal 2 wt.%) and water were charged. Then the reactor was pressurized with H 2 (5 MPa) and
heated at 463 K for 24 h. Cellulose was converted into sorbitol (yield 25%) and mannitol (6%) over Pt/-
Al 2 O 3 with 88% selectivity of the sugar alcohols. Among the catalysts tested, supported Pt and Ru catalysts
gave high yields of the sugar alcohols, while Rh, Pd, Ir and Ni ones showed low activity. The separation of
products and catalysts was easy by filtration, and the recovered catalysts were recyclable in repeated
catalytic runs. Metal-free supports showed only 3 % yield of glucose, suggesting that in situ generated acid
sites are responsible for the hydrolysis of cellulose. Then glucose is readily converted to sorbitol by the
reduction over the metal with H 2 . Pre-treatment of cellulose with ball-milling is significantly effective to
increase the cellulose conversion and product yields.
Justification for acceptance
Cellulose is abundant in nature as inedible biomass, but the conversion of cellulose to chemicals has been a
challenge due to its robust crystal structure. We used the hydrogenolysis conditions in water with supported
metal catalysts and succeeded in the first catalytic conversion of cellulose into soluble sorbitol and related
sugar compounds.
References
[1] P. L. Dhepe, A. Fukuoka et al., Catal. Lett., 102 (2005) 163.
[2] A. Fukuoka and P. L. Dhepe, Angew. Chem. Int. Ed., 45 (2006) 5161.
HOH
H H OH
H H
H O
HO
HO H OH H
H
O O HO H OH
OH
HO
H
O
HO
OH HO
H
O
OH
H O
H H
H
H
OH
H H OH
n
HOH
H H OH
H H
H O
OH
H
HO
HO H
H
O O HO H OH
OH
HO
H
O
HO
OH H O H
O
OH
H O
H H H
OH
H H H
OH
n
H 2 O
Catalyst
Glucose
Cellulose
HOH
H 2
H O
HO
HO
H OH
OH
Catalyst
H H
CH2OH
H OH
HO H
CH2OH
Fig. 1 Catalytic conversion of cellulose into sorbitol.
H
H
OH
OH
Sorbitol

R-7 Telomerization of crude glycerol with 1,3-butadiene towards new surfactant molecules
R. Palkovits a , I. Nieddu b , C. Kruithof b , R. J. M. Klein-Gebbink b and B. M. Weckhuysen c, *
b Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr,Germany
b Group of Inorganic Chemistry and Catalysis, Utrecht University, Utrecht, 3584CA, The Netherlands
c Chemical Biology & Organic Chemistry group, Utrecht University, Utrecht, 3584CH, The Netherlands
*Tel: +31 30 253 4328, Fax: +31 30 251 1027, b.m.weckhuysen@.uu.nl
Background
Attractive technology to convert crude glycerol – the main by-product of biodiesel manufacture (226kg/t) - are of growing interest as governmental regulations in
the European Union induce an increasing biodiesel production as fuel additive and alternative. Telomerization of crude glycerol with 1,3-butadiene presents a
promising reaction type allowing direct access to C 8 -chain glycerol ethers as potential molecules for detergent applications. Surprisingly, only one study on the
telomerization of glycerol applying Pd/Tppts as catalyst exists. 1 Consequently, we investigated the telomerization of glycerol and could identify a new catalyst
system with superior activity and capability to directly convert crude glycerol.
Results
Pd-based complexes with methoxy-substituted PPh 3 ligands were identified as active catalyst systems for the telomerization of glycerol with 1,3-butadiene. 2 The
substitutions were varied from one methoxy-group just on one phenyl ring up to three methoxy-groups on every ring of the ligand. Therein, Pd/Tompp
(tris(ortho-methoxyphenyl)phosphine) with one methoxy-group on every ring showed highest activities reaching up to 8545 TONs in one run and a TOF of 3418
h -1 . In contrast, with Pd/Tppts TONs up to 990 with a TOF of 248 h -1 summing up to a total TON of 3300 as the catalyst system could be recycled five times was
realized. Pd/Tompp was tested with pure and crude glycerol showing TONs of 2626 and 2159, respectively, thus, no significant differences in activity for pure or
crude glycerol as substrate were found. Concerning the product distribution, Pd/Tppts results mainly in monoether formation, while Pd/Tompp leads to the
formation of mono-, di- and triethers of glycerol emphasizing the capability of Pd/Tompp to telomerize sterically demanding nucleophiles as secondary alcohols.
Justification for acceptance
We believe the integration of existing renewable-based processes being essential for a successful feedstock change in chemical industry. The telomerization of
crude glycerol at the biodiesel plant enables the production of valuable products for detergent and surfactant applications from cheap starting materials.
References:
[1] A. Behr, M. Urschey, Adv. Synth. Catal. 345 (2003) 1242 -1246.
[2] R. Palkovits, I. Nieddu, R.J.M. Klein-Gebbink, B.M. Weckhuysen, Chem. Sus. Chem. (2008), in press (DOI: 10.1002/cssc.200700147).
We would like to acknowledge ACTS-ASPECT for financial support.
R-8 Catalytic valorization of bioethanol over mixed oxides Cu-Mg-Al catalysts
Nathalie Tanchoux a* , Ioan-Cézar Marcu b , Didier Tichit a , François Fajula a
1 Institut Charles Gerhardt Montpellier, Equipe MACS, UMR5253 CNRS/ENSCM/UM1/UM2, 8 rue de l'Ecole Normale, 34296, Montpellier cedex 5, France.
2 Dept. of Technological Chemistry and Catalysis, Univ. Bucharest, 4-12 Blv. Regina Elisabeta, 030018, Bucharest, Romania
* Corresponding author. Tel +33 4 67 16 34 65, Fax : +33 4 67 16 34 70, e-mail: Nathalie.tanchoux@enscm.fr
Background
The incorporation of bioethanol in diesel fuels may constitute an option to achieve the objective of 5.75 % of biofuel share in transportation fuels by 2010
according to a European directive [1]. But, as bioethanol cannot be used directly in diesel fuel because of its non-miscibility with diesel blends, transformation
processes must be considered. We report in this work the catalytic transformation of ethanol into acetals and/or butanol in a one-pot, multi-step synthesis. The
catalysts used are multifunctional catalysts, such as Cu-Mg-Al-O mixed oxides, which possess acid, basic and metallic active sites and have already been used for
multi-step reactions, as the Guerbet reaction for example [2].
Results
A series of catalysts has been prepared from Layered Double Hydroxides precursors, with varying Mg/Al
ratios and Cu content. The catalytic transformation of ethanol leads to two main products: 1-butanol and
1,1-diethoxyethane, whose respective selectivities depend on the reaction conditions and on the
equilibrium between the different functions of the catalyst. The results obtained show that the Cu content is
a key factor, with an optimum content comprised between 5 and 10 at.%. Other parameters such as
recyclability, influence of water (real bioethanol charge) or temperature have been studied. All these results
will be presented in more details during the conference.
Acknowledgements. The authors would like to thank the ANR program BioEdiesel.
Justification for acceptance
The novelty of this work lies in the nature of the molecules synthesized that have been scarcely
investigated in the past, particularly with catalysts obtained from LDH precursors. We really feel that this
work should be presented during ICEC as our goal is to develop new routes and/or new molecules
ultimately leading to energy sources more respectful of the environment, using at the same time "greener"
processes and starting materials coming from renewable sources.
[1] Directive 2003/30/EC, EN Official Journal of the European Union, 2003, L 123/44.
[2] H. Hattori, Chem. Rev. 95 (1995) 537; M. J. L. Gines, E. Iglesia, J. Catal. 176 (1998) 155.

R-9 Hydrogen from Glycerol by Aqueous-Phase Reforming
K. Lehnert, P. Claus *
Technische Universität Darmstadt, Ernst-Berl-Institut, Technische Chemie II, Darmstadt, Germany.
* Corresponding Author. Tel: +49 6151 164733, Fax: +49 6151 164788,
e-mail: claus@ct.chemie.tu-darmstadt.de
Background
Due to the increasing demand of energy and the continuously rising oil prize the use of renewables as a feedstock for the production of fuel and chemicals has
become more and more important during the last few years [1]. The production of biodiesel for instance is an example for the industrial application of biomass.
A major by-product of this process is glycerol [2]. Possible routes for efficient utilization of glycerol are oxidation to glyceric acid and dihydroxyacetone [3] or
aqueous-phase reforming (APR) using platinum based catalysts and mild reaction conditions (200-250°C, 20-25 bar) for the production of hydrogen and light
alkanes [4]. In this contribution the main focus lies on the influence of different alumina support materials and the importance of metal particle size of platinum
catalysts on the catalytic activity and selectivity for the APR reaction. Furthermore the effect of catalyst poisoning should be discussed on the basis of impurities
found in crude glycerol.
Results
All catalysts were prepared by incipient wetness technique from aqueous solutions of various platinum salts. The amount of precursor was calculated to achieve a
metal loading of 3 wt%. Different alumina supports were used. APR reactions were carried out in a stainless steel tubular reactor at 20 bar and 250°C using
300 mg of the appropriate catalyst. Aqueous solutions of the reactants (10 wt%) were introduced to the reactor by an HPLC pump at a flow rate of 0.5 ml/min.
The product gas mixture was analyzed by online gas chromatography. Samples of the liquid effluent were analyzed by HPLC.
Catalysts prepared from a variety of metal precursors showed similar activities (40 % glycerol conversion) and also identical selectivity towards hydrogen
(85 %). In contrary, variation of support material from pure -Alumina to a mixture of -, - and -phases (Puralox®) lead to an increase in hydrogen production.
The use of crude glycerol as starting material was successful. However, due to impurities (e.g. NaCl) the rate of hydrogen production was lower than observed
for pure glycerol and decreased dramatically after about 4 hours time on stream. Besides, the selectivity to hydrogen was found to be higher than 90 % in steady
state.
Justification for Acceptance
For a deeper understanding and improvement of hydrogen selectivity of the APR reaction using glycerol, the effect of different catalyst properties,
such as metal particle size or support material, is hitherto unknown. By demonstrating that even polluted starting material, such as crude glycerol,
can be converted in the APR process, a broader range of real practical application of the reaction is given.
References
[1] G. W. Huber, A. Corma, Angew. Chem. Int. Ed. 46 (2007) 7184.
[2] P. Gallezot, Catal. Today 121 (2007) 76.
[3] S. Demirel-Gülen, K. Lehnert, M. Lucas, P. Claus, Appl. Cat. B: Environmental 70 (2007) 637.
[4] G. W. Huber, J. A. Dumesic, Catal. Today 111 (2006) 119.

ORAL
PRESENTATION
ABSTRACTS
GREEN CHEMISTRY

GC-1
Carbon dioxide and methane in chemical synthesis: direct catalytic carboxylation of methane and acetylene to vinyl acetate
J.J. Spivey 1* , E.M. Wilcox 2,a , G.W. Roberts 2,3
1 Cain Dept. Chem. Engineering, Louisiana State University, Baton Rouge, LA USA; 2 Dept. Chem. and Biomolecular Engineering, N.C. State Univ. 3 Adjunct Professor, Cain
Dept. Chem. Engineering, Louisiana State Univ; a current affiliation: Range Fuels, Broomfield, CO USA
*Corresponding author. Tel: +1 225 578 3690, Fax : +1 225 578 1476, e-mail: jjspivey@lsu.edu
Background
Carbon dioxide is seldom used in chemical synthesis because of the severe thermodynamic limitations associated with its use as a reactant.
Similarly, the stability of the methane molecule usually requires indirect methods such as steam reforming to syngas to produce higher value
products such as liquid fuels or oxygenates.
Results
Here, we report what we believe to be the first evidence of the direct formation of vinyl acetate from the one-step reaction of CO 2 , methane, and
acetylene:
(1) CO 2 + CH 4 + C 2 H 2 CH 3 CO 2 CH=CH 2 G r (298K) = +7 kJ/mol
The study of this reaction is based on recent work showing the formation of acetic acid by direct carboxylation of methane [1,2], and the well
known reaction of acetic acid and acetylene to then produce vinyl acetate [3]. Temperature programmed reaction flow experiments using an
equimolar mixture of CO 2 , methane, and acetylene at 1 atm over 5% Pt/Al 2 O 3 show that vinyl acetate is formed beginning at around 250C, and is
produced at steady state at 400C. Although vinyl acetate is formed over the 5% Pt/Al 2 O 3 catalyst alone, an admixture of this catalyst and a Zn
acetate/carbon catalyst, which is known to be active for the conversion of acetic acid and acetylene to vinyl acetate, was more active for vinyl
acetate formation. However, this admixture was deactivated at temperatures above about 325C, apparently by carbon deposition.
Justification for acceptance
The use of two potential greenhouse gases in the synthesis of vinyl acetate, a commodity chemical, using a conventional supported metal catalyst at
mild conditions, offers the possibility of more widespread use of CO 2 and methane. This includes more cost-effective processes for the synthesis
acetate derivatives based on acetic acid [1,2].
References
1. S. Mukhopadhyay, M. Zerella, A.T. Bell, Studies in Surface Science and Catalysis, X. Bao, Y. Xu, eds., 147 (2004) 523.
2. E.M. Wilcox, G.W. Roberts, J.J. Spivey, Catal. Today, 88 (2003) 83.
3. J.I. Kroschwitz, ed., Kirk-Othmer Encyclopedia of Chemical Technology. 5 th ed. John Wiley & Sons, New York, 2004-2005.
GC-2
CO 2 conversion via one-step synthesis of dimethyl ether (DME)
A. Narvaez-Dinamarca, L. Torrente-Murciano, Y.K. Chan, C.L. Tang, D. Chadwick *
Department of Chemical Engineering, Imperial College London, SW7 2AZ (UK)
* e-mail: d.chadwick@imperial.ac.uk
Background
As a result of the increasing energy demands and environmental concerns, development of sustainable and environmental friendly sources of energy is of great
significance and urgency. Dimethyl ether (DME) has emerged as a promising GTL or CTL energy source to replace conventional petroleum sources which can be
used not only as substitute LPG but also as a clean diesel fuel. DME is synthesised by methanol dehydration or from pure syngas producing CO 2 as by-product.
This paper investigates the utilization of CO 2 in DME synthesis which provides an opportunity for mitigating release of CO 2 waste from industrial processes.
Results
Synthesis of DME from syngas is a chemical equilibrium restricted process which consists of methanol synthesis
followed by methanol dehydration. By coupling both reactions in one-step synthesis, the methanol formed in the first
reaction is thermodynamically trapped in the second one, obtaining a synergetic effect [1].
Several studies have been made of the conversion of CO 2 to DME using dual functional catalysts [2, 3]. DME synthesis
from CO 2 produces CO as by-product and DME synthesis from syngas produces CO 2 as by-product. In order to increase
carbon yield in an industrial scale process, syngas and CO 2 must be recycled. Aspen simulations are carried out to
investigate the configuration and optimal CO/CO 2 ratios in the recycle stream. The paper investigates the behaviour of
dual functional catalysts containing CuO-ZnO-Al 2 O 3 combined with a dehydration component such as -alumina,
HZSM-5 or mordenite in the one-step synthesis of DME at relevant CO/CO 2 /H ratios. Fig 1 shows the influence of feed
CO 2 fraction on the DME yield when CuO-ZnO-Al 2 O 3 / -alumina is used as a catalyst.
Justification for acceptance
Due to the increasing importance of DME as energy source and the pressing CO 2 problem, this study evaluates whether
the DME synthesis could be used to consume syngas containing high levels of CO 2 instead of a pure syngas, and the recycle requirements which increase total
carbon yield.
References
[1] Ng, K.L, D. Cahdwick and B.A. Toseland. Chemical Engineering Science, 54 (1999) 3587 – 3592.
[2] Jun, K.W et al. Advances in Chemical Conversions for Mitigating Carbon Dioxide, 114 (1998) 447-450.
[3] J. Ereña et al. Catalysis Today 107 – 108 (2005) 467 – 473.
Yield (%)
25
20
15
10
5
0
0 0.2 0.4 0.6 0.8 1
[CO2/(CO2+CO)] inlet
Fig1. Influence of the CO 2 fraction on
DME yield using CuO-ZnO-Al 2 O 3 /alumina
as catalyst.

GC-3
Green Chemistry with CO 2 : synthesis of carbamates and cyclic carbonates
Ion Angelica a* , Parvulescu Vasile b , Jacobs Pierre a , De Vos Dirk a
a Catholic University of Leuven, Centre for Surface Science and Catalysis, Kasteelpark Arenberg 23, 3001 Leuven, Belgium; b University of Bucharest, Department of Catalysis,
B-dul R. Elisabeta 4-12, 030016 Bucharest, Romania;
*Corresponding author. Tel: (+32) 16 32 14 64, Fax: (+32) 16 32 19 98, e-mail: angelica.ion@biw.kuleuven.be
Background
Carbon dioxide is a major greenhouse gas. So, its use as a raw material in chemical synthesis is a research area of extraordinary scientific, economic and
ecological interest. CO 2 is an ideal raw material in many respects as it is a renewable, abundant, cheap and non-toxic source of functional carbon units. Two of
the major paths for CO 2 utilization are the synthesis of carbamates and cyclic carbonates. Carbamates have tremendous application potential (e.g. polyurethanes)
while cyclic carbonates find extensive applications as pharmaceutical/fine chemicals intermediates, solvents or monomers for polycarbonates preparation.
Results
Here we report that a large range of carbamates were efficiently synthesized in good yields from amines and alcohols using basic catalysts and CO 2 as a carbon
source. The used catalysts were able to convert both linear and branched aliphatic amines to their corresponding carbamates in mild reaction conditions, even in
the absence of dehydrating agents. Only when a sterically hindered amine like t-butylamine was involved, a dehydrating agent was necessary. It was found that a
71% yield in carbamate could be attained in 24h using only 25 atm of carbon dioxide. This is a major advance over previous reports 1a,b , which use metal catalysts,
extremely high pressures (e.g. 300 atm of CO 2 ) and dehydrating agents (e.g. dimethoxypropane) to achieve similar yields. Mechanistic investigations revealed
two main pathways for carbamate formation, viz. a direct pathway with isocyanates as reaction intermediates, and an indirect one via urea alcoholysis. The effects
of substitution and steric hindrance on amine reactivity were also analyzed 2 .
In another approach, cyclic carbonates were successfully prepared starting from epoxides and supercritical CO 2 in the presence of heterogenized Si Lewis acids as
catalysts. Catalysts containing t-butyldimethylsilyltriflate (TBDMST) were successfully immobilized in a silica matrix and then tested in the coupling of CO 2
with various epoxides without any solvent. The catalysts proved to be very active and yields > 90% were obtained. The heterogeneity of the catalyst and the
effect of the supercritical conditions will be critically assessed.
Justification of the acceptance
In summary, this is the first systematic study proving that basic catalysts can promote the transformation of a large variety of amines and alcohols into carbamates
in appreciable yields, in mild reaction conditions, even without dehydrating agents. Benefits of using scCO 2 were illustrated for the reactions of epoxides with
CO 2 .
References
[1] a) M.Abla J.C.Choi, T.Sakakura, Chem.Comm (2001), 2238 ; b) M.Abla, J-C. Choi, T. Sakakura, Green Chem. 6 (2004), 524.
[2] Ion A., Van Doorslaer C., Parvulescu V., Jacobs P., De Vos D., Green Chem. 10 (2008) 111.
GC-4
Green synthesis of DMC by transesterification of ethylene carbonate over solid bases
Georgiana Stoica a , Sònia Abelló a and Javier Pérez-Ramírez a,b, *
a Institute of Chemical Research of Catalonia, Avinguda Països Catalans 16, 43007 Tarragona, Spain.
b Catalan Institution for Research and Advanced Studies, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
*Corresponding author. Tel: +34 977 920236, Fax: +34 977 920224, e-mail: jperez@iciq.es
Background
Dimethyl carbonate (DMC) is a green building block for replacing phosgene and dimethyl sulphate in the synthesis of valuable chemicals like carbamates and
isocyanates. DMC can be produced via phosgene-free routes, by the reaction of methanol with CO 2 or by a two-step process, consisting in the reaction of
ethylene or propylene oxide with CO 2 and further transesterification with methanol [1]. Besides phosgene-free operation, these processes (re)utilize carbon
dioxide, the most important contributor to the global warming. Accordingly, two important environmental problems can be simultaneously tackled. We have
investigated the transesterification of ethylene carbonate with methanol over various families of solid bases.
Results
A series of hydrotalcite-like compounds and dawsonite-type materials with different Mg/Al ratios and the oxides derived by calcination or rehydration were
studied in the title reaction. Catalysts reported in the literature (metal oxides and liquid inorganic bases), which are usually tested under high pressure conditions,
were also used as reference materials. Temporal analysis of products (TAP) was applied to determine the density of basic sites using CO 2 as the probe molecule.
High-throughput parallel screening using a fully automated liquid-phase reactor system enabled us to accelerate the rate of catalyst discovery and optimization.
The Mg(Al)Ox mixed oxide resulting from thermal decomposition of hydrotalcite (Mg/Al=3) demonstrated to provide the highest DMC yield under mild
conditions among the catalysts tested. The rehydrated hydrotalcite is less active than the calcined counterpart, suggesting that stronger basic sites with Lewis
nature are responsible for the observed catalytic activity. Subsequently, a broad range of reaction parameters was mapped with excellent reproducibility. The
optimized conditions for the calcined Mg-Al hydrotalcite in batch laboratory (ml) were successfully upscaled into the bench scale (l) with on line ATR-FTIR
monitoring, which also demonstrated the remarkable agreement with off-line GC analysis. Accordingly, the ethylene carbonate conversion and DMC yield
increase gradually reaching 75% and 40%, respectively, after 5 h of reaction.
Justification for acceptance
A variety of catalyst families for DMC production via transesterification of ethylene carbonate with methanol have been studied. This green route is a promising
alternative to phosgene-mediated synthesis. The results of our investigations, including high-throughput lab-screening, reaction kinetics, nature of the active sites,
and scale up studies will be presented. We particular dwell on activated hydrotalcites as the most active system identified.
References
[1] D. Delledonne, F. Rivetti , U. Romano, Appl. Catal. A 221 (2001) 241.

GC-5
Activity and Selectivity Control in the Synthesis of Alicylic Amines
K.F. Graham, K.T. Hindle, S.D. Jackson*, D.J.M. Williams and S. Wuttke
WestCHEM, Department of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK
*Tel: +44 141 330 4443, Fax: +44 141 330 4888, E-mail: sdj@chem.gla.ac.uk
Background.
Alicyclic amines are important for use as pesticides, plasticizers, explosives, inhibitors of metal corrosion, sweetening agents and as intermediates in the
pharmaceutical industry. The current synthesis of alicyclic amines does not utilise a heterogeneously catalysed route. The potential advantages for industry
include an enhanced throughput, improved product selectivity and a cleaner, greener chemical process. To achieve this we need to understand the reaction
mechanism and correct choice of catalyst, solvent and temperature.
Results.
Higher reaction temperatures increased the rate of hydrogenation and decreased the cis/trans ratio of products in line with kinetic and thermodynamic
expectations. When catalysts with different metal crystallite sizes were tested it was found that as metal crystallite size increased so did the Turn-Over Frequency
(TOF). This unusual antipathetic particle size effect suggests hydrogenation is preferred at plane face/terrace sites rather than edge or corner sites. The rate of
hydrogenation for both 4-methylaniline and 4-tert-butylaniline tended to zero at ~0.35nm.
The rate of 4-methylaniline and 4-tert-butylaniline hydrogenation was monitored in polar primary and secondary alcohols and non-polar solvents. The reaction
rates varied by an order of magnitude depending on the solvent used, with the maximum reaction rate achieved when using propan-2-ol. The ratio of cis/trans
isomers is proportional to the dielectric constant of the solvent. As dielectric constant increases the polarity of the solvent also increases. This affects the relative
thermodynamic stability not of the final products but of the partially hydrogenated enamine and imine intermediates. The imines hydrogenate to the respective
cis isomer.
Analysis of the reaction kinetics revealed that the system deactivated. This was shown to be a function of the amount of product in the system. The primary
amine product is a stronger base (pKa ~10.5) than the starting aromatic amines (pKa ~ 4.5) and inhibits reactant adsorption, hence deactivating the system.
Justification for acceptance
Using a combination of metal crystallite size, solvent and temperature it is possible to control catalyst activity and stereoselectivity independently. This allows
the yield of the desired cis isomer to be enhanced 40-fold. Control of the catalytic chemistry provides the potential for developing a new sustainable industrial
process for the production of alicyclic amines.
GC-6
Use of Gold Catalysts to Promote the Ultra-Selective Sustainable Production of Aromatic Amines
F. Cárdenas-Lizana*, M.A. Keane
a Chemical Engineering, Heriot-Watt University, Edinburgh EH14 4AS, Scotland.
* Corresponding author. Tel: +44 (0) 131 451 4719, e-mail: fl47@hw.ac.uk
Background
Increasingly stringent environmental legislation has lead to a pressing demand for the development of cleaner sustainable manufacturing processes. Catalysis is
now well established as an essential tool for the application of “green chemistry” to chemical production. Aromatic amino compounds are extensively used as
intermediates in the manufacture of pesticides, herbicides, pigments, pharmaceuticals and cosmetic products. The standard production route employs Fe
based catalysts for the reduction of the corresponding nitro compound in acidic media. This approach generates significant toxic Fe/FeO waste with low
associated target product yields: the development of a cleaner alternative is now crucial.
Results
The viability of the gas phase reduction of mono- and di-substituted nitroarenes at atmospheric pressure has been demonstrated over (Al 2 O 3 or TiO 2 ) supported
Au, Pd, Ni, Au-Pd and Au-Ni [1-3]. Taking the hydrogenation of p-chloronitrobenzene (p-CNB) as a model reaction, the following activity sequence has been
established: Pd/Al 2 O 3 >Ni/Al 2 O 3 >Au/Al 2 O 3 . While Au delivered lower specific hydrogenation rates, exclusive (and time invariant, up to 80 h on-stream)
formation of p-chloroaniline was achieved [2]. This is the first time such product exclusivity has been achieved in gas phase operation. The Pd and Ni systems
were non-selective (nitrobenzene and aniline were principal products) and suffered severe temporal deactivation. Moreover, we have achieved an exclusive
formation of the corresponding halo-aniline over Au/Al 2 O 3 for a series of mono- and di-substituted halo nitroarene reactants, where an electron withdrawing
substituent activation effect is observed [2]. The incorporation of Au in Pd/Al 2 O 3 via reductive deposition (Pd/Au = 10) did not influence p-CNB hydrogenation
activity/selectivity and characterisation analysis suggests negligible surface Pd/Au interaction. The Pd/Au ratio is a crucial variable and the synthesis of
bimetallics with a lesser Pd content (Au/Pd >1) via co-deposition precipitation resulted in enhanced activity while maintaining 100% selective -NO 2 reduction. In
the hydrogenation of m-dinitrobenzene over Al 2 O 3 supported Au, Ni and Au-Ni it is possible to control the product composition in terms of partial (over Au) or
complete reduction (over Ni) or a combination of both (over Au-Ni). Surface alloy formation, metal particle size and metal/support interactions are demonstrated
as having a critical impact on hydrogenation performance.
Justification for Acceptance
Our results demonstrate for the first time that catalytic hydrogenation over gold-based catalysts in continuous flow gas operation is a viable, clean high
throughput route to aromatic amines. This work represents a critical advancement in the sustainable production of high value fine chemicals.
References
[1] F. Cárdenas-Lizana, S. Gómez-Quero, M. A. Keane, Appl. Catal. A: Gen. 334 (2008) 199.
[2] F. Cárdenas-Lizana, S. Gómez-Quero, M. A. Keane, Catal. Commun. 9 (2008) 475.
[3] F. Cárdenas-Lizana, S. Gómez-Quero, M. A. Keane, ChemSusChem. in press.

GC-7
Molecular biological designed biotemplates for catalysts with reduced precious metal content
S. Roos a , D. Keck a , J. Hofinger a , A. Springer b , M. Berndt c
a Namos GmbH, Tatzberg 47, 01307 Dresden, Germany
b Institute for Materials Science, University of Technology Dresden, 01062 Dresden, Germany
c Interkat Katalysatoren GmbH, Eduard-Rhein-Straße 25, 53639 Königswinter, Germany
e-mail: Juergen.Hofinger@namos.de
Background
Current support materials for heterogeneous catalysts are highly available while being optimized regarding to their efficiency in catalytic processes. The
simplicity in the structure however implies a far less than optimal distribution of precious metals, especially on the nanoscale. Intended nanostructures on the
surface to improve sinter stability is accompanied by a system of micro pores, which is accessible to precious metal complexes at production through diffusion
mechanisms but not for the gas flow during service life. Conventional sealing of the porous material affects the nanostructure on the surface and therefore
increases sintering of precious metal particles at elevated temperatures.
Results
To overcome the limitations of conventional materials science complex biomolecules have been used as templates for nanostructuring and positioning of precious
metals on surfaces. Advanced possibilities of molecular biology could therefore be used during manufacturing while possible negative influences on the catalytic
performance have been avoided by finally removing the biomaterial. Different types of Al 2 O 3 support materials have been coated with Pt nanoparticles with
biomolecular templates as additives as well as using standard methods as a reference. Various kinds of biotemplates have been used including self organizing
proteins and globular proteins for the preparation of precious metal precursors. Scanning Transmission Electron Micrographs (STEM) could reveal the selective
positioning of precious metal nanoparticles on designated locations on the support avoiding any deposition in unused micro pores. Catalytic turnover of CO to
CO 2 has been measured using gas chromatography to evaluate the light off performance of coated cordierit granulate and catalyst cores. The experiments could
proof that application of biomolecular templates as simple additives in the manufacturing of exhaust gas catalysts can significantly reduce the need precious metal
load.
Justification for acceptance
The need of precious metals for heterogeneous catalysts is constantly growing, regardless of any efforts of recycling technologies and searches for alternative
materials. The proposed biomimetic approach is highly innovative and promises significant cost savings while maintaining maximum compatibility to well
established processes.
GC-8
Alkylation of benzene with ethane into ethylbenzene over PtH-ZSM-5 bifunctional catalyst at low temperatures
K. S. Wong, T. Vazhnova and D. B. Lukyanov*
Department of Chemical Engineering, University of Bath, Bath, BA2 7AY, United Kingdom
*Corresponding author. Tel: +44 1225 383329, Fax: +44 1225 5713
e-mail: D.B.Lukyanov@bath.ac.uk
Background
Ethylbenzene (EB), the primary feedstock for the synthesis of polystyrene, is currently produced via acid catalysed benzene alkylation with ethene [1], which is a
product of highly endothermic and energy intensive processes [2] . The new catalytic reaction, which uses ethane for benzene alkylation, instead of ethene, would
eliminate the ethene production step, thus, minimising the energy consumption in the EB manufacturing and leading to the reduction of CO 2 emissions. The aim
of the present work was to perform in-depth investigation of benzene alkylation with ethane into EB over a PtH-ZSM-5 catalyst at low temperatures (290-410 o C)
in order to establish the effect of temperature on the reaction pathways and catalyst performance, thus, determining the optimum reaction temperature.
Results
Benzene alkylation with ethane over Pt (1 wt.%) supported H-ZSM-5 (Si/Al = 40) bifunctional catalyst was studied at atmospheric pressure in a continuous flow
reactor at 290, 330, 370 and 410 o C. Our results show very stable catalyst performance at all four temperatures, with no changes in benzene conversion during
nearly 50 hours on stream. Similar reaction pathways of benzene alkylation with ethane into EB were established at all temperatures, based on the kinetic data
obtained at different feed conversions. As expected, the catalyst activity was increasing with increasing temperature. However, it is shown that temperature has
different effects on the rates of the different reaction steps, and this leads to the different product distributions. Taking into consideration catalyst activity and
selectivity, we can conclude that 370 o C is the optimum temperature, at which very stable catalyst performance (46 h on stream) is observed and the EB selectivity
above 90 mol.% is achieved at benzene conversion of 12.5%, which is very close to the maximum equilibrium conversion of benzene into EB at this temperature
(13.6%). At lower temperatures (290 and 330 o C), the catalyst activity was significantly lower than at 370 o C, while at 410 o C a decrease in the EB selectivity was
observed.
Justification for acceptance
Direct alkylation of benzene with ethane into EB represents a new, environmentally benign process of EB production. Our work reveals the pathways of this
reaction and demonstrates its potential for EB manufacturing.
References
[1] T.F. Degnan Jr., C.M. Smith, C.R. Venkat, Appl. Catal. A: Gen. 221 (2001) 283.
[2] J.A. Moulijn, M. Makkee, A. van Diepen, Chemical Process Technology, John Wiley & Sons, Chichester, Chapter 4 (2001).

GC-9
An examination of reaction pathways accessible in the manufacture of trichloroethene
and tetrachloroethene via the oxy-chlorination process
David Lennon 1* , John. M. Winfield 1 , Iain W. Sutherland 1 , Neil Hamilton 1 , Christopher C. Dudman 2 and Peter Jones 2 .
1. Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow, G12 8QQ, U.K.
2. Ineos Chlor Ltd, Runcorn Site, PO Box 9, Runcorn, Cheshire WA7 4JE, U.K.
*Corresponding author. Tel: +44 141 3304372 Fax: +44 141 3304888 Email: davidle@chem.gla.ac.uk
Background
The development of hydrofluorocarbon refrigerants (HFCs) is one of the major achievements of green chemistry, with HFC-134a and 125 being two of the
current refrigerants of choice for many applications [1]. HFCs are non-ozone depleting, non-toxic, and have a negligible global warming potential and, as such,
have proved to be the ideal replacement for environmentally damaging chlorofluorocarbons (CFCs) [2]. Two important processes for the industrial scale
manufacture of HFC-134a and 125 use either trichloroethene or tetrachloroethene as feedstocks. Both of these reagents can be produced simultaneously by the
oxy-chlorination of 1,2-dichloroethane over a supported copper catalyst, with the overall process described by the following equations:
ClCH2CH2Cl + HCl + O2 C2HCl3 + 2 H2O (1)
2 ClCH2CH2Cl + 4 HCl + 3 O2 2 C2Cl4 + 6 H2O (2)
In some examples of the process, molecular chlorine is also used. Oxy-chlorination processes can suffer from low selectivity, and it is opportune to optimise this
process to lead to a more efficient and sustainable supply chain. As part of an initiative to improve the operational efficiency of the oxy-chlorination process, this
communication describes an investigation to consider how the catalyst could be modified to deliver improved selectivity.
Results
Batch and continuous flow experiments have established that the overall process has both homogenous and heterogeneous contributions to the observed
chemistry. A reaction scheme has been developed which describes the interplay between reagents, temperature, catalyst composition, residence time, chlorine
supply and reaction intermediates. Reaction mechanisms are proposed for the majority of these transformations. Collectively, these experiments provide an
improved understanding of the fundamental steps that constitute this intricate and dynamic process, which will lead to catalyst specifications that could increase
yields for these valuable feedstocks.
Justification
The Montreal Protocol represents a milestone in global environmental action, with heterogeneous catalysis prominent as an enabling technology. This
communication illustrates how improvements in understanding of the production of the key feedstocks for the new refrigerants can further enhance operational
efficiency.
References
[1] R.L. Powell, J. Fluorine Chem. 114 (2002) 237
[2] D. Lennon, A.A. Freer, J.M. Winfield, P. Landon and N. Reid, Green Chem. 4 (2002) 181.
GC-10
Selective aerobic oxidation of alcohols
A.F. Lee, * S.F.J. Hackett, A.D. Newman and K. Wilson
a Department of Chemistry, University of York, Heslington, York, YO10 5DD
*Corresponding author. Tel: +44 1904 434470, Fax : +44 1904 432586, e-mail: afl2@york.ac.uk
Background
Heterogeneous catalysts offer new environmentally benign routes to diverse chemical products for the petrochemical, fine chemical and pharmaceutical sectors.
The aerobic selective oxidation (selox) of hydrocarbons exemplifies this approach, wherein powerful solid catalyst technologies can circumvent the use of
stoichiometric reagents or expensive homogeneous complexes, and their associated process and safety disadvantages. 1 Supported palladium clusters are
promising candidates to catalyse the direct selox of alcohols to their corresponding aldehydes/ketones for use in fragrances and flavourings. Here we address
fundamental issues relating to the nature of the active site and on-stream deactivation in such systems.
Results
Time-resolved surface science studies over model palladium surfaces, and corresponding
X-ray measurements on dispersed Pd/Al 2 O 3 catalysts, have identified the active site in
cinnamyl and crotyl alcohol selox to their respective aldehydes. XAS and XPS reveal
efficient oxidative dehydrogenation requires Pd 2+ active sites. Deactivation is associated
with oxide reduction; this exposes metallic Pd 0 surface sites which favour aldehyde
decarbonylation, resulting in adsorbed CO/alkylidynes and associated self-poisoning.
This insight has allowed us to develop exceptionally active catalysts, utilising a
mesoporous alumina support to stabilise atomically dispersed Pd 2+ centres (Figure 1). 2
These high performance tailored catalysts are recyclable and efficient in batch and
continuous operation modes.
Pore
channel
Alumina
support
Pd 2+ Al 3+ O 2-
Figure 1. Scanning transmission electron micrograph of catalyticallyactive,
isolated Pd atoms dispersed over a mesoporous Al 2 O 3 support.
Justification for acceptance
The clean synthesis of high value chemical intermediates by heterogeneously catalysed routes offers exciting alternatives to current energy intensive and atomuneconomical
processes, helping to reduce CO 2 emissions and preserve natural resources. This presentation highlights important criteria in designing such
catalysts and is ideally suited for the session on ‘Catalysis in a sustainable fine chemical industry’.
References
[1] A. Baiker, T. Mallat, Chem. Rev. 104 (2004) 3037.
[2] S.F.J. Hackett, R.M. Brydson, M.H. Gass, I. Harvey, A.D. Newman, K. Wilson, A.F. Lee, Angew. Chem. Int. Ed. 46 (2007) 8593.
Air

GC-11
Green Organic Syntheses with Alcohols by Concerto Metal Catalysts Using Inorganic Crystallites
Kiyotomi Kaneda*
Research Center for Solar Energy Chemistry, Osaka University,
1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
*Corresponding author. Tel & Fax: +81-6-6850-6260, e-mail: kaneda@cheng.es.osaka-u.ac.jp
Background
Atom-efficient catalytic reactions are one of the most promising solutions for the environmentally-benign organic syntheses. Heterogeneous catalysts have the
advantages of being operationally simple and enabling unprecedented reactions based on the specific ensemble sites on the surface. We have developed high
performance Concerto metal catalysts using inorganic crystallites of hydrotalcites, montmorillonites, and hydroxyapatites[1]. These catalysts exhibit excellent
performances in the transformation of alcohols, e.g., oxidations[2], C–C and C–N bond formations[3], and one-pot reactions[4]. Here, the prominent activities of
the solid catalysts for the transformations are focused in relation to the concerted functions between the surface properties of the inorganic crystallites and the
metal active species.
Results
Alcohol oxidation: Oxidation of alcohols to carbonyl compounds is one of the most important functional transformations in a variety of chemical processes.
Recently, we have developed the highly efficient alcohol oxidation system using hydrotalcite-bound silver nanoparticle catalyst [5]. The solid catalyst could
convert alcohols to the corresponding carbonyl compounds together with molecular hydrogen, where none of the oxidants were required.
Nucleophilic substitution of alcohols: In the carbon–carbon and carbon–heteroatom bond formations, the use of alcohols instead of alkyl halides and acetates as
electrophiles is considered to be an ideal method which prevents waste salt formation. However, catalytic substitution of hydroxyl group in alcohols is difficult
due to its poor leaving ability and there are few examples of the homogeneous catalytic systems. We have found the proton- and metal-exchanged
montmorillonites acted as solid acid catalysts having high activities for nucleophilic substitution of alcohols to form C–C and C–N bonds[6].
Justification of acceptance
These catalysts are easily prepared and recycled, and exhibit outstanding performances in alcohol oxidations and C–C and C–N bond forming reactions, thereby
opening a new avenue for sustainable green organic syntheses.
References
[1] K. Kaneda, et al. Bull. Chem. Soc. Jpn. 79 (2006) 981.
[2] K. Kaneda, et al. J. Am. Chem. Soc. 122 (2000) 7144; ibid, 124, (2002) 11572; ibid, 126 (2004) 10657; Angew. Chem., Int. Ed. 44 (2005) 3423; Chem. Mater. 19 (2007)
1249.
[3] K. Kaneda, et al. J. Am. Chem. Soc., 125 (2003) 10486; Chem. Eur. J. 11 (2005) 288; Angew. Chem., Int. Ed. 46 (2007) 3288.
[4] K. Kaneda, et al. J. Am. Chem. Soc. 126 (2004) 5662; ibid, 127 (2005) 9674; Chem. Eur. J. 12 (2006) 8228.
[5] K. Kaneda, et al. Angew. Chem., Int. Ed. 47 (2008) 138.
[6] K. Kaneda, et al. Angew. Chem., Int. Ed. 45 (2006) 2605; J. Org. Chem. 72 (2007) 6005.
GC-12
Implication of the support in the Au/TiO 2 -catalyzed aerobic epoxidation of stilbene
P. Lignier, B. Jouguet, S. Bennici, A. Auroux, J.-L. Rousset, V. Caps*
IRCELYON (CNRS / University of Lyon), 2 avenue Albert Einstein, 69626 Villeurbanne Cedex, France
*Corresponding author. Tel : +33 472 445 331, Fax : +33 472 445 399, e-mail : valerie.caps@ircelyon.univ-lyon1.fr
Background
Activating molecular oxygen for the synthesis of oxygenated fine chemicals from petrochemicals is one way to making these processes cleaner. Supported gold
nanoparticles have demonstrated a unique potential for aerobic epoxidation of bulky alkenes in the liquid phase [1]. We have recently proposed a plausible
mechanism for these transformations, involving highly selective free-radicals [2]. However the role of the catalyst remains unclear. Here, we use a colloidal
deposition method to prepare similar dispersions of gold nanoparticles on various titanias in order to study supports effects in this reaction.
Results
The colloidal deposition method allows to prepare gold nanoparticles with similar size distributions (3.0±0.2 nm), loadings (1.0±0.2 wt.%) and optical
environments (XPS and UV/vis), on commercial anatase titania supports (UV100, PC500 and AK350). These materials are evaluated in the epoxidation of transstilbene
(tS), using tS (1 mmol), methylcyclohexane (20 mL), Au/TiO 2 (2.1±0.2 mol Au), tert-butylhydroperoxide (0.05 mmol), air, atmospheric pressure, 80°C,
24h. This allows us to assess the effect of the titania surface composition (especially the presence of boron species during the gold deposition process) and the
titania morphology / degree of crystallinity on the catalytic reaction. By applying various calcination temperatures, the density of surface hydroxyl groups can be
tuned (as shown by TG-DTA) and the catalytic activities of the materials as well. Activities thus seem to depend on the titanol concentration. On the other hand,
selectivities towards epoxide remain similar (80-90%), which is related to a basically unchanged average gold particle size. Additional acidity studies (FTIR after
pyridine adsorption/desorption and adsorption calorimetry of NH 3 ) on both the naked supports and the corresponding supported catalysts at each calcination
temperature allow to account for the lower activity observed at higher calcination temperatures except for Au/AK350 at 450°C. The role of titanol groups and
promotion by boron species will be discussed in detail.
Justification for acceptance
One implication of this work is that direct oxidation of cyclohexane to cyclohexanol and cyclohexanone over gold catalysts under mild conditions seems possible,
upon fine tuning of the catalytic material. This presentation could thus stimulate discussion in the « Catalysis in a sustainable fine chemical industry » session.
References
[1] M.D. Hughes, Y.-J. Xu, P. Jenkins, P. McMorn, P. Landon, D.I. Enache, A.F. Carley, G.A. Attard, G.J. Hutchings, F. King, E.H. Stitt, P. Johnston,
K. Griffin, C.J. Kiely, Nature 437 (2005) 1132.
[2] P. Lignier, F. Morfin, S. Mangematin, L. Massin, J.-L. Rousset, V. Caps, Chem. Commun. (2007) 186.

ORAL
PRESENTATION
ABSTRACTS
AIR AND WATER

AW-1
The utility of cyclodextrins for enhancing the hydrodechlorination of
carbon tetrachloride in water catalyzed by palladium on charcoal
Anne Ponchel a ,* Sophie Lamotte-Fourmentin, David Landy b and Eric Monflier a
a Unité de Catalyse et de Chimie du Solide, UMR 8181, Université d’Artois, Rue Souvraz SP18, 62307 Lens, France.
b
Laboratoire de Synthèse Organique et Environnement, ULCO, 145 Avenue Schumann, 59140 Dunkerque, France.
*Corresponding author. Tel: +33 (0) 3 21 79 17 54, Fax : 33 (0) 3 21 79 17 54, e-mail: anne.ponchel.@univ-artois.fr
Background
Chlorinated hydrocarbons (CHCs) are toxic compounds for which the environment has little assimilation capacity. Their effective removal or destruction is an
important task and the development of new abatement treatment methods remains a great challenge. In this context, the development of an eco-efficient process
of dechlorination of volatile CHCs that performs in-situ the absorption step and the catalytic step in a clean medium (water) and under mild reaction conditions
(low temperature) appeared to us particularly attractive. The treatment of gaseous effluents contaminated by volatile CHCs through an aqueous solution
containing cyclodextrins (CDs) and a heterogeneous palladium catalyst (Pd/C) could be considered as such a process. The organic pollutants are trapped in water
by cyclodextrins by forming inclusion complexes and dechlorinated on the palladium-based catalyst [1].
Results
To examine the feasibility of the process, we have studied the catalytic hydrodechlorination of carbon tetrachloride (CCl 4 ) chosen as a model pollutant. Catalytic
hydrodechlorination of CCl 4 into CH 4 and chloride salts has been carried out at 30°C in a batch reactor, in the presence of a Pd/C catalyst and gaseous hydrogen :
Pd/C
CCl4
4 OH 4 H2
CH4
4 H2O
4 Cl
Our experimental results demonstrated that the addition of CDs (especially the modified ones) allowed to improve the rates of dechlorination of CCl 4 in water.
The role of CDs was investigated using different technique of characterization and seemed multiple under multiphase conditions. In fact, CDs can act as i)
classical mass transfer promoters increasing the solubility of CCl 4 in water via the formation of inclusion compounds but also as ii) dispersing agents of the Pd/C
catalyst improving the contacts of CCl 4 with the metal active sites [2].
Justification for acceptance
Finally, the “absorption/catalysis” combination can transform non-water soluble CHCs into alkane and chloride salts under mild conditions. The method has clear
advantages. No organic solvent is used. Cyclodextrins are non-toxic and biodegradable compounds. The catalyst can be recovered by filtration, to be reused or
recycled. The chlorinated pollutants are transformed into less toxic compounds, avoiding the formation of hazardous products (COCl 2 , Cl 2 ) or corrosive HCl.
References
[1] A. Cassez, A. Ponchel, H. Bricout, S. Fourmentin, D. Landy, E. Monflier Catal. Lett. 108 (2006) 209.
[2] A. Cassez, A. Ponchel, F. Hapiot, E. Monflier, Org. Lett. 8 (2006) 4823.
AW-2 Solvent and particle size effects in the liquid phase hydrodechlorination of 2,4-chlorophenol over Pd/Al 2 O 3
S. Gómez-Quero * , M.A. Keane
Chemical Engineering, Heriot-Watt University, Edinburgh EH14 4AS, Scotland.
*Corresponding author. Tel: +44 (0) 131 451 4704, e-mail: sg72@hw.ac.uk.
Background
Catalytic hydrodechlorination (HDC) has emerged as a progressive approach to treating toxic chlorinated waste in aqueous media. In HDC, chlorine is replaced
by hydrogen with the subsequent release of HCl, where Pd catalysts have been identified as the most efficient in terms of activity and resistance to deactivation.
The potential impact of bulk liquid conductivity and pH on reactant/catalyst interactions, the effect of the solvent and the role of the support and metal dispersion
have yet to be established. These issues must be resolved before effective practical application can be realised.
Results
The liquid phase catalytic HDC of 2,4-dichlorophenol (2,4-DCP) has been investigated over Pd/Al 2 O 3 at T = 303 K. 2,4-DCP HDC is predominately stepwise,
yielding 2-chlorophenol (2-CP) as the partially dechlorinated product. Solvent effects have been established, where lower 2,4-DCP consumption rates were
obtained with an increasing alcohol content in water+alcohol reaction media. Thermodynamic calculations demonstrate that the observed drop in activity is
related to the excess dielectric constant of the mixture and is the result of a disruption to the bulk liquid structure, which inhibits stabilization/solvation of the
arenium intermediate. This effect extends to water+THF and methanol+THF mixtures. Structure sensitivity is also confirmed over a wide range of Pd dispersions
(8-59 %) where smaller Pd particles ( 5 nm) exhibited higher specific (per m Pd 2 ) initial HDC rates. A greater than 20-fold decrease in specific HDC rate was
observed after controlled metal sintering (mean Pd diameter = 13 nm): smaller Pd particles are intrinsically more active where metal/support interactions
influence HDC performance. The reaction was also conducted under conditions of controlled pH (pH acid = 3 and pH basic = 13). At pH acid , higher Pd dispersions
delivered higher 2-CP selectivities due to a repulsion between chlorophenolic species in solution and a supported Pd-H + adduct; HDC at pH basic was insensitive to
Pd particle size. HDC performance is quantified in terms of solution ecotoxicity: an 81% decrease in toxicity has been recorded for reaction at higher Pd
dispersions and pH basic . [1]
Justification for acceptance
We present a comprehensive study that establishes, for the first time, a direct correlation of HDC activity with solvent thermodynamic properties. Structure
sensitivity and the impact of pH and support on catalyst performance are discussed. Our results demonstrate quantitatively the viability of catalytic HDC as a
detoxification methodology.
References
[1] S. Gómez-Quero, F. Cárdenas-Lizana, M.A. Keane. Ind. Eng. Chem. Res., submitted for publication.

AW-3
Tailoring of Pd-Catalysts for Application under Environmental Conditions
Katrin Mackenzie, Dalia Angeles-Wedler, Frank-Dieter Kopinke
UFZ – Helmholtz-Centre for Environmental Research, Department of Environmental Technology,
Permoserstr. 15, 04318 Leipzig, Germany; e.mail: katrin.mackenzie@ufz.de
Background
Palladium-catalyzed hydrodehalogenation bears a very high potential to become an alternative water treatment method for contaminated groundwater, wastewater
and other environmentally relevant water bodies. Hydrodehalogenation is the reduction of halogenated organic compounds (R-X) with hydrogen or a hydrogen
source represented by the equation R-X + H 2
catalyst R-H + HX. In the liquid phase, hydrodehalogenation using clean deionized water, Pd colloids and Pd
clusters on various supports were found to have a very high catalytic activity. However, the high sensitivity of the noble metal catalysts towards deactivation, e.g.
by poisoning due to reduced sulphur compounds or other omnipresent constituents of real waters, impede the full utilisation of the catalyst’s potential. Apart from
poisoning by sulphur species, deactivation can occur due to biofouling and blocking of active sites by inorganic salts and particulate matter during field
application.
Results
In order to make the high catalyst potential accessible for environmental application, measures against Pd deactivation must be taken. The presented work deals
with studies on the deactivation behaviour of Pd catalysts and the design of protection measures allowing the catalyst to remain active and stable. In order to
protect the active sites, thin hydrophobic films of polydimethyl-siloxane were applied onto commercially available Pd/Al 2 O 3 catalysts. These films allow organic
contaminants to diffuse to the reactive sites and make the catalyst resistant to inorganic salts and other ionic species. However, they do not provide a sufficient
protection against the permeation of fairly hydrophobic sulphur compounds such as un-dissociated H 2 S and organic reduced sulphur species. In a second
protection strategy, these undesired water constituents are oxidized, prior to contact with the catalytic system, by permanganate which itself does not interfere
with the hydrodehalogenation reaction. In addition, permanganate proved suitable to regenerate S-poisoned catalysts by oxidizing the bound sulphur on the Pd
surface. This full regeneration of Pd/Al 2 O 3 with permanganate is to our knowledge the only promising approach apart from that of Lowry et al. using
hypochlorite which was only partially successful [1].
Justification for acceptance
The presented work provides a tool for making Pd catalysts applicable for treatment of real waters, such as groundwater. By means of a combination of oxidative
water pre-treatment and hydrophobic catalyst protection the potential of Pd-catalyzed hydrodehalogenation can be utilized. Unprotected Pd/Al 2 O 3 which was
completely poisoned by sulphide could be reactivated by a combined treatment with permanganate and hydrazine.
References
[1] G. V. Lowry, M Reinhard, Environ. Sci. Technol. 34 (2000) 3217-3223.
AW-4
Unveiling the mechanism of the SO 2 -assisted N 2 O abatement over iron zeolites
Miguel A.G. Hevia a , Sònia Abelló a and J. Pérez-Ramírez a,b, *
a Institute of Chemical Research of Catalonia, Avinguda Països Catalans 16, 43007 Tarragona, Spain.
b Catalan Institution for Research and Advanced Studies, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
*Corresponding author. Tel: +34 977 920236, Fax : +34 977 920224, e-mail: jperez@iciq.es
Background
Remarkable progress toward implementation of technology for N 2 O mitigation in the chemical industry has been experienced in recent years. For example, the
Uhde EnviNOx process applies FeZSM-5 zeolite for catalytic N 2 O abatement in the tail-gas of nitric acid plants. The positive effect of NO on the rate of N 2 O
decomposition is decisive for application of this catalyst [1]. Building on this effect, we have discovered that SO 2 also accelerates the N 2 O removal over iron
zeolites independent of the framework type and preparation method. This result is remarkable as sulphur dioxide is a prototypical inhibitor/poison of catalysed
reactions. The efficiency of SO 2 with respect to other promoters and reducing agents has been compared and its mechanistic action has been elucidated using
transient and operando spectroscopic techniques. This result is attractive for N 2 O sources where SO 2 is present.
Results
Fe-zeolites (ZSM-5, beta, ferrierite, mordenite) were prepared using various routes (steam activation, ion exchange, chemical vapor deposition) and Fe loadings
(0.5-5 wt.%) in order to obtain materials with different iron constitution. The samples were extensively characterized and tested in N 2 O decomposition in the
range 473-873 K at different inlet partial pressures of SO 2 (SO 2 /N 2 O = 0-2). The positive effect of SO 2 on the N 2 O conversion occurred over all catalysts tested,
irrespective of the synthesis method and zeolite host. As a result, the conversion profiles were shifted 50-100 K to lower temperature compared to the direct N 2 O
decomposition in the absence of SO 2 . Differently to the NO-assisted N 2 O decomposition [1], the SO 2 -assisted N 2 O decomposition is stoichiometric, i.e. SO 2 acts
as a reductant and effectively scavenges atomic oxygen species from N 2 O leading to SO 3 and N 2 . The time-on-stream stability of iron zeolites in N 2 O+SO 2
mixtures was remarkable, even in the presence of O 2 and H 2 O. The magnitude of the positive SO 2 action in terms of de-N 2 O activity is very similar to that of NO
and superior to well-established reducing agents such as NH 3 . The mechanism of the SO 2 +N 2 O reaction has been studied by Temporal Analysis of Products.
Operando DRIFTS complemented TAP investigations and revealed the status of the catalyst surface under working conditions.
Justification for acceptance
Justification for acceptance attends to fundamental and practical reasons. The mechanism of the SO 2 -assisted N 2 O decomposition over Fe-ZSM-5 and the iron
site requirements are for the first time reported. The positive action of sulphur dioxide is general to iron zeolites. This effect is beneficial for N 2 O abatement in
SO 2 -containing tail gases, such as in caprolactam plants and FBC combustors.
References
[1] J. Pérez-Ramírez, F. Kapteijn, G. Mul, J.A. Moulijn, J. Catal. 208 (2001) 211.

AW-5
The catalytic performance of Cu-zeolites in the N 2 O decomposition: an unprecedented positive effect of H 2 O
P.J. Smeets a , B.F. Sels a , E.J.M. Hensen b and R.A. Schoonheydt a,*
a Center for Surface Chemistry and Catalysis, K.U.Leuven, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium
b Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, the Netherlands
* Corresponding author. Tel: +32 16 321592, Fax: +32 16 321998. E-mail: robert.schoonheydt@biw.kuleuven.be
Background
Due to its large global warming potential, the catalytic decomposition of N 2 O has attracted great interest [1]. The direct decomposition of N 2 O into N 2 and O 2
over TMI-exchanged zeolites is a very promising route. However, the presence of NO, H 2 O and O 2 in relevant tail gases exerts a negative effect on the N 2 O
decomposition activity over most catalysts. We present a study of the catalytic N 2 O decomposition over Cu-zeolites in the presence of NO, O 2 and H 2 O.
Results
Cu-zeolites can be divided into three groups according to their activity in the direct N 2 O decomposition: (i) catalysts containing mostly isolated (EPR-active) Cu 2+
sites (Cu/Al0.25) (EPR silent Cu 2+ ), the activity is greatly increased. This is
attributed to facilitated O atom migration as the average distance between Cu sites decreases. (iii) The third group consists of catalysts with Cu/Al > 0.22
containing active Cu dimers bridged by two deposited O atoms such as in ZSM-5 [2]. Here O-migration is not required, and these catalysts exhibit by far the
highest catalytic activity. All this points to the importance of O 2 desorption as the rate-limiting step [3, 4].
O 2 has no effect on the activity of Cu-zeolites. NO accelerates the N 2 O decomposition rate since it offers an alternative route of oxygen migration via gas phase
NO 2 . The effect is most pronounced for catalysts with low Cu content. In contrast with literature reports published, H 2 O exerts a positive effect on the N 2 O
decomposition over catalysts containing mostly isolated Cu sites, resulting in a shift of the conversion curve to lower temperatures with up to 100°C. At
increasing Cu content H 2 O has a negative effect. We envision two H 2 O effects counteracting each other: (1) competitive adsorption hindering N 2 O activation and
(2) H 2 O-induced Cu migration decreasing the distance between isolated Cu sites. The former dominates at high Cu loading, while the latter is predominant at low
Cu loadings. The effect of H 2 O was found to be fully reversible [4].
Justification for acceptance
A consistent global picture of the catalytic decomposition of N 2 O over Cu-zeolites is obtained with O recombination into O 2 as the rate determining step. This
picture allows us to explain the effects of H 2 O, NO and O 2 on the reaction. The effect of H 2 O, which can be positive or negative depending on the type of catalyst,
sheds new light on the ongoing search for a suited catalyst for decreasing the emission of the greenhouse gas.
References
[1] F. Kapteijn, J. Rodriguez-Mirasol, J.A. Moulijn, Appl. Catal. B 9 (1996) 25.
[2] M.H. Groothaert, P.J. Smeets, B.F. Sels, P.A. Jacobs, R.A. Schoonheydt, J. Am. Chem. Soc. 127 (2005) 1394.
[3] P.J. Smeets, M.H. Groothaert, R.M. van Teeffelen, H. Leeman, E.J.M. Hensen, R.A. Schoonheydt, J. Catal. 245 (2007) 358.
[4] P.J. Smeets, B.F. Sels, R.M. van Teeffelen, H. Leeman, E.J.M. Hensen, R.A. Schoonheydt, J. Catal. Submitted.
AW-6
Mechanistic origins governing catalytic de-N 2 O activity of Fe- and Rh-MFI zeolites
Evgenii V. Kondratenko a, * , Vita A. Kondratenko a , Marta Santiago b and Javier Pérez-Ramírez b,c
a Leibniz Institute for Catalysis, Branch Berlin, PO Box 96 11 56, 12474 Berlin, Germany
b Institute of Chemical Research of Catalonia (ICIQ), Avinguda Països Catalans 16, 43007, Tarragona, Spain
c Catalan Institution for Research and Advanced Studies, Passeig Lluís Companys 23, 08010, Barcelona, Spain
*Corresponding author: +49-30-63924454, E-mail address: evgenii.kondratenko@catalysis.de
Background
Metal-loaded zeolites are efficient catalysts for N 2 O abatement in tail gases of industrial and energy-related processes [1,2]. The practical relevance of these
materials stimulated extensive research for deriving relationships between the preparation method of the zeolite, the nature of the active metal species, and the
catalytic performance. However, serious attempts to develop rational de-N 2 O micro-kinetics for predicting catalytic performance and/or for catalyst
designing/improving are scarce. Therefore, the present contribution was focused on elucidating fundamental origins governing the catalytic activity in N 2 O
decomposition to N 2 and O 2 from elementary-step kinetic analysis. From this analysis, the requirements for highly active de-N 2 O catalysts were defined.
Results
The temporal analysis of products (TAP-2) reactor was applied for mechanistic analysis of N 2 O decomposition over differently prepared Fe- and Rh-ZSM-5. In
order to derive insights into plausible pathways leading to N 2 and O 2 from N 2 O, their transient responses upon N 2 O pulsing were simultaneously fitted to different
micro-kinetic models and discriminated. As a result, the near-to-elementary steps of the studied reaction were identified. The derived mechanisms of N 2 O
decomposition over Fe-ZSM-5 and Fe-ZSM-5 differ in the reaction pathways leading to N 2 and most importantly to O 2 . However, the nature of iron species
(isolated, oligomerised or FeO x nano-particles) and the method of catalyst preparation do not influence the reaction mechanism over Fe-ZSM-5. Only the rate of
the O 2 desorption seems to be a distinguishing factor for the different iron species. Similar to the Fe-ZSM-5 system, N 2 O decomposition over Rh-ZSM-5 takes
place over free metal sites and over oxygen species deposited on these sites by N 2 O. However, oxygen formation occurs directly via reaction of gas-phase N 2 O
with *-O over Rh-MFI-5, while the latter reaction over Fe-ZSM-5 leads to a surface bi-atomic oxygen species (O-*-O) followed by its transformation to *-O 2 .
This is probably a reason for the lower activity of Fe-ZSM-5 below 673 K as compared to Rh-ZSM-5. Moreover, collision frequencies of N 2 O over Rh species
are much higher than over Fe species favouring N 2 O decomposition. The influence of temperature and inlet N 2 O partial pressure on catalytic performance of Feand
Rh-MFI was additionally investigated for steady-state operation assuming the derived micro-kinetic schemes. Our micro-kinetics qualitatively describes the
steady-state results and correctly predicts the relative activity of the catalysts studied.
Justification for acceptance
This contribution elucidates and compares the near-to-elementary steps of N 2 O decomposition over Fe-ZSM-5 and Rh-ZSM-5 from the temporal analysis of
products. As result, possible mechanistic origins of the superior activity of Rh-ZSM-5 over Fe-ZSM-5 have been identified, which may be relevant for
developing or improving catalytic materials for direct N 2 O decomposition.
References
1. F. Kapteijn, J. Rodríguez-Mirasol, J.A. Moulijn, Appl. Catal. B 9 (1996) 25.
2. Pérez-Ramírez, J., Kapteijn, F., Schöffel, K., Moulijn, J.A., Appl. Catal. B 2003, 44, 117.

AW-7
Maintaining the activity of gold catalysts for cleaning water and air
Richard Holliday a , Jason McPherson b , Thabang Ntho b and David Thompson ab*
a
World Gold Council, 55 Old Broad Street, London, UK
b
Project AuTEK, Mintek, Private Bag X3015, Randburg 2125, South Africa
*Corresponding author. Tel +44 118 984 2551, Fax +44 118 984 5717, E-mail: DTThompson@aol.com
Background
Gold catalysts are very active for a variety of commercially significant pollution control reactions [1] and there is clear evidence of increasing R&D and patent
activity involving gold and gold-platinum group metal combinations: this is likely to result in new applications in air cleaning, protective gas masks, and water
pollution control [2]. We have produced three catalysts, i.e. 1wt%Au/TiO 2 , 0.8wt%Au/Al 2 O 3 and 1wt%Au/ZnO (AUROlite TM ) in 15kg quantities and the
methods devised are suitable for further scale-up. Results of commercial significance will be described for use of these catalysts in respirators and other pollution
control applications.
Results
Recent results indicate that both ionic and nanoparticulate metallic gold may be playing a role in the mechanism of some heterogeneous gas-phase processes, and
catalytic gold has significantly more durability and poison resistance potential than was previously implied [1]. Further optimisation of its durability properties
could mean that in gas phase pollution control applications such as removal of harmful impurities from living atmospheres, and in their use in gas mask catalysts
and low light off autocatalysts, gold systems could become the catalysts of choice. Nanostellar in California has designed a cost effective Au-Pd-Pt diesel
oxidation catalyst that has proven to be extremely durable at the highly elevated temperatures and challenging operating conditions found in exhaust systems; and
a Au-Pd catalyst is the best for the hydrodechlorination of trichloroethene in groundwater, providing an effective means of removing this major pollutant derived
from degreasing metals and textile cleaning [3]. Stability has already been firmly established in the liquid phase, where the oxidation of glucose to gluconic acid
has high activities and selectivities in a continuous reactor for 110 days using Au/Al 2 O 3 [4].
Methods used for increasing the gas-phase durability of gold catalysts by the addition of other metal oxide to the support materials and inclusion of other metals
as well as gold will be described. Gold catalysis is contributing a new aspect to the catalyst science scene and operation at room temperature means that
poisoning by deposition of carbonate or bicarbonate is more likely to account for deactivation as opposed to sintering of the metal. The addition of water to the
feed gas under certain conditions can inhibit deactivation of Au/TiO 2 used for CO oxidation.
These results have produced a radical change in the perception of the potential of gold as a catalyst; and the much greater availability and lower price of gold
compared with platinum is another important factor making gold attractive for applications deriving from recent R&D [2].
Justification for acceptance
Gold is readily available and could make a large and unique contribution to pollution control of both gaseous and liquid-borne species. Whereas early studies in
the gas phase demonstrated that the gold catalysts activity decreased quite rapidly, recent work using mixed metal and multicomponent supports in both the liquid
and gas phases has indicated ways to make these catalysts commercially interesting.
References
[1] G.C. Bond, C. Louis and D.T. Thompson, ‘Catalysis by Gold’, Imperial College Press, London,. 2006.
[2] C.W. Corti, R.J. Holliday and D.T. Thompson, Topics Catal. 44 (2007) 331.
[3] M.O. Nutt, K.N. Heck, P. Alvarez and M.S. Wong, Appl. Catal. B: Env. 69 (2006) 115.
[4] N. Thielecke, K.-D. Vorlop and U. Prüsse, Catal. Today, 122 (2007) 266.
AW-8
Ceria-supported gold catalysts for wastewater treatment: influence of the pre-treatment conditions.
N. D. Tran a , M. Besson a , C. Descorme a, *, K. Fajerwerg b , C. Louis b and C. Méthivier b
a CNRS / Université de L.yon, IRCELYON, Villeurbanne, France
b UPMC Univ Paris 06, Laboratoire de Réactivité de Surface, Paris, France
*Corresponding author. Tel: +334 7244 5307, Fax: +334 7244 5399, email: claude.descorme@ircelyon.univ-lyon1.fr
Background
Since the discovery by Haruta et al. that supported gold nanoparticles are catalytically active for the oxidation of CO 1 , a wide range of applications has been
proposed 2 . Among these, the treatment of aqueous model pollutants using Au/TiO 2 catalysts has been described by Besson et al. 3 . The key parameters have been
shown to be the gold particle size, which has a drastic impact on the catalyst performances, and, the stability under reaction conditions. In this study, the Catalytic
Wet Air Oxidation (CWAO) of carboxylic acids over Au/CeO 2 catalysts is presented and the effect of the catalyst pretreatment is analyzed.
Results
Au was supported on a commercial CeO 2 support (280 m 2 g -1 ) via the method of deposition-precipitation with urea (DPU) and two different Au loadings (1 and 4
wt%) were selected. Catalysts were activated under various conditions to influence the oxidation state of gold, as earlier shown by Delannoy et al. 4 . Calcination at
500°C of the 1 wt% Au catalyst led to cationic Au whereas metallic gold (Au°) was obtained in the case of 4 wt% Au/CeO 2 . On the other hand, after reduction
under H 2 at 300°C, only Au° was observed, whatever the Au loading. CWAO experiments were performed in a 300 mL stirred batch reactor (5 MPa, 190°C). 150
mL aqueous solution and 0.4 g or 0.2 g catalyst were used for the 1 and 4 wt % Au, respectively. Succinic (42 mM L -1 ) and acetic (20 mM L -1 ) acids were
selected as model pollutants. CeO 2 alone was active in the CWAO of succinic acid but it was inactive in the CWAO of acetic acid. For a given carboxylic acid,
the specific activity of the reduced catalysts was similar whatever the Au loading whereas the performances of the calcined catalysts depended greatly on the
nature of the targeted pollutant and the gold loading. The reduced 1wt%Au/CeO 2 catalyst was markedly more active in the CWAO of acetic acid compared to the
calcined one (165 vs. 35 mM acetic acid mM Au -1 h -1 ), indicating that Au° species are required to achieve high catalytic performances. Additionally, as the gold
dispersion decreased upon CWAO, the gold catalyst performances decreased as well.
Justification of acceptance
This study, dealing with the increasingly important wastewater treatment problem, clearly shows the impact of the catalyst pre-treatment on the performances in
the CWAO reaction and demonstrates the implication of metallic gold species as the active centres.
References
[1] M. Haruta, T. Kobayashi, H. Sano, N. Yamada, Chem. Lett. 2 (1987) 405
[2] G.C. Bond, C. Louis, D.T. Thompson, Catalysis by Gold, Imperial College Press, 2006
[3] M. Besson, A. Kallel, P. Gallezot, R. Zanella, C. Louis, Catal. Commun. 4 (2003) 471
[4] L. Delannoy, N. Weiher, N. Tsapateris, A.M. Beesley, N. Chari, S.L.M. Schroeder, C. Louis, Topics Catal. (2007) 263.

AW-9
Relevance of oxygen-containing VOC as model molecule for the study of dioxin total oxidation on VO x /TiO 2 catalysts.
R. Delaigle, D.P. Debecker, E.M. Gaigneaux*
Unité de catalyse et de chimie des matériaux divisés, Université Catholique de Louvain,
Louvain-la-Neuve, Belgium
*Corresponding author. Tel: +32 10 47 36 65, Fax: +32 10 47 36 49, email: eric.gaigneaux@uclouvain.be
Background
Catalytic total oxidation is the most promising solution to destroy dioxin. For this application, VO X /TiO 2 catalysts are widely developed [1-2]. Model molecules
are generally used to study this reaction. Chlorobenzene derivatives are frequently chosen as chlorinated aromatic VOC model. However, the oxygenated ring of
a dioxin is not taken into account by this approach [3]. Therefore, we studied the catalytic abatement of two oxygen-containing volatile organic compounds (O-
VOC) as alternative model molecules for dioxins: furan was chosen as a model for the central ring of a PCDF, while 2,5-dimethylfuran was studied in order to
consider the steric hindrance existing around the oxygenated moiety of the modeled pollutant.
Results
The behavior of the O-VOC models during catalytic tests was compared to the results obtained with chlorobenzene. Furan tends to adsorb rapidly and strongly on
the catalyst surface, without being quantitatively oxidized, even leading to a carbonaceous deposit composed of maleate species. 2,5-dimethylfuran behaves in the
same manner even with its steric hindrance. This behavior is opposite to what is observed with Cl-VOC models. The adsorption of chlorobenzene indeed appears
as a rate limiting step compared to the fast oxidation of the adsorbed species. Moreover, in the course of intermolecular competition, the O-containing models win
against the Cl-containing models. Indeed, the conversion of chlorobenzene is dramatically impeded in the presence of both investigated O-VOC. As this is also
true with 2,5-dimethylfuran against chlorobenzene, it should also be the case in the course of the intramolecular competition that occurs during dioxin abatement.
Justification for acceptance
Our investigations show that the nature of the pollutant-to-catalyst interaction could be decisively dictated by the presence of an O-moiety and not by the
presence of a Cl-function. This information is crucial for further studies on the evaluation and/or optimization of catalyst formulations for the purpose of dioxin
abatement.
References
[1] K. Everaert , J. Baeyens, Waste Manage. 24 (2004) 37-42.
[2] F. Bertinchamps, C. Gregoire , E. M. Gaigneaux, Appl. Catal. B: Environ. 66 (2006) 1-9.
[3] D.P. Debecker, F. Bertinchamps, N. Blangenois, P. Eloy, E.M. Gaigneaux, Appl. Catal. B: Environ. 74 (2007) 224–233.
AW-10
A time-resolved in situ XANES study of transient methane oxidation over alumina supported platinum
E. Becker a,b *, P-A. Carlsson a,b , H. Grönbeck a,c and M. Skoglundh a,b
a Competence Centre for Catalysis, b Department of Chemical and Biological Engineering, and c Department of Applied Physics, Chalmers University of Technology, SE-412 96
Göteborg Sweden
*Corresponding author: Tel +46 31 772 3372 Fax: email: elinb@chalmers.se
Background
X-ray absorption spectroscopy (XAS) is a powerful technique for analysis of, e.g., the oxidation state of solids. In an XAS spectrum the X-ray Absorption Near
Edge Structure (XANES) region provides information about the electronic structure of the absorbing atom and can thus reveal information about the chemical
state of catalyst surfaces. Different methods to extract both qualitative and quantitative [1-3] information from XANES spectra have been used, however, here a
method enabling time-efficient analysis of time-resolved XANES spectra has been developed. We adopt this method to follow the catalytic process in situ during
methane oxidation over Pt/Al 2 O 3 at transient conditions [4].
Method development and results
The method is based on utilising the white-line area (WLA) to follow small changes in Pt/O surface ratio. The WLA is defined as the integrated peak area above
the baseline of the L III edge jump, with a lower bound of the L-edge itself. In specific, the WLA of each spectrum was calculated by selecting the first minimum
of absorption after the edge (denoted as S 0 ) as a starting point, and then finding the corresponding energy, e 2 . The WLA is thereafter calculated by integration of
the absorption spectrum S(), from energies e 1 to e 2 , followed by subtraction of S 0 [4]. The relevance of the method is confirmed by first principles calculations
that exemplify how adsorbates modify the electronic structure of Pt. The present method has the advantage of being less sensitive to the normalisation of the
spectra.
Using this method, changes in surface O/Pt ratio has been correlated to changes in the methane oxidation activity. In particular, activity maxima observed at the
switches during lean-rich cycling are correlated to intermediate surface O/Pt ratio. For a rich-lean switch the activity maximum is most likely owing to the
combined effect of high availability of CH x adsorbed during the rich period and the transition through a surface O/Pt ratio with high activity. The surface O/Pt
ratio is thus crucial for the methane oxidation activity. An oxygen-rich surface seems to suppress the dissociative adsorption of methane which results in low
methane oxidation activity at oxygen excess. This has also been supported by microkinetic modelling. The results suggest that in applications, transient operation
(O 2 or H 2 pulsing) of the gas composition could be beneficial to maintain a surface composition favourable for high methane conversion.
Justification for acceptance
The new method for quick analysis of time-resolved in situ XANES measurements is likely of relevance for many fields within catalysis research. Furthermore,
low-temperature catalytic oxidation of methane may be an important reaction striving towards a sustainable society.
References
[1] J. Horsley, J. Chem. Phys. 76 (1982) 3
[2] H. Yoshida, S. Nonoyama, Y. Yasawa, T. Hattori, Phys. Scr. T1115 (2005) 813.
[3] M. Casapu, J-D. Grunwaldt, M. Maciejewski, A. Baiker, S. Eckhoff, U. Göbel, M. Wittrock, J. Catal 251 (2007) 28.
[4] E. Becker, P-A. Carlsson, H. Grönbeck, M. Skoglundh, J. Catal 252 (2007) 11.

AW-11
Activation and oxidation of methanol over ceria and titania-supported Au catalysts:
an operando IR study of the active site and reaction mechanism.
S. Rousseau a , P. Bazin a , F.C. Meunier a , O. Marie a * , V. Harlé b , S. Verdier b , M. Daturi a
a LCS, ENSICAEN-University of Caen-CNRS, 6, boulevard Maréchal Juin, 14050 Caen Cedex, France.
b Rhodia Recherches, 52 Rue de la Haie Coq, F-93308 Aubervilliers Cedex, France
* +33 231 452 822, marieo@ensicaen.fr
Background
Supported Au catalysts are active materials for the low-temperature oxidation of pollutants such as volatile organic compounds (VOCs). Au-based materials are
also being considered as promising electrodes for the electrochemical conversion of alcohols in fuel cells. With a view at designing better and durable VOCs
catalysts and electrodes, the mechanisms of methanol activation and oxidation over Au-containing materials were studied as a model reaction with a view at
identifying the promoting role of Au.
Results
Operando FTIR spectroscopy and mass spectrometry were used to study the mechanism of methanol oxidation at 303 and 323 K on 1% Au/CeO 2 and 0.6%
Au/TiO 2 catalysts. The simultaneous analysis of adsorbed surface species and gaseous compounds allowed identifying crucial steps in the oxidation pathway,
active sites and intermediate species. The Au/TiO 2 catalyst presented no steady-state activity for methanol conversion (while this sample was active for CO
oxidation). On the contrary, the Au/CeO 2 catalyst exhibited a methanol conversion of 15 % at 303 K and 50 % at 323 K. The nature and concentration with time
on stream of the surface species formed over the Au/CeO 2 sample were investigated in detail. Various methoxy species were observed, but only one of those was
further reacted to form a surface formate species. The formate species was then further decomposed into CO 2 and water. A similar mechanism of methanol
oxidation was already observed on CeO 2 -based samples, but at significantly higher temperatures (> 473 K) [1]. In the present case, the gold nanoparticules are
thought to favour O 2 dissociation and increase ceria oxygen mobility, likely via a spillover of oxygen. The formation of the reactive methoxy species on the
support is proposed as the rate determining step over the highly active Au/CeO 2 .
Justification for acceptance
This work reports an in-depth analysis of the promoting role of Au nanoparticles (3 nm diameter) on the oxidation activity of redox oxides used for a range of
catalytic reactions pertaining to the elimination of VOCs and fuel cell electrodes used for the oxidation of alcohols.
Reference
[1] E. Finocchio, M. Daturi, C. Binet, J.C. Lavalley, G. Blanchard, Catalysis Today 52 (1999) 53.
AW-12
Plasma-assisted total catalytic oxidation of methane.
On the effects of energy deposition, feed composition, and catalytic phase
Rui Marques a , Stéphanie Da Costa b , Stephane Carpentier b , Patrick Da Costa a *
a UPMC Paris 6, Laboratoire de Reactivité de Surface, UMR 7609, 4 Place Jussieu Paris, Case 178, 75252 Cedex 05, France, b Gaz de France, Direction de la Recherche, 361 av.
du président WILSON, 93211 Saint Denis la Plaine cedex, France. *Corresponding author: Fax number:+33 1 44 27 60 33, E-mail address: Patrick.da_costa@upmc.fr
Background
The huge world-wide presence of natural gas makes it an attractive alternative to other energy sources. Although natural gas combustion provides several
advantages, the emission of unburned methane, which is the main component of natural gas, is a drawback given that methane is a potent greenhouse gas, which
is recognized to contribute more to global warming than CO 2 at equivalent emission rates. The total oxidation of methane raises numerous difficulties. Indeed, the
high stability of the methane molecule together with the following reaction conditions: the low temperatures at which the catalyst must operate; the low
concentrations of methane; the large amounts of H 2 O, CO 2 , O 2 , and the presence of SOx and NOx did not lead to an ideal catalyst.
Results
The total oxidation of methane was carried out within a dielectric barrier discharge (DBD) reactor. The effect of energy deposition was studied. In the current
study, we also investigated the combined process of a dielectric barrier discharge and -alumina catalyst in the total oxidation of methane. In order to separate the
catalytic effects from the plasma activation, the work included both purely catalytic and plasma activation processes. It was found that the catalytic activity
depended on the energy deposition and the temperature. The plasma process leads to methane conversion in a lower temperature range than when only a catalyst
was present [1]. Furthermore, the addition of CO 2 in the feed does not affect the methane conversion. The presence of -Al 2 O 3 leads to CO+CO 2 , whereas for the
plasma induced process, CO is the major product of the reaction. Finally, we investigated the combined process of a dielectric barrier discharge and -Al 2 O 3
noble metal catalysts such as platinum and palladium. It was found that the presence of complete feed, within 4% of water, leads to increase the methane
conversion in purely plasma activation processes. Moreover, a higher efficiency for methane oxidation in CHP conditions was observed with the plasma-
Pd(X)/Al 2 O 3 systems.
Justification of acceptance
Nowadays, there is no satisfactory catalytic process for the treatment of residual methane due to durability and stability of the catalysts. The catalysis assisted by
plasma could be an alternative solution. This study led to a Patent in collaboration with Gaz De France.
References
[1] R. Marques, S. Da Costa, P. Da Costa, Applied Catal. B, (2008), in press

AW-13
Efficient removal and detoxification of organic pollutants by catalytic wet-air oxidation
A. Pintar*, J. Batista and T. Tišler
National Institute of Chemistry, Hajdrihova 19, P.O. Box 660, SI-1001 Ljubljana, Slovenia
*Corresponding author. Tel: +386 1 4760283, Fax: +386 1 4760300, e-mail: albin.pintar@ki.si
Background
Catalytic wet-air oxidation (CWAO) is a promising technique for destructive removal of toxic and non-biodegradable organic compounds from industrial
wastewaters [1]. In this process, the organic pollutants are oxidized at mild operating conditions by activated oxygen species in the presence of a solid catalyst
into biodegradable intermediate products or mineralized into CO 2 , water and associated inorganic salts. Titania and zirconia supported Ru catalysts exhibit high
activity and chemical resistance in CWAO of various model pollutants and industrial effluents [2,3].
Results
In this work, the performance of various Ru/TiO 2 catalysts to promote oxidation of aqueous solutions of formic acid, acetic acid and phenol was investigated in a
continuous-flow trickle-bed reactor. Oxidation experiments were carried out at T=328-523 K and total pressures up to 50 bar. The residence time of the liquid
phase in the catalytic bed was in the range from 0.12 to 0.33 min. Chemical analyses (TOC, HPLC) and bioassays (48-h and 30-min acute toxicity tests using
Daphnia magna and Vibrio fischeri, respectively) were used to get information about the toxicity impact of the feed and treated solutions. It was found out by a
thorough TPR/TPO examination of fresh and used catalysts that transformation of metallic Ru clusters to RuO 2 takes place in parallel to the oxidation of
pollutants. Complete oxidation of formic acid was obtained at mild operating conditions (383 K), and no catalyst deactivation occurred that could be attributed to
the dissolution of active ingredient material. It was observed that besides oxidation route thermal decomposition contributes significantly to the removal of formic
acid; Ru/TiO 2 catalysts could be thus efficiently used for transformation of HCOOH to H 2 and CO 2 in an inert atmosphere. Liquid-phase oxidation of recalcitrant
acetic acid was found to be structure sensitive; the highest catalyst activity was obtained, when Ru phase on the catalyst surface prevailed in zero-valent state.
The employed Ru/TiO 2 catalysts enable complete removal of phenol and more than 99 % removal of TOC at temperatures above 473 K; at these conditions, no
carbonaceous deposits were accumulated on the catalyst surface. Bioassays were found as a complement to chemical analyses for reducing the toxicological
impact on the ecosystem. In the presence of a Ru/TiO 2 catalyst, the toxicity to Daphnia magna and Vibrio fischeri of the oxidized materials was greatly reduced
compared with that of the starting solutions; for example, toxicity of aqueous phenol solution treated by the CWAO process was reduced by more than 98 %.
Justification for acceptance
This study based on an interdisciplinary approach demonstrates that the use of a Ru/TiO 2 catalyst in the CWAO process carried out in a continuous-flow tricklebed
reactor, enables long-term operation as well as complete removal and detoxification of typical model pollutants.
References
[1] V.S. Mishra, V.V. Mahajani, J.B. Joshi, Ind. Eng. Chem. Res. 34 (1995) 2;
[2] A. Pintar, M. Besson, P. Gallezot, Appl. Catal. B 30 (2001) 123;
[3] D.P. Minh, G. Aubert, P. Gallezot, M. Besson, Appl. Catal. B 73 (2007) 236.
AW-14
Wet Air Oxidation of Phenol over ceria and doped-ceria supported platinum and ruthenium catalysts: Analysis of the
Carbonaceous Deposit and Study of its impact on the catalytic activity
S. Keav, J. Barbier Jr.* and D. Duprez
University of Poitiers, LACCO UMR CNRS 6503, Laboratoire de Catalyse par les Métaux,
40, Avenue du Recteur Pineau, F-86022 Poitiers Cedex, France.
*Corresponding author. Tel: +33 (0)5.49.45.48.31, Fax: +33 (0)5.49.45.37.41,
e-mail: jacques.barbier.jr@univ-poitiers.fr
Background
During the last decades, Catalytic Wet Air Oxidation (CWAO) has proved to be an efficient technique to dispose of wastewaters containing toxic pollutants.
Homogeneous as well as solid catalysts were tested, the latter offering the advantage of being easily recoverable and reusable. Amongst them, ceria supported
noble metal catalysts, although resistant to leaching, revealed to be prone to deactivation. This loss of activity was attributed to the deposition of carbonaceous
materials on the surface of the catalyst [1, 2]. The following study was focused on the analysis of this deposit and on the determination of its influence on the
oxidation reaction of phenol.
Results
Several catalysts, supported on CeO 2 or Zr 0.1 Ce 0.9 O 2 and Zr 0.1 (Ce 0.75 Pr 0.25 ) 0.9 O 2 mixed oxides, were tested. In comparison with ruthenium based catalysts, those
containing platinum appear to be, on the one hand, more active for phenol conversion and TOC removal and, on the other hand, more selective for carbon
dioxide. Used catalysts were subjected to Elemental Analysis, Temperature Programmed Oxidation (TPO), Differential Thermal Analysis (DTA) and Soxhlet
extraction followed by GC-MS analysis, which allowed both the elemental and molecular compositions of the carbonaceous deposits to be determined. The
amount of carbonaceous materials deposited on the catalytic surface is more significant for mixed oxides than for ceria. It seems to be related to the nature of the
support rather than to that of the metal. In situ as well as ex situ regenerations were performed. In situ reactivation revealed to be more efficient for ruthenium and
ceria based catalysts while ex situ regeneration by thermal oxidation made it possible to recover the initial activity, whatever the nature of the support and the
metal phase.
Justification for acceptance
Catalytic Wet Air Oxidation remains one of the most promising catalytic processes for water pollution abatement. However, full control of this technique will not
be achieved unless more detailed studies about the deactivation phenomenon and regeneration methods are carried out. The present work, which fits into the
context of Catalysis for Clean Water, is directed to this aim.
References
[1] P. Massa, F. Ivorra, P. Haure, F. Medina Cabello, R. Fenoglio, Catalysis Communications 8 (2007) 424-428.
[2] J. Barbier Jr, L. Oliviero, B. Renard, D. Duprez, Topics in Catalysis 33 (2005) 77-86.

POSTER
ABSTRACTS
Autocatalysis

113 Synthesis, phase stability and catalytic activity of Pd-doped La-based perovskites during SCR-NO x with C 3 H 6
G.C. Mondragón Rodríguez*, B. Saruhan
German Aerospace Center (DLR), Institute of Materials Research, Linder Hoehe 51147, Cologne Germany
*Corresponding author: Tel: +49 (02203) 6013869, Fax: +49 (02203) 6013249
E-Mail: extern.mondragon-rodriguez@dlr.de
Background
A wide variety of perovskite combinations functions as host materials for precious metals (e.g. Pt, Rh, Pd, Ru) [1]. This is because the synergic interaction
between the metal and the host perovskite structure occurs under redox conditions leading to improved catalytic properties [1]. As it is reported, a reversible
diffusion of Pd ions in and out of the crystal lattice takes place under stoichiometric combustion conditions (=1) [2]. We studied the redox behaviour of
palladium ions in LaFe 0.65 Co (0.35-x) Pd x O 3 (x=0, 0.05) catalysts under reducing and oxidizing conditions, and tested its catalytic performance during the SCR NO x -
reaction with C 3 H 6 under lean-burn conditions.
Results
A modified citrate route was successfully employed to synthesize palladium substituted perovskites. XRD results show the presence of pure orthorhombic
perovskite with composition LaFe 0.65 Co 0.3 Pd 0.05 O 3 that begins to crystallize at approx. 600°C and completes its crystallization at temperatures slightly below
700°C. According to the crystallization behaviour we can postulate that our catalyst is metastable up to 700°C. Our XRD results show that this catalyst displays a
reversible behaviour under redox conditions. The exposure of LaFe 0.65 Co 0.3 Pd 0.05 O 3 catalyst calcined preliminary at 700°C, to 5vol. %H 2 in N 2 at 600°C/1h leads
to diffusion of Pd ions as metallic sites (10 to 15nm size) which reversibly disappear after re-oxidation process in static air at 600°C/1h detected with ex-situ
SEM and TEM analysis.
The catalytic test during the SCR-NO x with C 3 H 6 model reaction shows an improved catalytic performance of the Pd-doped perovskite (LaFe 0.65 Co 0.3 Pd 0.05 O 3 )
catalyst compared to the Pd-supported (Pd/LaFe 0.65 Co 0.35 O 3 -700°C) catalyst. The Pd-free perovskite LaFe 0.65 Co 0.35 O 3 -700°C shows only negligible activity under
the same reaction conditions. The LaFe 0.65 Co 0.3 Pd 0.05 O 3 -700°C catalyst shows NO conversion up to 40% at 275°C even at high space velocities (SV~220 800hr -1 ).
Justification for acceptance
Automotive catalysts that selectively eliminate NO x and other harmful emissions under lean-burn conditions are strongly needed. The integration of precious
metals ions such as Pd into perovkite structure provides an alternative to produce new generation of catalysts with improved catalytic properties. The 5 th ICEC
provides a suitable platform to address this subject.
References
[1] H. Tanaka, M. Misono, Current Opinion in Sol. State and Mat Sci. 5 (2001) 381-387.
[2] Y. Nishihata, J. Mizuki, T. Akao, H. Tanaka, M. Kimura, T. Okamoto and H. Hamada, Nature 418, 164-167 (2002).
122 In situ FT-IR investigation on Pd/SA for the selective catalytic reduction of NO with CH 4
Hongyan Zhang a, b , Aiqin Wang a , Lin Li a , Xiaodong Wang a and Tao Zhang a, *
a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, CAS, Dalian 116023, China
b Graduate School of the Chinese Academy of Sciences, Beijing, 100049, China
*Corresponding author. Tel: +86 411 84379015, Fax: +86 411 84691570, e-mail: taozhang@dicp.ac.cn
Background
In our previous work [1], Pd supported on sulfated Al 2 O 3 (SA) has been found to be an efficient catalyst for selective catalytic reduction (SCR) of nitric oxide
with methane. However, the respective role of Pd and sulfation of the Al 2 O 3 support is not yet clear. In the present work, in situ FT-IR was employed to track the
adsorption of NO on different catalysts, as well as the intermediate species formed on the surface, in an effort to clarify the reaction mechanism on this Pd/SA
catalyst.
Results
FT-IR measurements were performed on a Bruker spectrometer. Prior to the adsorption measurements, the samples were activated at 773 K in oxygen for 30 min,
followed by evacuation at the same temperature for 1 h. The spectra were collected at room temperature. The results showed that the adsorption of NO on Al 2 O 3
produced bands at 1624, 1540, 1458, 1318, 1230, and 1074 cm -1 , which could be attributed to nitro/nitrito surface compounds. Supporting Pd on the Al 2 O 3
support was found to increase significantly the intensity of these bands, implying Pd promotes the adsorption of NO. Similarly, sulfation of the Al 2 O 3 support also
improved the NO adsorption. On the other hand, for the co-adsorption of NO and O 2 , various surface nitrate species with adsorption bands at 1304, 1564, 1585,
and 1619 cm -1 , are identified. Moreover, it was found that sulfation of the Al 2 O 3 support largely restrained the formation of surface nitrates, as revealed by the
decreased stability of the surface nitrate species on the SA and Pd/SA samples. This result suggests that sulfation of the support can activate the surface nitrate
species and make it react towards CH 4 more easily.
Justification for acceptance
Selective catalytic reduction of NO with CH 4 under oxygen-rich atmosphere has been thought as a potentially promising way to abatement of automotive
emissions. Our previous activity test has shown that Pd/SA was very active and selective for this reaction. Therefore, detailed characterization on this catalyst to
clarify the role of the active components is very important for further improvement of the SCR catalysts.
References
[1] N. Li, A. Q. Wang, X. D. Wang, L. L. Ren, T. Zhang, Appl. Catal. B 50 (2004) 1.

127 Catalytic activity for soot combustion of birnesite and criptomelane.
I. Atribak a , A. Bueno-López a,* , A. García-García a , P. Navarro b , D. Frías b , M. Montes b .
a
MCMA Group. Inorganic Chemistry Department. University of Alicante, Ap-99, E-03080 Alicante, Spain.
b Chemical Engineering Group, Applied Chemistry, University of Pais Vasco, Paseo Manuel de Lardizabal 3, 20018 San Sebastián, Spain.
*Corresponding author. Tel: +34 965903400 (ext.2226), Fax : +34 965903454, e-mail: agus@ua.es
Background Catalyzed soot combustion in diesel engine exhausts is an issue of ongoing research due to the environmental and health impact of soot emission.
Among the different catalysts proposed for diesel soot removal, metal oxides such as CeO 2 and mixed oxides (Ce-Zr, Ce-La, for instance) [1, 2] show promising
behavior and could substitute current Pt-based catalysts. On the other hand, certain manganese oxides have shown high catalytic activity for gas oxidation
reactions (VOC combustion [3] as an example). This has motivated the study of the activity of two octahedral manganese oxides (birnesite and cryptomelane) for
catalyzed soot combustion both under O 2 and NOx/O 2 gas mixtures.
Results Birnesite and cryptomelane (20 and 108 m 2 /g, respectively) were prepared following the
100
procedure described elsewhere [4,5], and the formation of the desired phases was confirmed by XRD. As
birnesite
observed on Figure 1, both oxides lowered the soot combustion temperature, birnesite being more active than 75
criptomelane, while some other stoichiometric manganese oxides tested (MnO 2 , Mn 2 O 3 , Mn 3 O 4 ) did not show
cryptomelane
50
significant catalytic activity. The enhanced activity of birnesite and cryptomelane is tentatively attributed to: (i) the
presence of Mn cations in different oxidation states, III/IV, which favors oxygen transfer throughout a redox
25
No catalyst
mechanism. In fact, the average oxidation states determined by H 2 -TPR are 3.53 and 3.89, respectively, and/or (ii)
0
the promoter effect of the K + cations that balance the manganese mixed oxides charge. The BET surface area of
300 400 500 600 700
Temperature (ºC)
the catalyst plays a minor role. NOx removal takes place along with soot conversion, reaching 40% NOx removal Figure 1. Soot conversion in temperature
programmed reactions at 10ºC/min performed
at 410ºC for birnesite.
under 500 ppm NOx + 5%O 2 .
References
[1] A. Bueno López, K. Krishna, M. Makkee, J.A. Moulijn, J. Catal. 230 (2005) 237.
(model soot = Printex-U Degussa; GHSV= 30000 h -1 ; soot
:catalyst wt. ratio = 1:4; loose contact)
[2] I. Atribak, A. Bueno López, A. García-García, Catal. Commun. 9 (2008) 250.
[3] I. Barrio, I. Legorburu, M. Montes, M.I. Domínguez, M.A. Centeno, A. Odriozola, Catal. Lett. 101 (2005) 151.
[4] J. Luo, Q. Zhang, A. Huang, S.L. Suib, Micropor. Mesopor. Mat. 35 (2000) 209.
[5] S. Ching, J. A. Landrigan, M. L. Jorgensen, N.G. Duan, S.L. Suib, C.L. O`Young, Chem. Matter. 7 (1995) 1604.
Soot conversion (%)
131 Manganese Based Materials for Diesel Exhaust SO 2 Traps
O. Kröcher * , K. Tikhomirov, M. Elsener, M. Widmer, A. Wokaun
Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
*Corresponding author. Tel: +41 56 310 20 66, Fax : +41 56 310 23 23, e-mail: oliver.kroecher@psi.ch
Background
Deactivation by sulfur is one of the major challenges in the development of automotive catalysts, which restricts the range of applicable components to sulfurinsensitive
chemical elements and compounds. One possibility to overcome this problem is the application of a SO x trap upstream of the catalyst.
Results
We found manganese oxide (MnO x ) to be a simple and cheap material for the storage of SO x , which seems to be superior to all previously described SO x trap
materials. In order to reach nearly constant SO x storage efficiencies, the material has to be prepared in amorphous form. This results in a labile crystal structure,
which is easily converted during sulfatization resulting in a much smaller diffusion resistance. The moderate decline in activity, discernible in a long-term
experiment, is simply caused by the consumption of MnO x during reaction. The material could be optimized with respect to the average exhaust gas temperature.
The activity of KNO 3 -MnO x , for example, did not change with time at a lower temperature of 200 °C and it was always clearly higher than that of the undoped
one. The storage efficiency stayed the same for particle sizes within a broad range, i.e. SO x storage is only a chemically controlled process. For prolonged SO 2
dosing total conversion to manganese sulfate was observed, showing that the storage potential of the material was fully exploited. SO 2 and SO 3 were stored with
the same efficiency. Unlikely many SO x storage materials, the SO 2 storage over MnO x does not require the preliminary oxidation of SO 2 to SO 3 , since manganese
sulfate is directly formed from manganese oxide and SO 2 : MnO 2 + SO 2 MnSO 4 . However, a large part of the manganese oxide is present as Mn 2 O 3 and either
SO 2 or Mn 2 O 3 has to be oxidized in the reaction sequence (SO 2 + ½ O 2 SO 3 or Mn 2 O 3 + ½ O 2 2 MnO 2 ). The almost equal storage efficiencies of SO 2 and
SO 3 imply that the binding of SO 2 or SO 3 on manganese is the rate limiting step, whereas the above mentioned oxidation reactions must be faster. The storage
activity of manganese oxide is a first order reaction with regard to the amount of MnO x as well as the SO 2 concentration. Therefore, reaction engineering for this
process has to aim at providing as much MnO x as possible in view of practical considerations.
Justification for acceptance
The results of this project show that it is possible to quantitatively absorb SO 2 from exhaust gases with a relatively simple and cheap material. This opens up new
vistas for the application of sulfur sensitive materials in exhaust gas catalysts, such as NO x storage and reduction (NSR) catalysts.
References
[1] K. Tikhomirov, O. Kröcher, M. Elsener, M. Widmer, A. Wokaun, Appl. Catal. B 67 (2006) 160-167.

132 New Insights into the Reactions between NH 3 , NO and NO 2 over Fe-ZSM5
O. Kröcher * , M. Elsener
Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
*Corresponding author. Tel: +41 56 310 20 66, Fax : +41 56 310 23 23, e-mail: oliver.kroecher@psi.ch
Background
The forthcoming Euro6 emission limits for Diesel vehicles necessitate the combination of urea-SCR systems for the reduction of NO x with Diesel particulate
filters (DPF) for the abatement of soot emissions. Metal-exchanged zeolites, such as Fe-ZSM5, are currently investigated as SCR catalysts, since they resist the
high temperatures during regeneration of the DPF over the lifetime of the aftertreatment system. The SCR chemistry over Fe-ZSM5 involves the oxidation of NO
to NO 2 and the formation of nitric acid/ammonium nitrate and nitrous acid/ammonium nitrite, the former decomposing to N 2 O and the latter to nitrogen [1-4].
Results
High-precision measurements of the SCR activity and selectivity of Fe-ZSM5 over a broad range of NH 3 /NO/NO 2 /HNO 3 concentrations at different temperatures
in steady-state and transient-response experiments allows us to explain all of the observed reaction products (N 2 , HNO 3 , NH 4 NO 3 , N 2 O, NO) and stoichiometries
and resulted in new insights into the mechanism of the underlying reaction network.
NO-SCR:
fast fast fast
H 2 O
fast
NO + HNO 2 [NH 4 NO 2 ] N 2 + 2H 2 O
O 2
-H
2NO 2NO ads
2
+
+
NO
H 2 O
-H + NH ads
3
NH ads
3
NO ads
2 NH ads
3
NO - 3 HNO 3 HNO 2 [NH 4 NO 2 ] N 2 + 2H 2 O
fast
H 2 O
fast
NH ads
3
fast
NO + HNO 2 [NH 4 NO 2 ] N 2 + 2H 2 O
-H 2NO 2 2NO ads
2
+
+
H 2 O NO NO 2 NH ads
3 NO - 3 HNO 3 HNO 2 [NH 4 NO 2 ] N 2 + 2H 2 O
-H + rate determining
NH ads
3
fast
NH 4 NO 3
NH 4 NO 3
NO/NO 2 -SCR
References
[1] O. Kröcher, 1 st MinNOx Conference – Minimization of NOx-Emissions Through Exhaust Aftertreatment, 1-2 February 2007, Berlin, Germany.
[2] M. Devadas, O. Kröcher, M. Elsener, A. Wokaun, N. Söger, M. Pfeifer, Y. Demel, L. Mussmann, Appl. Catal. B 67 (2006) 187-196.
[3] M. Devadas, O. Kröcher, M. Elsener, A. Wokaun, G. Mitrikas, N. Söger, M. Pfeifer, Y. Demel, L. Mussmann, Catal. Today 119 (2007) 137-144.
[4] O. Kröcher in P. Granger (Ed.): Past and Present in DeNOx catalysis - From Molecular Modelling to Chemical Engineering, Vol. 171, Elsevier, Amsterdam
2007, ISBN 978-0-444-53058-5.
133 Chemical Deactivation of V 2 O 5 /WO 3 –TiO 2 SCR Catalysts by Additives and Impurities from Fuels,
Lubrication Oils, and Urea Solution
O. Kröcher * , M. Elsener, D. Nicosia, I. Czekaj
Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
*Corresponding author. Tel: +41 56 310 20 66, Fax : +41 56 310 23 23, e-mail: oliver.kroecher@psi.ch
Background
V 2 O 5 /WO 3 -TiO 2 catalysts are widely employed for the selective catalytic reduction (SCR) of nitrogen oxides with urea in Diesel trucks in Europe. Over the
lifetime of a heavy-duty Diesel vehicle equipped with an SCR system, a considerable amount of combustion products of different lubrication oil additives and
impurities in the fuel or the urea solution are deposited on the surface of catalyst, thereby affecting its activity and selectivity.
Results
The influence of the combustion products of different lubrication oil additives (Ca, Mg, Zn, P, B, Mo) and impurities in Diesel fuel (K from raps methyl ester) or
urea solution (Ca, K) on the activity and selectivity of V 2 O 5 /WO 3 –TiO 2 SCR catalysts were investigated. It was found that potassium strongly reduced the
adsorption equilibrium constant K NH3 of ammonia. Calcium caused less deactivation than potassium and did not affect the ammonia adsorption to the same extent,
but it lowered the intrinsic SCR reaction rate. Moreover, deactivation by calcium was much reduced if counter-ions of inorganic acids were present (order of
improvement: SO 2- 4 > PO 3- 4 > BO 3- 3 ). Zinc was again less deactivating than calcium, but the positive effect of the counter-ions was weaker than in case of
calcium.
The combination of NH 3 -TPD, DRIFT spectroscopy, XPS and theoretical DFT calculations allowed us to explain the deactivation mechanism for K and Ca.
These elements stabilize the non atomic holes of the (0 1 0) V 2 O 5 phase. As a consequence, V–OH Brønsted acid sites and V 5+ =O sites are inhibited, which are
both of crucial importance in the SCR process. Our deactivation model also gives an explanation to the very low concentrations of potassium needed to deactivate
the SCR catalyst, since one metal atom sitting on such a non-atomic hole site deactivates up to four active vanadium centers.
Justification for acceptance
Ten thousands of urea-SCR systems with V 2 O 5 /WO 3 -TiO 2 catalysts are on the road in Europe. Our study provides information about the deactivation potential of
the different elements as well as a chemical deactivation mechanism, which is a pre-requisite for the further development of vanadia-based catalysts as well as
lubrication oils, fuels and urea solution. The results confirm the efforts in industry to develop metal-free lubrication oils and the low ISO/DIN limits for the
alkaline content of urea solution.
References
[1] D. Nicosia, I. Czekaj, O. Kröcher, Appl. Catal. B 77 (2008) 228-236.
[2] O. Kröcher, M. Elsener, Appl. Catal. B 75 (2008) 215-227.

137 Hydrogen Effect on Urea-SCR by Ag/alumina: Practical and Mechanistic Aspects
Ken-ichi Shimizu*, Atsushi Satsuma
Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
* Corresponding author. Tel. : +81-52-789-4608 FAX : +81-52-789-3193,
e-mail : kshimizu@apchem.nagoya-u.ac.jp
Background
There is a possibility that fuel optimised engines combined with the selective catalytic reduction of NO by urea system (urea-SCR) could reduce fuel
consumption by 7%, resulting in less CO 2 emission in a global perspective. In order to reduce the volume of SCR system, new catalysts should be developed
which have a high NO conversion under high GHSV condition over wide temperature range as well as a high stability. Following the report by Satokawa [1] and
our research group [2] on the dramatic promotional effect of H 2 on HC-SCR by Ag/Al 2 O 3 , Richter et al. discovered an unusual activity enhancement of Ag/Al 2 O 3
for NH 3 -SCR [3]. Knowing the fact that urea hydrolysis to yield NH 3 and CO 2 is catalyzed by acid catalysts such as alumina, we have develpoed the H 2 assisted
urea-SCR by Ag/Al 2 O 3 as a highly effective De-NOx system. On the basis of the kinetic and spectroscopic results of H 2 assisted NH 3 -SCR on Ag/Al 2 O 3 ,
comprehensive reasons for the hydrogen effect in NH 3 -SCR is discussed focusing on the role of Ag + n cluster and reductively activated oxygen species on NH 3 -
activation.
Results
The addition of 0.5% H 2 in urea-SCR by Ag/Al 2 O 3 drastically increased the NO conversion. Among various silver-based catalysts Ag/Al 2 O 3 showed highest
activity for H 2 assisted urea-SCR, and high NO conversions (above 84%) were achieved over a wide temperature range (200-500°C) at GHSV of 75,000 h -1 .
After H 2 assisted urea-SCR at 250°C with 10% H 2 O and 50ppm SO 2 under GHSV of 380,000 h -1 for 24 h, NO conversion over Ag/Al 2 O 3 decreased from 48% to
30%, though original activity was recovered when the deactivated catalyst was heated at 500°C in the urea-SCR condition for 1h. Additional advantage of this
catalytic system is its high activity for H 2 assisted HC-SCR reaction at high temperature (500°C), indicating a possibility of urea-free de-NOx catalysis at high
temperature region. The above properties are suitable for diesel de-NO x catalysis, which must be operated under transient conditions in a wide temperature
window [4]. The NO reduction rate of Ag/Al 2 O 3 for NH 3 -SCR at 200°C increased by a factor of 630, when H 2 (1%) was added to the reaction gas mixture.
Kinetic studies indicate that H 2 addition increased the rate of NH 3 reaction in NH 3 + O 2 below 400°C and decreased the activation energy for NH 3 + O 2 reaction.
This indicates that H 2 addition is effective for the oxidative activation of NH 3 . In situ UV-vis results under the reaction condition show that Ag + ion and Ag
+
n
cluster (n 8) co-exist during H 2 -NH 3 -SCR. ESR spectra of the catalyst treated under the reaction condition show that the superoxide ion is formed on the
catalyst, and its amount increased with H 2 concentration. The NO reduction rate and the relative amount of the cluster during the reaction increased with H 2
concentration, and the rate correlates fairly well with the relative amount of the cluster, indicating that the cluster acts as active species in H 2 -NH 3 -SCR.
Combined with the recent kinetic results by Kondratenko et al. [5], it is concluded that Ag
+ n cluster formed by H 2 -reduction of Ag + ions is involved in the
reductive activation of molecular oxygen into superoxide ion, which should act as effective oxidant for N-H activation of NH 3 to NH x intermediate [6].
References
[1] S. Satokawa, Chem. Lett., 2000 (2000) 294.
[2] K. Shimizu, A. Satsuma, Phys. Chem. Chem. Phys. 8 (2006) 2677.
[3] M. Richter, R. Fricke, R. Eckelt, Catal. Lett. 94 (2004) 115.
[4] K. Shimizu, A. Satsuma, et al., Appl. Catal. B, 77 (2007) 202.
[5] E. Kondratenko, V.A. Kondratenko, M. Richter, R. Fricke, J. Catal. 239 (2006) 23.
[6] K. Shimizu, A. Satsuma, J. Phys. Chem. C, 111(2007) 2259.
140 Kinetics and mechanism of carbon oxidation with NO 2 and O 2 in presence of Ru/Na-Y catalyst
M. Jeguirim a* , V. Tschamber a , K. Villani b , J.F.Brilhac a , J.A. Martens b
a Laboratoire Gestion des Risques, Environnement 25, rue de Chemnitz 68200 Mulhouse – France
b Centrum voor Oppervlaktechemie en Katalyse, K.U. Leuven, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium
* Corresponding author: Tel: +33-3-89327658; fax: +33-3-89327661, E-mail address: mejdi.jeguirim@uha.fr
Background
Diesel Particulate Filter (DPF) appears to be an effective technology to control soot emission and to comply with emission standards. The principle of DPF
systems is based on the soot trapping followed by its combustion in order to regenerate the filter. However, even if various DPF systems are in use today, filter
regeneration technology remains a technical challenge [1]. Among catalysts developed for the regeneration strategy,Pt shows a higher catalytic activity for soot
oxidation [2]. Recently, a comparison between ruthenium and platinum based catalysts activity showed that Ru is more active for the soot oxidation [3].
Results The investigation of carbon oxidation by NO 2 and O 2 in presence of Ru/Na-Y was carried out in a fixed-bed reactor in conditions close to automotive
exhaust gas aftertreatment. Isothermal oxidation experiments of a physical mixture of 50 mg carbon black and 50 mg catalyst were performed in the temperature
range 300-400°C for 0-600 ppm NO 2 and 0-10% O 2 . A remarkable increase of the carbon oxidation rate by NO 2 and O 2 in presence of Ru/Na-Y catalyst was
observed. The global mechanism for carbon oxidation in these experimental conditions may be written as follows:
C + O 2 CO 2 (1)*
C + NO 2 CO+ NO (2)
C + 2 NO 2 CO 2 + 2 NO (3)*
C + ½ O 2 + NO 2 CO+ NO 2 (4)
C + O 2 + NO 2 CO 2 + NO 2 (5)*
*: Reactions catalysed by Ru.
The overall gasification rate of carbon oxidation by the NO 2 -O 2 mixture in presence of Ru/Na-Y catalyst is the sum of the direct C-O 2 (Eq 1), C-NO 2 (Eq 2-3),
reactions and the co-operative C-NO 2 -O 2 (Eq 4-5), reaction. The overall carbon gasification rate, r is expressed as follows:
cat cat cat
r r r r
dirO dirNO coop (6)
2
2
The intrinsic carbon gasification rates r cat ,
cat
cat
r and r
dirO
coop were determined using a mono-dimensional model of the reaction through the fixed bed. The
2 dirNO2
experiments of the carbon oxidation by NO 2 and O 2 in presence of Ru allow to describe the temperature dependence of the different intrinsic carbon gasification
rates as following:
cat 1
cat
3
84520
rdirO
( s ) k
5.56 10 exp
2
dirO
P
2 tot
X
O
x P
2
tot
X
(7)
O2
RT r cat
( s 1
) k cat
P k cat
P dirNO
2 CO2
NO
= 9.1 x 10 -4 exp (-
40900
2 CO NO
) + 1.8 x 10 -3 exp (-
58300 ) (8)
2
RT
RT
cat 1
cat
0.2 cat
0.2
rcoop
( s ) kO2,CO
P
2 NO
X
2 O
k
2 O2,CO
PNO
X =13.1exp(-
85430
2 O2
) P X 0. 2
+0.4exp(- 76260
NO2 O
RT
2
) P X 0. 2
(9)
NO2 O
RT
2
References
[1] C. Gorsmann, Monatshefte fir chemie 136(2005) 91-106. [2] M. Jeguirim, V. Tschamber, P. Ehrburger, App. Cat. B 76 (2007) 235-240.
[3] V. Tschamber, M. Jeguirim, K. Villani, J. Martens, P. Ehrburger, App. Cat. B 74 (2007) 299.

143 Novel Preparation Method for Ag/Al 2 O 3 HC-SCR Catalysts
Hannes Kannisto * , Hanna Härelind Ingelsten and Magnus Skoglundh
Competence Centre for Catalysis, Chalmers University of Technology, SE-412 68 Göteborg, Sweden
* Corresponding author. Tel: +46 31 772 3372, Fax: +46 31 16 00 62, e-mail: hannes.kannisto@chalmers.se
Background
A new preparation method for Ag/Al 2 O 3 catalysts for HC-SCR applications has been developed [1]. The preparation technique is a sol-gel based method with
freeze-drying to preserve the pore structure of the catalyst. This method enables the silver to be finely dispersed throughout the alumina matrix. For comparison,
samples prepared by impregnation and by sol-gel with thermal drying were also studied. The nominal silver content of all samples was 5 wt% and the samples
were characterized by nitrogen sorption, XRD, XPS and TEM. Activity studies with propene and n-octane as reductant were also performed.
Results
The samples show similar specific surface area and narrow pore size distribution. However, the mean pore diameter is significantly lower for the sol-gel samples
than for the impregnated sample. The combined results of the XRD, XPS and TEM characterization show that the dispersion of silver is higher for the sol-gel
samples than for the impregnated sample. Further, the oxidation state of silver is higher in the freeze-dried sol-gel sample than in the impregnated sample. For
propene as reductant, the freeze-dried sample shows high NO x reduction albeit at high temperatures, while the impregnated sample shows very low NO x
reduction at a similar temperature interval. For n-octane as reductant, the NO x reduction is generally lower, while the thermally dried sol-gel sample shows the
similar high NO x reduction as for propene. The temperature window is broadened for all samples, compared to propene as reducing agent. Furthermore, the
temperature corresponding to the maximum NO x reduction is generally shifted towards lower temperatures, except for the freeze-dried sol-gel sample. A
comparison of the CO 2 formation shows high CO 2 levels for the impregnated sample, whereas the CO 2 formation is considerably lower for the sol-gel samples,
regardless of reductant. This pattern is similar for the NO 2 formation with high levels for the impregnated sample, but significantly lower levels for both sol-gel
samples. Together with the characterization results, this indicates that the freeze-dried sol-gel sample contains well dispersed silver throughout the alumina
matrix, probably mainly as non-metallic silver species. The results suggest that the non-metallic silver is able to reduce NO to N 2 , while metallic silver is required
to activate the hydrocarbons, especially at lower temperatures.
Justification
A novel preparation method for Ag/Al 2 O 3 catalysts is presented. Characterization results suggest that this catalyst contain very well dispersed, non-metallic Ag
species, showing high activity for propene-SCR. Mechanistic aspects of the different preparation methods will be discussed.
References
[1] H. Kannisto, H. Härelind Ingelsten, M. Skoglundh, To be submitted (2008)
144 CeO 2 and CeO 2 -ZrO 2 mixed oxides as catalysts for the combined removal of NO x and soot from diesel exhausts.
I. Atribak a , A. Bueno-López a , A. García-García a,* .
a
MCMA Group. Inorganic Chemistry Department. University of Alicante, Ap-99, E-03080 Alicante, Spain.
*Corresponding author. Tel: +34 965909419, Fax : +34 965903454, e-mail: a.garcia@ua.es
Background Controlling diesel exhaust gas
100
emissions is an important challenge nowadays. In the
future several diesel emissions control systems will
Average soot oxidation be combined into a single unit to minimise space
rate (g soot/s)
requirements, and for cost and efficiency 75
considerations [1]. In this sense, a versatile and durable
CeO 2-500
11.4
catalyst, loaded on a particulate filter, able to
CeO 2-1000
catalyse the NO x -soot reaction under driving conditions
1.2
would be very desirable. Over the last three decades 50
Ce 0.76Zr 0.24-500
14.9
Highest NOx
removal and soot there has been a huge investigation about the excellent
behaviour of ceria and ceria-zirconia systems (high
Ce 0.76Zr 0.24-1000
4.1
oxidation rate
OSC, thermal stability….), as essential components of
TWC catalysts. These features are very interesting 25
for diesel emission catalysts as well. Therefore, the aim
of this work was to investigate the feasibility of ceria
and different formulations of ceria-zirconia mixed oxides
for the combined removal of NO x and soot from 0
diesel exhaust.
0 25 50 75 100
Results Cerias and ceria-zirconia mixed
Soot conversion (%)
oxides, with different Ce/Zr ratios were prepared by Figure 1. NOx elimination profile versus soot
using a precipitation or co-precipitation route as
conversion for selected catalysts from isothermal
reaction at 500°C, under 500 ppm NOx + 5%O 2 .
described elsewhere [2]. The different formulations (model soot = Printex-U Degussa; GHSV= 30000 h -1 soot
were calcined in the range of 500-1000°C. The
:catalyst wt. ratio = 1:4; loose contact)
Uncatalysed reaction did not take place at 500ºC.
textural and structural characterisation was
performed by N 2 adsorption, XRD and Raman Spectroscopy. Most of the catalysts prepared resulted to be very active for soot combustion, even decreasing the
temperature at which 50 percentage of soot conversion is reached in 100°C, --for the case of the catalyst exhibiting the best performance (Ce 0,76 Zr 0,24 O 2, calcined
at 500°C)--. As observed on Figure 1, these catalysts are very efficient for the combined removal of NO x and soot under isothermal conditions, but the
corresponding profiles are very dependent on catalyst formulation and calcination temperature. High NO x conversions are observed up to 25% of soot
consumption, but the activity is progressively seen decreased due to the lower amount of reductant in the reactor. N 2 O emission as reaction product was not
detected under our experimental conditions. The BET surface area of the samples prepared plays an important role as well as the ceria-based materials’ ability to
catalyse NO oxidation to NO 2 , thus promoting soot combustion.
Justification for acceptance This work forms part of one of the most significant topics of this Conference on Environmental Catalysis: the Automotive
Emission Control. In particular, the removal of nitrogen oxides and soot from diesel exhausts, which is one of the most challenging issues of current scientific and
technological research.
References
[6] M.V. Twigg, Appl. Catal. B 70 (2007) 2.
[7] I. Atribak, A. Bueno-López, A. García-García, Proceedings of Catalysis for Environment: Depollution, Renewable Energy and Clean Fuels; ISBN 978-83-916351-3-1 (2007) 137.
NO x elimination (%)

148 Role of enolic species in the selective catalytic reduction of NOx with hydrocarbons over Ag/Al 2 O 3
H. He * , Y.B. Yu, Q. Wu and X.L. Zhang
Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, P. R. China
*Corresponding author. Tel: +86 10 62849123, Fax: +86 10 62923563, e-mail: honghe@rcees.ac.cn
Background
Emission control of NOx from diesel and lean-burn engine exhausts remains one of the major challenges for environmental catalysis. The selective catalytic
reduction (SCR) of NOx with hydrocarbons over Ag/Al 2 O 3 is a highly promising technology. [1,2] We have found a novel enolic surface species formed on
Ag/Al 2 O 3 and proposed a new mechanism to explain the high efficiency of the SCR of NOx with ethanol over Ag/Al 2 O 3 . [2] The present work is to investigate the
role of the enolic species on the tolerances to SO 2 and H 2 O for the SCR of NOx with hydrocarbons over Ag/Al 2 O 3 using in situ DRIFTS and DFT calculations.
Results
The effects of H 2 O and SO 2 on the SCR of NOx with various reductants over Ag/Al 2 O 3 were carefully studied. When using C 3 H 6 as the reductant, the conversion
of NOx dramatically decreased by the addition of water vapor to the gas stream, especially in the temperature range of 573773 K. With C 2 H 5 OH as the
reductant, however, the presence of water vapor significantly enhanced the reduction of NOx at lower temperatures. In situ DRIFTS study showed that the
presence of water vapor selectively inhibited the formation of acetate, whereas it led to a slight increase in the concentration of enolic species on Ag/Al 2 O 3 during
the reduction of NOx by C 3 H 6 or C 2 H 5 OH. In the SCR of NOx by C 3 H 6 , the formation of acetate and its subsequent reaction play a key role, so that the presence
of water vapor leads to a decrease in the conversion of NOx by C 3 H 6 . In the case of the reduction of NOx by C 2 H 5 OH, however, the main mechanistic pathway is
connected with the enolic species, which was promoted in the presence of H 2 O. The decrease in the surface concentration of acetate favors the formation of enolic
species and the subsequent reaction. As a result, NOx reduction by C 2 H 5 OH is promoted by water vapor.
Activity tests showed that the efficiency order of the reductants for the SCR of NOx in the presence of SO 2 is as follows: C2 (C 2 H 5 OH) > C4 (1-butanol) > C3
(C 3 H 6 , IPA, 1-propanol). Evidence from the in situ DRIFTS spectra shows that the presence of sulfate species on Ag/Al 2 O 3 not only inhibited the formation of
NO 3 - , but also inhibited the reaction of enolic species with NO 3 - to form –NCO species, which is responsible for the deactivation of Ag/Al 2 O 3 during the SCR of
NOx with C3 and C4 reductants in the presence of SO 2 . In contrast, no pronounced deactivation effect of SO 2 was observed when C2 oxygenated reductant was
used under the identical experimental conditions. The C2 enolic species formed from the partial oxidation of C2 reductants can inhibit the formation of sulfate
species on Ag/Al 2 O 3 in the presence of SO 2 . In this way, we could provide a new idea that it is possible to alter surface reaction to synthesize a SO 2 -resistant
surface structure in situ by using different reactants.
References
[1] R. Burch, J.P. Breen, F.C. Meunier, Appl. Catal. B 39 (2002) 283.
[2] H. He, Y.B. Yu, Catal. Today 100 (2005) 37.
154 H 2 –SCR NO x catalytic activity and N 2 -selectivity of Pd-exchanged perovskites
G. C. Mondragón Rodríguez* a , B. Saruhan a , J. Breen b
a German Aerospace Center (DLR), Institute of Materials Research, Linder Hoehe 51147, Cologne Germany
b CenTACat, School of Chemistry and Chemical Engineering, Queens University Belfast, BT9 5AG
Northern Ireland
*Corresponding author: Tel: +49 (02203) 6013869, Fax: +49 (02203) 6013249
E-Mail: extern.mondragon-rodriguez@dlr.de
Background
As demonstrated in the literature, palladium exchanged perovskites offers enhanced catalytic performance in TWC applications [1]. Concerning the elimination
of nitrogen oxides under lean conditions over perovskite catalysts, the use of hydrogen as a reducing agent has been less studied [2]. Considering the stringency
of the legislation for emission in engines, the use of hydrogen as a reducing agent to eliminate NO x under lean conditions and at relatively low temperatures may
be a feasible solution in the forthcoming future. In this work we compare two palladium exchanged perovskite catalysts (La 0,95 Ce 0,05 Fe 0,95 Pd 0,05 O 3 and
BaTi 0,95 Pd 0,05 O 3 both calcined at 900°C) in terms of their catalytic activity regarding the NO-reduction employing H 2 as reducing agent. The effect of H 2 O + CO 2
or CO to the catalytic activity is also reported paying special attention to the N 2 -selectivity of the catalysts.
Results
Both catalysts showed similar NO-conversion capability (70-75%) under a feedstock composition of 720 ppm NO, 5% O 2 and 1% H 2 . Under these conditions, the
catalytic performance of the BaTi 0,95 Pd 0,05 O 3 catalyst was at low temperatures compared to the La 0,95 Ce 0,05 Fe 0,95 Pd 0,05 O 3 catalyst (150°C vs. 225°C). In the
presence of H 2 O and CO 2 in the feedstock, the maximum NO-conversion achieved at 240°C with the La 0,95 Ce 0,05 Fe 0,95 Pd 0,05 O 3 was 55% whilst 70% with the
BaTi 0,95 Pd 0,05 O 3 catalyst. Addition of 0.25% CO to the feedstock (without H 2 O and CO 2 ) reduced the NO-conversion capability of both catalysts drastically (50 %
with BaTi 0,95 Pd 0,05 O 3 and 60% with La 0,95 Ce 0,05 Fe 0,95 Pd 0,05 O 3 catalyst). N 2 -selectivity was higher with BaTi 0,95 Pd 0,05 O 3 (over 80%) compared to
La 0,95 Ce 0,05 Fe 0,95 Pd 0,05 O 3 (65-75%) at temperatures below 200°C under lean conditions, indicating a more selective character at low temperatures for single-site
catalyst. N 2 -selectivity of both catalysts was very little influenced in the presence of H 2 O and CO 2 in the feedstock, whereas it was reduced down to 50-60% with
the addition of CO.
Justification for acceptance
Selective NO x –reduction at lower temperatures is an issue related to the cold-start problems at the automotive catalysts. Palladium exchanged single-site
perovskite catalyst can offer a solution under lean conditions with relatively high NO x -reduction rate on addition H 2 as reductant at temperatures below
200°C.
References
[1] R. Karita, H. Kusabe, K. Sasaki, Y. Teraoka, Catal. Today 119 (2007) 83-87.
[2] I. Twagiraschema, M. Engelman-Pirez, M. Frere, L. Burylo, L. Gengembre, C. Dujardin, P. Granger, Catal. Today 119 (2007) 100-105.

158 Screening of different MnO x -CeO 2 doped catalysts for low-temperature SCR reaction
Maria Casapu, Oliver Kröcher, Martin Elsener
Paul Scherrer Institute, CH-5232 Villigen PSI, Aargau, Switzerland
Corresponding author: Tel: +41563102066, e-mail: oliver.kroecher@psi.ch
Background
The selective catalytic reduction (SCR) with NH 3 is successfully applied since several decades to reduce NO x emissions in the exhaust of stationary plants,
industry processes and recently also automotive applications [1-3]. Nevertheless, one of the remaining challenges is the broadening of the active temperature
window towards lower temperatures for a given catalyst volume. Various systems have been shown to posses some potential for low temperature applications,
including MnO x -CeO 2 recently reported by Qi and Yang [4].
In this study we carried out a screening of different MnO x -CeO 2 based catalysts for the NH 3 -SCR reaction in the low-temperature region. For this purpose MnO x -
CeO 2 was doped with oxides of iron, niobium, zirconium and tungsten.
Results
The systematic studies on MnO x -CeO 2 based catalysts were performed in the temperature range of 100-450°C using catalyst coated monoliths at a GHSV of
52,000 h -1 . The gas feed was composed of 1000 ppm NO, 1000 ppm NH 3 , 10% O 2 and 5% H 2 O. The results showed that among all tested systems the Nb 2 O 5
doped catalyst is the most efficient. The SCR activity and particularly the selectivity of the MnO x -CeO 2 catalyst were significantly improved by the addition of
Nb 2 O 5 . At 250°C 95% of NO was removed on NbO 5 -MnO x -CeO 2 whereas a DeNOx activity of 74% was observed for MnO x -CeO 2 . Moreover, at the same
temperature the selectivity towards N 2 O formation was reduced to only 5% for the Nb-containing catalyst while on MnO x -CeO 2 the N 2 O selectivity was 32%.
Besides, a significant broadening of the reaction temperature window towards higher temperatures was observed for NbO 5 -MnO x -CeO 2 . In contrast, modest SCR
performances and very pronounced N 2 O formation were measured for Fe 2 O 3 , ZrO 2 and WO 3 doped catalysts.
References
[1] P. Forzatti, Appl. Catal. A 222 (2001) 221
[2] www.daimler.com
[3] M. Koebel, M. Elsener and M. Kleemann, Catal. Today 59 (2000) 335
[4] G.Qi and R. T. Yang, Chem. Commun. 7 (2003) 848
168 Mercury oxidation and reduction by SCR-DeNOx-catalysts in coal fired power plants - Micro scale investigations
Raik Stolle a, *, Heinz Gutberlet b , Joachim Tembrink b , Heinz Koeser a
a Centre of Engineering Science, Chair of Environmental Technology, Martin-Luther-University Halle-Wittenberg,
D-06099 Halle/Saale, Germany
b E.ON Engineering GmbH, Alexander-von-Humboldt-Straße 1, D-45896 Gelsenkirchen, Germany
* Corresponding author. Tel: +49 3461 46 2705; Fax: +49 3461 46 2710; e-mail:
raik.stolle@iw.uni-halle.de
Background
The combustion process releases the coal mercury (Hg) in the elemental form (Hg 0 ). This Hg 0 from power plants is a major contributor to anthropogenic Hg
emissions. A promising way for reducing Hg in flue gases is the oxidation of the Hg 0 to water soluble compounds (Hg ox ) followed by sequestration in existing gas
cleaning devices. This oxidation reaction of Hg 0 in flue gases can be catalysed by SCR-DeNOx-catalysts [1]. In the present study the findings of a detailed lab
scale research programme on Hg oxidation by commercial SCR-DeNOx-catalysts under raw flue gas conditions of coal fired power plants are given.
Results
The investigation showed that the oxidation of Hg 0 to Hg ox in the presence of V 2 O 5 /WO 3 (MoO 3 )/TiO 2 based DeNOx catalysts depends substantially on the HCl
and HBr concentration in the flue gas. The oxidation velocity of Hg 0 by HBr is about 10 times faster then by the same mass based amount of HCl under otherwise
identical conditions. However, in most bituminous coal applications the chlorine effect is predominant because of the natural abundance of the two elements. At a
given hydrogen halide content - the Hg oxidation activity follows a first order kinetics with regard to the Hg 0 concentration. This first order Hg oxidation activity
constant of the different catalysts investigated can be numerically equal to the activity constant of the DeNOx reaction. Thus Hg oxidation is obviously a
comparatively fast reaction. Hg 0 oxidation rates enhanced to the Vanadium content of the catalysts. There are further dependent on the pitch or the cell opening of
the catalyst. There is a strong reverse effect on Hg 0 oxidation caused by the DeNOx-reaction (NO and NH 3 , DeNOx-active catalyst). The same effect can be
observed, if volatile organic compounds are oxidized at the catalyst. Under these conditions a reduction of Hg ox occurs whereby the overall Hg el oxidation is
strongly affected. This effect is supposed to be the result of the reduced vanadium species of the active sites of the SCR-DeNOx catalyst interacting with the
Hg ox . Possibilities to optimize mercury oxidation by SCR-catalysts will be discussed.
Justification for acceptance
In the future it will be necessary to decrease Hg emission from power plant considerably. The presented results give a deeper understanding of the catalytic Hg 0
oxidation processes, the first step for an efficient Hg removal process. These previously unpublished results will aid the development of efficient Hg removal
processes in power plants.
References
[1] Gutberlet, A. Spiesberger, F. Kastner, J. Tembrink, VGB Kraftwerkstechnik 72 (1992) 636-641

169 Support Modification to Improve the Sulphur Tolerance of Ag/Al 2 O 3 for SCR of NO x with Propene under Lean-Burn Conditions
Neelam Jagtap 1 , Shubhangi B. Umbarkar 1 , Pascal Granger 2 and Mohan K. Dongare 1*
1 Catalysis Division, National Chemical Laboratory, Pune-411008, India
2
Unité de Catalyse et de Chimie de Solide UMR CNRS 8181, Bât C3, Universite´des Sciences et Technologies de Lille, 59655 Villeneuve D’ascq Cedex, France
* Corresponding author. Tel.: +91-20-25902044; fax: +91-20-25902633, E-mail: mk.dongare@ncl.res.in
Background: Removal of NO x from lean burn engine exhaust is a major challenge to fulfill future restrictive standard emissions. Hydrocarbon selective catalytic
reduction (HC-SCR) of NOx is a powerful technique for the removal of NO x , CO and unburned hydrocarbon. Ag/Al 2 O 3 is one of the most active and selective
catalyst reported so far [1-2] due to its inherent thermal and hydrothermal stability [3], and its wide operating window in the presence of heavy hydrocarbons and
H 2 [4]. The only drawback is its low SO 2 tolerance and hence to improve SO 2 tolerance support modification has been attempted by doping with SiO 2 or TiO 2 and
the results are reported here.
Results: Catalytic activity was tested for 2% Ag/Al 2 O 3 (AgAl) and 1 % SiO 2 (AgSiAl) or TiO 2 (AgTiAl) doped AgAl in a fixed-bed flow reactor under steady
state at various temperatures 623-723K with 1000 ppm NO, 2000 ppm C 3 H 6 , 10 % CO 2 , 5 % O 2 and in the presence or in the absence of 80 ppm SO 2 . NO was
converted to only N 2 and no other by products such as N 2 O or NO 2 were formed.
Without SO 2 With 80 ppm SO 2
As shown in Fig. 1 a higher activity is obtained after Si and Ti incorporation in presence of
SO 2 , which has been related to a higher SO 2 tolerance. The improved SO 2 tolerance may be
due to the poor sulfating nature of SiO 2 and TiO 2 doped Al 2 O 3 support as well as increase in
the acidity which may help in easy desorption of SO 2 from the support thereby reducing the
extent of sulfation of Ag and Al 2 O 3 . Subsequent operando spectroscopic measurements
were carried out in order to examine related changes in the nature of adsorbed species which
could be involved during deNO x process.
Figure 1
References:
1. R. Burch, J.P. Breen, F.C. Meunier, Appl. Catal. B 39 (2002) 283.
2. W. Held, A. Koenig, T. Ritcher, L. Puppe, SAE Paper 900496 (1990).
3. H. Hamada, Catal. Today 22 (1994) 21.
4 K. Eränen, F. Klingstedt, K. Arve, L-E. Lindfors, D. Y. Murzin, J. Catal. 227 (2004) 328.
171 The influence of surface area and redox behaviour in soot oxidation over CeO 2 -ZrO 2
Eleonora Aneggi*, Carla de Leitenburg, Giuliano Dolcetti and Alessandro Trovarelli
Dip. di Scienze e Tecnologie Chimiche, Università degli studi di Udine, Udine, 33100, Italy
*Corresponding author: tel:+390432558865, Fax: +390432558803, e-mail: eleonora.aneggi@uniud.it
Background:
Removal of soot from diesel exhaust gas is a challenging topic. Recently, it has been reported that the use of ceria-based materials confers interesting properties
to soot combustion catalysts due to high availability of surface oxygen and high surface reducibility [1-3]. In several studies the key role of surface area and
oxygen storage capacity was taken into account but their relative importance was not investigated in detail so far. The purpose of this work is to gain further
insights into the dependence of activity against surface area and redox behaviour in ceria-zirconia and evaluate which parameter governs the activity.
Results:
Ceria-zirconia solid solution in all the composition range were prepared by coprecipitation starting from nitrates. For each sample a complete structural/textural
characterization was performed by conventional techniques (XRD, TPR, TGA, BET) along with complete activity tests carried out by running thermogravimetry
analysis (TGA) under controlled conditions over soot (Printex-U, Degussa AG)-catalyst mixtures. As a measure of activity we used the temperature at which 50%
of weight loss is observed (T50, corresponding to removal of 50% of soot). Surface areas in the range of 10-100 m 2 /g were obtained at the different calcination
temperatures. Within each composition the surface area has a key role in determining the activity, and a decrease in surface area leads to a decrease in activity.
On the other hand, formulations with the same surface area and different composition show very different activity. In this case, samples with an higher amount of
ceria results to be more active. While on average it is observed that activity increases by increasing surface area there are several samples which show similar
values of T50 while having very different surface area. It seems therefore that surface area only cannot explain the order of activity.
In order to gain further insights on this behavior activity data were compared with the total surface oxygen available (which depends on the amount of ceria) and
the total oxygen storage capacity measured independently. There is a strict dependence of the activity against the total surface oxygen availability. A decrease in
surface oxygen leads to a clear increase in T50 with an almost linear behavior. No clear correlation was found by comparing activity data with oxygen storage
capacity. These results points out the key role of surface oxygen availability, while seems to indicate that bulk oxygens (total OSC) are not influencing the
activity.
References
[1] E. Aneggi, C. de Leitenburg, G. Dolcetti, A. Trovarelli, Catal. Today, 2006, 114, 40;
[2] K. Krishna, A. Bueno-Lopez, M. Makkee, J.A. Moulijin, Appl. Catal. B 2007, 75, 201;
[3] X. Wu, D. Liu, K. Li, J. Li, D. Weng, Catal. Comm. 2007, 8, 1274.

181 Effect of ceria on the sulfation and desulfation characteristics of lean NO x trap catalysts
Y. Ji a , V. Easterling a , M. Crocker a, *, T.J. Toops b , J. Theis c , J. Ura c , R.W. McCabe c
a University of Kentucky Center for Applied Energy Research, Lexington, KY 40511, USA
b Fuels, Engines and Emissions Research Center, Oak Ridge National Laboratory, Knoxville, TN 37932, USA
c Chemical Engineering Department, Ford Research and Innovation Center, Dearborn, MI 48121, USA
*Corresponding author. Tel: +1 859 257 0295, Fax: +1 859 257 0302, e-mail: crocker@caer.uky.edu
Background
Lean NO x Traps (LNTs) represent a promising technology for the abatement of NO x from lean exhaust emissions. A major issue remaining for LNT catalysts is
that of deactivation due to sulfur poisoning. Theis and co-workers reported that the addition of ceria to LNT catalysts improved their sulfur tolerance [1]. It is
well known that ceria is able to store sulfur (as sulfate), which may help to protect the main NO x storage component from sulfur poisoning. To better understand
the role of ceria in alleviating the sulfur deactivation of LNTs, we have investigated the NO x storage capacity (NSC) of ceria-containing and ceria-free powder
LNT catalysts before and during sulfation. The desulfation behavior of the powder catalysts was also studied and compared with results obtained for fully
formulated monolithic LNTs.
Results
NO x storage measurements were performed at 300 °C using two model LNT catalysts, Pt/BaO/Al 2 O 3 (hereafter denoted as PBA) and a physical mixture of
Pt/BaO/Al 2 O 3 and Pt/CeO 2 (74:26 weight ratio, denoted as PBAC). After pretreatment at 750 °C in H 2 , PBA was found to possess slightly higher intrinsic NSC
than PBAC under continuous lean conditions (60 min duration). However, sulfation at 300 °C caused a dramatic decrease in NSC for PBA, whereas only a slight
decrease was observed for PBAC. Desulfation studies employing H 2 -TPR showed that sulfur was released from both catalysts mainly as H 2 S. Release of H 2 S
occurred at ~650 °C from PBA, whereas PBAC showed two discrete H 2 S release events at ~520 °C and ~650 °C. From this it follows that the H 2 S release at
~520 °C corresponds to desulfation of the ceria phase, with Ba desulfation occurring at the higher temperature. Significantly, PBAC displayed much lower H 2 S
evolution from the Ba phase than PBA, suggesting that the presence of ceria in PBAC lessened the degree of sulfur accumulation on the Ba phase. Studies were
then extended to fully formulated monolithic LNT catalysts containing different amounts of ceria in the washcoat. Consistent with the powder experiments, ceria
content was found to exert a significant influence on catalyst desulfation characteristics, the required desulfation temperature decreasing with increasing ceria
content.
Reference
[1] J. Theis, J. Ura, C. Jr. Goralski, H. Jen, E. Thanasiu, Y. Graves, A. Takami, H. Yamada, S. Miyoshi, SAE Technical Paper Series 2003-01-1160.
182 Carbon nanotube supported catalysts for NO x reduction using hydrocarbon reductants
E. Santillan-Jimenez and M. Crocker*
University of Kentucky Center for Applied Energy Research, Lexington, Kentucky 40511, USA.
*Corresponding author. Tel: +1 859 257 0295, Fax: +1 859 257 0302, e-mail: crocker@caer.uky.edu
Background
The Selective Catalytic Reduction of NO x with hydrocarbons (HC-SCR) is a potential solution for the abatement of NO x emissions from diesel engines, for
which operating temperatures typically range from ~150ºC to ~500ºC. Since a catalyst active throughout this temperature span has yet to be found, we propose a
system in which two catalysts are placed in parallel, with gas switching to utilize the appropriate formulation depending on the exhaust gas temperature. At
temperatures below 300 ºC, platinum group metals supported on activated carbon are among the most active HC-SCR catalysts. Unfortunately, carbon supports
tend to combust at low temperatures. However, multi-walled carbon nanotubes (MWNTs) have a higher resistance to oxidation than activated carbon, which
makes them of interest as supports for HC-SCR catalysts.
Results
Highly dispersed Pt was supported both on pristine (as prepared) MWNTs and on MWNTs which had been subjected to acid treatment so as to introduce –COOH
and –OH functionalities (fMWNTs). The superior stability of the resulting Pt/MWNTs and Pt/fMWNTs catalysts in oxidizing atmospheres, as compared to
Pt/activated carbon, was confirmed by means of thermogravimetric analysis. NO reduction was investigated over the two catalysts, using propene as the
reductant. Compared to pristine MWNTs, the use of acid-functionalized MWNTs as the support had two effects: (i) the maximum for NO conversion was shifted
to lower temperature, and (ii) the temperature window for NO conversion was slightly widened. Given that the Pt loading (2 wt%) and dispersion were essentially
the same in the two catalysts, these findings are consistent with the idea that support acidity plays a significant role in HC-SCR, with acidic supports participating
in the activation of the hydrocarbon. The Pt/fMWNTs catalyst also showed higher NO conversion and lower light-off temperature in comparison with a Pt/Al 2 O 3
reference catalyst of similar Pt loading and dispersion. Given this promising result, a route to monolithic Pt/fMWNTs catalysts was developed. Optimal results
were obtained by first growing MWNTs on a metallic monolith by means of a simple chemical vapor deposition technique, activating the MWNTs with 0.5%
NO 2 /N 2 at 300 °C, and subsequently depositing Pt via an in situ chemical reduction process. The resulting catalyst has been tested on a diesel engine using diesel
fuel as the reductant.
Justification for acceptance
The use of acid-functionalized MWNTs as a catalyst support has been found to yield superior Pt HC-SCR catalysts, and a method has been developed for the
preparation of Pt/fMWNTs on metallic automotive monoliths. Thus, this research makes applied and fundamental contributions to the field of automotive
emission control.

199 The effect of NOx traps on the combustion of carbonaceous particulate matter.
J.A. Sullivan and P.Dulgheru*
UCD School of Chemistry and Chemical Biology, Belfield, Dublin 4, Ireland,
petrica.dulgheru@ucd.ie
Background:
Diesel engine exhausts invariably contain large concentrations of NOx and carbonaceous particulate matter (PM). Both are recognised pollutants. On the other
hand diesel engines combust fewer hydrocarbons and thus their exhausts contain far less CO 2 than gasoline equivalents (with consequent benefits in terms of fuel
economy and greenhouse gas emissions). Currently, proposals for removing NOx centre on NSR systems while particulates are trapped and oxidised using
O 2 /NO mixtures on catalysed or uncatalysed soot filters. A primary step in the operation of a NOx trap is the oxidation of NO to NO 2 and the subsequent
formation of Ba(NO 3 ) 2(s) through reaction with BaO. This is the same step that operates in the promotion of soot combustion (where the generated NO 2 reacts
with PM). This suggests that the combination of these systems may be possible. Such a combination of NSR systems with PM combustion catalysts in the aftertreatment
system of a diesel engine exhaust would be a major advancement in the development of 4-way catalytic after-treatment systems [1,2].
Results
In this work we have evaluated the effect of the presence of a NOx trapping component (BaO) upon the activity of a model 1% Pt/Al 2 O 3 catalysts for promoting
the combustion of soot. Furthermore we have looked at the effect that the presence of PM has on the functioning of a (1% Pt/BaO/Al 2 O 3 ) NOx trap.
We have studied (using RGA Mass spectrometry and TPD measurements) the adsorption and desorption of NO/O 2 mixtures onto (and from) various
combinations of Pt/BaO/Al 2 O 3 catalysts. We have specifically looked at variables such as (a) NO/O 2 dose time, (b) BaO concentration and (c) levels of soot
present and studied their effects on (i) NOx trapping capacity and (ii) soot combustion.
We have also studied the nature of adsorbed/trapped NOx using in-situ DRIFTS FTIR and also used TEM and XRD to study the both the composite materials and
soot before and after doses in NO/O 2 .
Justification for acceptance
The Euro V regulations due in September 2009 will cut C (s) allowable to only 3% of the 1993 limits. Euro VI rules to be implemented in 2014 are even more
stringent, therefore improvements in this area are essential. The combination of lean burn exhaust NSR technology with a soot combustion catalyst would result
in a major step change in diesel after-treatment systems.
References
[1] J.A. Sullivan, O. Keane and A. Cassidy, Appl. Catal. B: Env., 75, (2007), 102-106.
[2] J.A. Sullivan and O.Keane, Catal. Today, 114, (2006), 340.
201 On the characterisation of silver species on Ag/Al 2 O 3 catalysts for SCR of NO x with ethanol
A., Musi 1,2 , P., Massiani 1 , J.M., Trichard 2 , and P., Da Costa 1 ,*
1 Université Pierre et Marie Curie, Laboratoire de Réactivité de Surface, CNRS UMR 7609, case 178, 4 place Jussieu, 75252 Paris, France, 2
Renault SA, Technocentre Renault, 1 Avenue du Golf, 78280 Guyancourt France,
*Corresponding author. Tel.: +33 144275512; fax: +33 144276033, E-mail address: patrick.da_costa@upmc.fr (P. Da Costa).
Background
Reducing of nitrogen oxydes (NO x ) in a lean exhaust gases has become one of the most important environmental concerns. Among the different active phases
studied for NO x reduction reaction, silver-based catalysts supported over alumina show good performances using, as reducing agents, either hydrocarbons or
oxygenated compounds [1]. Nevertheless, a good understanding of the mechanism reaction has not been reached yet. This comprehension requires a better
caracterisation of the silver-based catalysts system.
Results
In our study, Ag/Al 2 O 3 catalysts showed high efficiency in NO x reduction using ethanol as reducing agent. The conversion plots, in steady state conditions for the
different samples Ag/Al 2 O 3 (0.8-3.5 % Ag wt.), show a great dependance of the activity with the metal loading. The optimal silver loading has been established
around 2% wt. Increasing the silver loading, the temperature of maximal NO x conversion shifted toward the lower temperatures. According to the literature, a
reduced and an oxide phase of silver have been observed by UV-Vis spectroscopy [2]. The ratio between the two phases is changing with the silver loading.
However, TPR measurements reveal the presence of two types of oxide phases. TPR reveal the coexistence of a silver oxide phase (Ag 2 O), according to a
production of water in the course of the reaction, and a non-oxygenated phase attributed to isolated Ag + cation.
Justification for acceptance
The present work deals with connection existing between the metal loading and the nature of the different silver species existing on the catalyst. An original way
using TPR measurements has been developed to differenciate the various oxydized phases. The aim of this caracterization is to correlate the catalyst’s activity
with the observed silver phases, in order to understand the nature of phase active for NO x reduction at low temperatures.
References
[1] Kameoka, S., Ukisu, Y., Miyadera, T., P. C. C. P. 2 (2000) 367
[2] N. Bogdanchikova, F.C. Meunier, M. Avalos-Borja, J.P. Breen, A. Pestrykov, Applied Catal. B 36 (2002) 287

211 Selective catalytic reduction of nitrogen oxide with propene in the presence of excess oxygen over gold based catalysts
Background
L. Delannoy * , L. T. Nga Nguyen, P. Lakshmanan, V. Richard, C. Potvin and C. Louis
UPMC Univ Paris 06, Laboratoire de Réactivité de Surface, Paris, France
*Corresponding author. Tel: +33 1 44272113, Fax : +33 1 44276033, e-mail: laurent.delannoy@upmc.fr
The selective catalytic reduction of NO with hydrocarbons (HC-SCR) such as methane, olefins or higher alkanes for lean-burn exhaust has been extensively
studied during the past decade over supported noble metals, such as platinum or palladium. Less attention has been paid to the potential of gold catalysts for the
HC-SCR of nitrogen oxide but previous reports have shown that gold could offer a compromise between low temperature activity and selectivity to N 2 [1,2]. We
present results obtained in NO reduction with C 3 H 6 over gold based catalysts supported on several oxides and mixed oxides.
Results
Gold catalysts (1 wt% Au) supported on TiO 2 , Al 2 O 3 , CeO 2 and CeO 2 /Al 2 O 3 (1.5 and 10 wt% CeO 2 ) were prepared using the Deposition-Precipitation with Urea
(DP Urea) method. The catalysts were activated before reaction under various conditions as it has been previously reported that the activation treatment can have
a strong influence on the gold oxidation state, especially in the case of Au/CeO 2 for which gold is stabilized in cationic form after calcination up to 500°C [3].
The HC-SCR of NO with propene was carried out with a reactant mixture of 200 ppm NO, 400 ppm C 3 H 6 , 9% O 2 in helium (space velocity = 50,000 h -1 ).
Au/Al 2 O 3 is the most selective catalyst (40% NO x conversion with 100% selectivity to N 2 at 350°C) whereas Au/CeO 2 is active at lower temperature, but
produces higher amount of N 2 O (35% NO x conversion with 45% selectivity to N 2 at 200°C). For the Au/CeO 2 catalyst, reduction under H 2 leads to a slight
decrease in selectivity to N 2 , compared to the calcined sample, indicating that the presence of metallic gold on CeO 2 seems to favor the formation of N 2 O. The
association of ceria and alumina in Au/CeO 2 /Al 2 O 3 samples allows to achieve high selectivity at lower temperature than Al 2 O 3 (35% NO x conversion with 100%
selectivity to N 2 at 250°C for the calcined Au/10wt%-CeO 2 /Al 2 O 3 ). In the case of the Au/CeO 2 /Al 2 O 3 systems, the activation conditions strongly affect the
selectivity and enhanced N 2 O formation is observed after reduction under H 2 . This may result from the preferential interaction of gold with the ceria domains
isolated on the alumina surface, evidenced by Energy-Filtered Transmission Electron Microscopy (EFTEM), which may alter the reducibility of the gold (III)
species deposited on the CeO 2 /Al 2 O 3 support.
Justification for acceptance
The association of gold with a combination of metallic oxides having different redox properties, such as CeO 2 /Al 2 O 3 , leads to active and very selective catalysts
for NO x removal at moderate temperature (< 300°C). These catalytic systems are promising for an application for automotive emission control.
[1] A. Ueda, T.Oshima and M. Haruta, Appl. Catal. B 12 (1997) 81.
[2] G.R. Bamwenda, A. Obuchi, A. Ogata, J. Oi, S. Kushiyama and K. Mizuno, J. Mol. Catal. A: Chem. 126 (1997) 151.
[3] L. Delannoy, N. Weiher, N. Tsapatsaris, A.M. Beesley, L. Nchari, S.L.M. Schroeder and C. Louis, Top. Catal. 44 (2007) 263.
213 Soot oxidation characteristics as function of diesel fuel composition.
Ing. H.Jansma a , Dr. R. Uitz b , Dr.Ir. M.Makkee a , *
a
Delft University of Technology, DCT-CE, Julianalaan 136, NL 2628 BL, Delft, The Netherlands.
b Shell Global Solutions GmbH, PAE Labor, GSMR/1, Hohe-Schaar-Strasse 36, D-21107 Hamburg, Germany
*Corresponding author. Tel: +31 15 2781391, Fax: +31 15 2785006, e-mail: m.makkee@tudelft.nl
Background
In Euro V emission standards for cars and light trucks, implementation in 2009, the level of soot in exhaust has to be decreased 5 times in comparison with Euro
IV regulations [1]. Normally diesel soot can be oxidized by oxygen to CO + CO 2 around 600 °C. During most of the diesel engine operations the exhaust gas
temperature is, however, around 300 °C, which is too low to initiate continuous un-catalyzed soot oxidation. Therefore, soot is collected on a filter and can be
oxidized into CO 2 at high temperatures to regenerate the filter. To improve fuel economy the duration of the regeneration should be as short as possible and at the
same time ensure complete trap generation. The European Fuels Directive has forced changes on fuel properties (less sulfur and aromatics) and the soot from the
combustion of this more severely hydro-processed diesel can have different oxidation characteristics. For practical application it is important to know if the fuel
properties have an impact on the temperature required for a complete regeneration of diesel soot closed filters. Amount of soot is also crucial to DPF
regeneration; however this study focuses solely on the fuel’s impact on oxidation temperature.
Results
The soot oxidation temperature (SOT) of several fuels containing different amounts of aromatics and sulfur have been investigated. After collecting soot from
different types of fuel, the SOT of these soots is determined by Temperature Programmed Oxidation (TPO) in either a TGA or a 6-flow reactor [2] using a
temperature programme up to 650 °C and using a total flow of 200 ml/min. For the flow reactor several exhaust gas compositions (NO and SO 2 ) have been
simulated with different diesel soot oxidation reactor configurations based on Platinum. Oxidation with only O 2 shows a large fuel dependency on the oxidation
temperature. The SOT for low aromatic fuel is higher for the first time in our experience than the temperature of the very refractory reference soot Printex-U.
This will have a major impact on the induced diesel soot abatement regeneration strategies. Soot oxidation in the presence of NO and a Pt-catalyst resulted a
lower oxidation temperature. SO 2 had an inhibiting effect leading to a higher SOT. Also on the last two cases the oxidation temperature of the low aromatic diesel
is higher than that of the reference.
Justification for acceptance
For future diesel soot abatement technology, based on an induced regeneration strategy, FUEL properties, especially the aromatic content, are real and of an
important concern, since they have a dramatic negative effect on the soot oxidation temperature.
References:
[1] http://www.dieselnet.com./standards/
[2] S.J. Jelles, Diesel Exhaust Aftertreatment, ISBN 90 6464 5221 (1999).

214 A systematic examination of the effect of preparation variables on the properties and the SCR-NH 3
and SCR-Urea activities of Fe ZSM-5 catalysts.
Background
S. Burnham*, J. A. Sullivan, P. Dulgheru and L.Sherry
UCD School of Chemistry and Chemical Biology, Belfield, Dublin 4, Ireland.
*Corresponding author. Tel:+353 1 7162135, Fax: +353 1 716 2127, e-mail: sarah.burnham@ucdconnect.ie
Lean-burn combustion in a diesel engine allows passive exhaust catalysts to remove hydrocarbons and CO by oxidation to H 2 O and CO 2 but do not remove NOx
since the exhaust gas mixture is very oxidising. NOx causes acid rain, photochemical smog and is also considered an irritant to the alveoli of the lungs. To resolve
this, NOx (rather than the large excess of O 2 ) can be selectively reduced. This can be accomplished using NH 3 or Urea (a precursor of NH 3 ) over a suitable
catalyst e.g. FeZSM-5 [1, 2]. There are many confusing reports regarding the activity and selectivity of FeZSM-5 catalysts in several reactions, e.g. the SCR-HC
reaction [3] and selective oxidation using N 2 O [4].
Results
In this work we have undertaken a systematic analysis of several variables (initial Fe counter-ion, Fe oxidation state, Zeolitic counter ion, oxalic acid leaching of
Fe 2 O 3 , pH of preparation, etc.) in the preparation of FeZSM-5 catalysts and studied their effects on the composition of the catalysts (%Fe), surface properties
(concentration of acid sites and nature of acidity, NOx trapping capacity) and activities in SCR reactions (using NH 3 and urea as reductants). The
characterisations have been carried out using RGA-TPD, in-situ FTIR, AA and ESR while activities have been measured using a chemiluminescent NOx
analyser. Of the catalysts prepared it was those made using Fe (II) salts that expressed the highest deNOx activity. These catalysts were orange in colour;
showing the presence of bulk Fe 2 O 3 arising due to ion exchange between pH 2.0 and 4.5. Upon removal of Fe 2 O 3 (through reflux in oxalic acid solutions) there is
no change in activity, showing that presence of bulk oxide does not detrimentally affect this reaction. This is in contrast to the reactions named above where
Fe 2 O 3 decreases catalyst selectivity [3,4].
Justification for acceptance
In 2014, Euro VI will implement significantly lower NOx emissions from diesel cars, allowing only 32% of the current emission limit. The current emission
standards for light commercial vehicles running on diesel is 250mg NOx / km (Euro IV), increasing to 180mg/km (Euro V) and eventually 80mg/km (Euro VI).
The implementation of SCR-Urea systems onto larger vehicles is a realistic option and obviously more research into optimising this process is required.
References
[1] H. Bosch, F. Janssen, Catal. Today 2 (1988) 369-379
[2] M. Koebel, M. Elsener, M. Kleemann, Catal. Today 59 (2000) 335-345
[3] I. M. Saaid, A.R. Mohamed, S. Bhatia. Kinet. Catal, 75 (2002) 359-365.
[4] Q. Zhu, R. M. van Teeffelen, R.A. van Santen, E.J.M. Hensen. J. Catal. 221 (2004) 575-583.
221 Influence of sulphur on Pd/Ce-Zr-based catalysts in CO, C 3 H 6 , and C 3 H 8 oxidation
T. Kolli a,* , M. Huuhtanen a , A. Hallikainen a , K. Kallinen b and R. L. Keiski a
a Department of Process and Environmental Engineering, P.O.Box 4300, FI-90014 University of Oulu, Finland.
b Ecocat Oy, Typpitie 1, FI-90650 Oulu, Finland.
* Corresbonding author. Tel: +358 8 5537661, Fax: +358 8 5532369, e-mail: tanja.kolli@oulu.fi
Background Poisoning of catalytic surfaces is a serious problem in the design of more efficient diesel exhaust catalysts [1]. Sulphur is still present in diesel
and gasoline in small amounts [2], and has been found to have a negative effect on the oxygen storage compounds [3]. Cerium oxide has been found to react with
sulphur to cerium sulphates [4] and sulphides [5] on the catalyst surface as well as in bulk material. Zirconium oxide adsorbs sulphur only as sulphates [5]. All
the above mentioned reactions depend on the reaction conditions i.e. temperature and gas phase.
Results Fresh and sulphur-treated Pd/CeO 2 , Pd/ZrO 2 , and Pd/Zr 0.15 Ce 0.85 O 2 catalysts were studied. The amount of Pd in the washcoat was 4 wt-% for each
catalyst studied. The gas phase poisoning of these catalyst powders was carried out at 400 °C. The catalyst was exposed for 5 hours to the poisoning gas mixture
containing 100 ppm of SO 2 and 10 vol-% of air, balanced with N 2 . The amount of sulphur was for the Pd/CeO 2 catalyst 2.1 % and for the Pd/Zr 0.15 Ce 0.85 O 2
catalyst 1.8 %, both analysed by ICP-OES. On the Pd/ZrO 2 catalyst the sulphur content was 0.7 % analysed by XRF.
Catalytic activity was measured by using laboratory scale light-off experiments. A lean gas mixture contained 1000 ppm CO, 650 ppm C 3 H 6 , 180 ppm C 3 H 8 and
12 vol-% O 2 , balanced with N 2 . The concentrations of feed and product gases were measured by Gasmet TM FT-IR gas analyser. The light-off temperatures of CO,
C 3 H 6 , and C 3 H 8 were the lowest for the fresh Pd/ZrO 2 catalyst compared to the two other studied fresh catalysts. After the sulphur treatment, the activity of the
Pd/ZrO 2 catalyst in CO and C 3 H 6 oxidation was lowered more than that of the Pd/CeO 2 and Pd/Zr 0.15 Ce 0.85 O 2 catalysts, based on the difference between fresh and
sulphur-treated light-off temperatures. Instead, in the case of C 3 H 8 oxidation, the sulphur-treated Pd/ZrO 2 catalyst had preserved its activity. More studies are
needed to find out the reasons for this phenomenon. The small amount of sulphur on the Pd/ZrO 2 catalyst had a significant effect on the dispersion, but not on the
BET surface area, both measured by ASAP 2020. Instead, for the ceria containing catalysts, sulphur treatment had a significant influence on both BET and
dispersion values.
Based on the results presented above, it can be concluded the Pd/ZrO 2 catalyst was least tolerant towards deactivation by sulphur.
Justification for acceptance It is essential to study sustainable and environmental-friendly diesel oxidation catalysts, which are also durable for poisons
originating from fuels and lubricant oils. The aim of this research was to study the sulphur tolerance of Pd/Ce-Zr-based catalyst in dry conditions and at low
temperatures as well as their catalytic activity.
References
[1] J. Kašpar, P. Fornasiero, N. Hickey, Catal. Today 77 (2003) 419.
[2] T.-C. Yu, H. Shaw, Appl. Catal. B 18 (1998) 105.
[3] M. Boaro, C. de Leitenburg, G. Dolcetti, A. Trovarelli, M. Graziani Topics in Catal. 16/17 (2001) 299.
[4] S. Yasyerli, G. Dogu, T. Dogu, Catal. Today 117 (2006) 271.
[5] T. Lou, R.J. Gorte, Appl. Catal. B 53 (2004) 77.

227 On the evolution of commercial Natural Gas Vehicle catalysts as function of mileage
M. Salaün a , A. Kouakou a , S. Da Costa b , P. Granger c , P. Da Costa a,*
a U.P.M.C. Paris 6, Laboratoire de Réactivité de Surface, UMR 7609, 4 place jussieu, 75252 Paris cedex 05, France
b Gaz de France, 361 Av. du Président Wilson, B.P. 33, 93211 La Plaine Saint-Denis Cedex, France
c Unité de Catalyse et de Chimie du Solide UMR 8181, USTL, 59655 - Villeneuve d'Ascq, France
*corresponding author: Patrick DA COSTA, + 33 1 44 27 55 12, patrick.da_costa@upmc.fr
Background
The use of alternative fuel such as natural gas is becoming increasingly attractive for both economic and environmental consideration. Thus, about 5 millions
natural gas vehicles are in operation nowadays. Natural gas used as a vehicle fuel can reduce, compared to conventional Diesel technology, 99% of particulate,
85% of nitrous oxides (NO x ), and 90% of carbon monoxide (CO). Comparing to gasoline the global warming impact (GWI) for dedicated natural gas vehicles
(NGVs) is generally more than 20 % lower. However, unburned methane is always present in the exhaust gases. Thus, the development of Three Way Catalysts
(TWC) for NGC becomes crucial. Catalysis improvement passes through decreasing of operating temperature and rising mileage resistance. The aim of this work
is to point out the major evolutions of the catalysts (mechanical, structural, etc.) during the ageing.
Results
Two TWC were extracted from European compact vehicle. The first one is a never used catalyst (fresh one) whereas the second one is after 20,000 km of
mileage. These commercial converters are analyzed by different techniques such as elementary analysis, Transmission Electronic Microscopy, Scanning Electron
Microscopy and X-ray Photoelectron Spectroscopy. The catalytic activities are studied over a carrot of about 25 cm 3 of catalyst using a representative exhaust
mixture.
By Elementary Analysis noble metals such as palladium, rhodium, gold, and also cerium, zirconium, lanthanum, baryium are detected [1]. After only 20,000 km
of mileage, the loss of noble metals is observed. This fact can be explained by a washcoat adhesion failure detected by SEM. This phenomenon is responsible for
the loss of 30% of noble metals according to Elementary Analysis. More over, by TEM a sintering of palladium particles is observed. Particles size increase from
2 nm for fresh catalyst to 40 nm after 20,000 km of mileage.
The evaluation of these catalysts in reducing emissions of CO, NOx and CH 4 was performed using a synthetic gas mixture representative of NGV emissions. The
hourly space velocity was equal to 70,000 h -1 .The catalytic runs revealed that the light of temperature (T 50 ) increased consequently from 30 to 65 K, depending on
the pollutant, after a mileage of 20,000 km [2].
References
[ 1 ] A.F. Diwell, R.R. Rajaram, H.A. Shaw, T.J. Truex, 71 (1991) 139.
[ 2 ] P. Da Costa, M. Salaün, S. Da Costa, G. Brecq, G. Djéga-Mariadassou, SAE, 2007-01-0039.
229 H 2 -SCR: NO x reduction at low temperatures in diesel passenger cars
F.J.P. Schott, S. Kureti*
University of Karlsruhe, Institute of Technical Chemistry and Polymer Chemistry, Germany
*Corresponding author. Tel: +49 721 608 8090, Fax : +49 721 608 2816, e-mail: Kureti@ict.uni-karlsruhe.de
Background Nitrogen oxides emitted from diesel vehicles contribute to various environmental problems, e.g. acid rain and formation of ozone. Therefore,
SCR and NO x storage catalyst technology have been developed to remove NO x from the oxygen rich diesel exhaust. However, a constraint of these techniques is
that NO x is efficiently converted only above 150 °C. In contrast to that, engine development led to decrease of exhaust temperature in the past and it is expected
that the temperature will further be lowered by future engine research. Already today in the driving cycle of the European Community the exhaust temperature of
diesel passenger cars is below 150 °C for about 60 % of cycle time. These facts show that a technique will be required in future by which NO x is substantially
converted at low temperatures. For this purpose the reduction of NO x by H 2 over platinum catalysts is considered to be a promising procedure.
Results The screening of effective H 2 -SCR catalysts led to a pattern that consists of Pt and a WO 3 /ZrO 2 carrier. This material reveals outstanding deNO x
activity under lean conditions ranging from very low temperatures (50°C) up to 400°C with an overall N 2 selectivity of 85% (feed composition: 500 ppm NO,
2000 ppm H 2 , 6% O 2 , Ar balance). Moreover, the transfer from powder to industrially relevant honeycomb system showed very encouraging results, even in
realistic diesel model exhaust [1].
From DRIFTS studies with CO as probe molecule as well as kinetic modeling of the O 2 -TPD we derive electronic interaction between the Pt component and the
carrier. This interaction leads to decrease of the oxygen coverage and lowering of the bonding energy of the Pt-O surface complexes thus resulting in an increased
number of active Pt sites and rapid regeneration of these sites by H 2 . These features are considered to be the reason for the high deNO x activity and N 2 selectivity
[2]. Additionally, in situ DRIFTS examinations indicate that the support is not involved in the deNO x reaction as compared to perovskite related carriers reported
in the literature [3].
References
[1] F.J.P. Schott, S. Kureti, MinNO x conference, Berlin, 2007.
[2] R. Burch et al., Appl. Catal. B 4 (1994) 65.
[3] C.N. Costa, V.N. Stathopoulos, V.C. Belessi et al., J. Catal. 197 (2001) 350.

231 Insights of NOx storage on ceria based NSR-catalyst compounds
M. O. Symalla a* , A. Drochner a , H. Vogel a , S. Philipp b , S. Eckhoff b
a Technische Universität Darmstadt, Ernst-Berl-Institut, Petersenstr. 20, 64287 Darmstadt, Germany
b Umicore AG & Co. KG, Rodenbacher Chaussee 4, 63403 Hanau, Germany
* Corresponding author. Tel: +49 6151 162065, Fax: +49 6151 163465, e-mail: symalla@ct.chemie.tu-darmstadt.de
Background
One way to reduce CO 2 emissions from passenger cars is the use of diesel or lean burn gasoline engines. The intrinsic problem with NOx after treatment of these
engines can be solved by the NOx-storage reduction-(NSR-) technology. NSR-catalysts store NOx under lean conditions and reduce it during short rich periods to
harmless nitrogen. Common catalysts consist of alumina supported (earth-) alkaline oxides like BaO for NOx storage and a noble metal like platinum for NOx
conversion. In this context ceria adds positive properties like oxygen- and NOx storage especially at low temperatures. These features make an application as
NSR-catalyst-compound very interesting.
Results
Beside structural information given by XRD and TEM images, the focus of this work lies on the in-situ investigation of NOx storage on ceria based NSR catalyst
compounds via DRIFTS [1] and via breakthrough curves performed in a tube reactor. With these methods it can be shown and explained why CO 2 and H 2 O
possess negative effects during NOx storage. As known from Ba/alumina systems [2] ceria is also able to store NO mainly as nitrites and NO 2 as nitrates. Oxygen
increases the NOx storage rate as well as the NOx storage capacity (NSC) and plays an important role due to a subsequent nitrite oxidation to nitrates. This
consecutive reaction can be observed in-situ. Other possibilities to oxidise adsorbed nitrites to nitrates on the catalyst surface will be discussed. Based on
proposed reaction models it is possible to estimate kinetic parameters (k and E A ) for reaction steps like the nitrite oxidation with the obtained kinetics of NOx
storage experiments. Furthermore, the influence of platinum on ceria based catalyst compounds will be shown. Beside an increased NSC, platinum plays an
important role as catalyst especially for the equilibrium reaction of NO 2 and NO/O 2 . An intermediate species resulting from adsorbed NO can be detected via
DRIFTS on platinum during the storage process. Barium oxide stores NOx preferred at higher temperatures, which is shown for a variation of the Ba-amount on
CeO 2 . The observed consecutive reaction of nitrite to nitrate on ceria takes also place at higher temperatures for an increased Ba-amount [3]. The presence of CO 2
during NOx storage leads for short treatment only to adsorbed carbonates, the formation of solid state barium carbonate occurs only after long CO 2 treatment.
Justification for acceptance
This work gives insights in NOx storage on ceria as promising catalyst compound for the low temperature NOx adsorption. Based on in-situ investigations,
mechanistic and kinetic data allow the transfer to reaction models and simulations which are essential for performing improved catalysts.
References
[1] A. Drochner, M. Symalla, H. Vogel, Bunsenmagazin 1 (2008) 10.
[2] I. Nova, L. Castoldi, F. Prinetto, V. Dal Santo, L. Lietti, E. Tronconi, P. Forzatti, G. Ghiotti, R. Psaro, S. Reccia, Top. Catal. 30/31 (2004) 181.
[3] M. O. Symalla, A. Drochner, H. Vogel, S. Philipp, U. Göbel, W. Müller, Top. Catal. 42/43 (2007) 199.
232 Influence of the three way catalyst design parameters on its conversion performance
H. Santos a and M. Costa b ,*
a
Mechanical Engineering Department, School of Technology and Management, Polytechnic Institute of Leiria, Portugal
b
Mechanical Engineering Department, Instituto Superior Técnico, Technical University of Lisbon, Portugal
* Corresponding author. Tel.: +351218417378; Fax: +351218475545; E-mail: mcosta@ist.utl.pt
Background
Nowadays TWC models are frequently used to predict the catalytic converter conversion. However, most of the models available in the literature neglected the
diffusion limitation within the washcoat (e.g., [1]), treating the washcoat as a black-box without knowledge of the characteristics and details of the phenomena
taking place in there. In the present work a single channel model accounting for the species diffusion inside the washcoat, validated and calibrated against
experimental data elsewhere [2], was used to obtain relevant information on the design parameters most critical for TWC conversion optimisation.
Results
The results demonstrate that (1) the internal mass transfer limitations affect the TWC conversions more than the external mass transfer limitations,
(2) there is a range of washcoat thicknesses that permits to achieve high TWC conversions, with the optimum washcoat thickness decreasing as the
operating temperatures increase, (3) the effective diffusivities are key parameters for the TWC conversions being its influence particularly
significant for operating conditions where the catalytic reactions take place close to the interface gas-solid, and (4) an increase of the precious metal
loading does not lead to significant increases in the TWC conversions.
Justification for acceptance
The aim of the present study is to elucidate the significance of different design parameters on the TWC conversion performance. The most significant feature of
the present model is that it considers the internal mass transfer limitations within the washcoat, in contrast with most of the earlier studies. This has allowed us to
study both the effects of channel and washcoat parameters. We feel that this subject will be of interest for a large number of researchers attending the 5 th ICEC.
References
[1] R. Holder, M. Bollig, D.R. Anderson, J.K. Hochmuth, Chemical Engineering Science, 61 (2006) 8010-8027.
[2] H. Santos, M. Costa, Modelling transport phenomena and chemical reactions in automotive three-way catalytic converters, submitted for
publication.

235 NO reduction by CO over gold catalysts based on doped ceria
L. Ilieva a* G. Pantaleo b , A. M. Venezia b , D. Andreeva a
a Insitute of Catalysis, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria
b Istituto per lo Studio DeiMateriali Nanostructurati, CNR, Palermo I-90146, Italy
*Corresponding author: Tel.: +359 29792572, Fax: +359 2 971 2967,
E mai : luilieva@ic.bas.bg
Background
The reduction of NO x has been extensively investigated in view of the strict automobile exhaust emissions regulations. Recently, it was established that
nanosized gold supported on ceria-alumina exhibits high NO+CO activity and very high selectivity to N 2 at about 200 o C [1-3]. The selection of gold catalysts
and optimal reaction conditions, which would maximize the catalytic activity preserving a high selectivity to N 2 is an important task.
Results
The reduction of NO by CO over gold catalysts supported on ceria, modified by Me 3+ , where Me=La, Sm, Gd and Y, was investigated in the present study. The
mixed oxide supports were synthesized by co-precipitation (10 wt% of the Me 3+ modifier). This method of preparation was chosen on the basis of our previous
results [3]. The gold (2 wt%) was introduced by deposition-precipitation method. The lattice parameters and average particle size of ceria were determined by
XRD. The Raman spectroscopy was applied for the evaluation of the defective ceria structure, including oxygen vacancies in the presence of dopants. The redox
behaviour of the catalysts was estimated by TPR of fresh samples and after re-oxidation. The catalytic activity test of NO reduction by CO was performed in a
wide temperature interval, all the reactants and products were monitored by mass-spectrometry and ABB IR and UV analysers. The catalytic activity
measurements were carried out under different conditions: 1) in the presence of hydrogen in the gas feed and 2) adding both hydrogen and water to the gas feed.
A high NO and CO conversion degree(about 100 %) was registered at around 200 o C, the highest one was over gold on CeO 2 /Sm 2 O 3 and the lowest one - on
CeO 2 /Y 2 O 3 . The most interesting result was the reaction selectivity to N 2 , depending on the temperature and on the feed gas composition.
Justification for acceptance
NO reduction is directly related to the lowering of the harmful emissions from vehicle’s engines.
References:
[1] L. Ilieva et al., Appl. Catal. B: Envir., 65 (2006) 101.
[2] L. Ilieva-Gencheva et al., JNN, doi:10.1116/jnn.2007.C108.
[3] L. Ilieva et al., Appl. Catal. B: Envir., 76 (2007) 107.
237 Importance of the WO x -ZrO 2 -supported catalyst composition in the C 3 H 6 - and C 3 H 8 -SCR of NO x
N. El Kolli, C. Potvin and C. Thomas*
Laboratoire de Réactivité de Surface, Université Pierre et Marie Curie-Paris6, UMR CNRS 7609, Paris, France.
*Corresponding author. Tel: +33 1 44 27 36 30, Fax: +33 1 44 27 60 33, e-mail: cthomas@ccr.jussieu.fr
Background
As diesel exhausts usually contain a complex mixture of unburnt hydrocarbons (HCs), it is of importance to estimate to which extent the nature of the HCs may
be decisive in the HC-SCR of NO x . It is well-established that unsaturated HCs are more effective NO x reductants than their saturated counterparts [1]. The
performances of Pd/WO x -ZrO 2 (Pd/WZ) catalysts in the HC-SCR of NO x have, however, been mainly studied with CH 4 as a reductant [2]. To our knowledge, the
C 3 H 6 -SCR of NO x has been reported only once [3], whereas C 3 H 8 -SCR has not been investigated yet.
Results
A series of Pd-or/and-Pt/WO x -ZrO 2 catalysts was synthesised (0.2-0.1 wt% Pd or Pt) by refluxing a commercial zirconium oxyhydroxide (MEL Chemicals,
XZO880/01) and ammonium metatungstate (Fluka) at 110 °C for 20 h. After drying, the samples were calcined at 650 °C for 3 h. The nature of the noble metal,
the W loading and the promotion of Pd by Pt were investigated in the C 3 H 6 - and C 3 H 8 -SCR of NO x . The C 3 -SCR of NO x (500 ppm C 3 , 7 % O 2 and 400 ppm NO x )
were studied in a quartz μ-reactor coupled to a set of specific detectors [4]. The nature of the reductant has a dramatic influence on the SCR of NO x , C 3 H 6 being
much more effective than C 3 H 8 . The incorporation of W to the catalysts is detrimental to the C 3 H 6 -SCR. The 40 % NO x conversion found on Pd/ZrO 2 in the C 3 H 6 -
SCR is about twice that found on Pd/W(6 wt%)ZrO 2 or Pd/W(13 wt%)ZrO 2 . In contrast, the addition of W promotes the C 3 H 8 -SCR of NO x . At about 380 °C, the
NO x conversions observed on Pd/W(6 wt%)ZrO 2 or Pd/W(13 wt%)ZrO 2 are three or two times greater, respectively, than that found on Pd/ZrO 2 . The activity of
Pd-Pt/WZ is slightly greater than those of the monometallic catalysts in the C 3 H 6 -SCR. In the case of C 3 H 8 -SCR, a spectacular synergistic effect is observed for
the bimetallic Pd-Pt catalyst, which shows a NO x conversion of 21 % at 300 °C, whereas those of Pd/WZ and Pt/WZ are 3.3 and 1.4 %, respectively. This
synergistic effect in the C 3 H 8 -SCR is attributed to the superior capacity of Pt to oxidise NO to NO 2 . It must be stressed, however, that such a prerequisite is not
sufficient to guarantee significant NO x conversions, as illustrated by the poor SCR performances of Pt/WZ.
Justification for acceptance
This study puts emphasis on the existence of various SCR mechanisms depending on the nature of the HC reductant or/and to a change in the rate determining
step in the SCR processes, NO oxidation to NO 2 being predominant in the C 3 H 8 -SCR of NO x .
References
[1] C.N. Montreuil, M. Shelef, Appl. Catal. B 1 (1992) L1.
[2] Resasco and co-workers, Catal. Today. 62 (2000) 159, Niwa and co-workers, Appl. Catal. B: Env. 41 (2003) 137.
[3] Y-H. Chin, W.E. Alvarez, D.E. Resasco, Catal. Today. 62 (2000) 291.
[4] C. Thomas, C. Fontaine, J.M. Krafft, F. Villain, G. Djéga-Mariadassou, Appl. Catal. B: Env. 63 (2006) 201.

238 On the unexpected promoting effect of the PdCl 2 precursor on the CH 4 -SCR of NO x for WO x -ZrO 2 -supported catalysts
M. Faticanti, X. Carrier, J.-M. Krafft, M. Che and C. Thomas*
Laboratoire de Réactivité de Surface, Université Pierre et Marie Curie-Paris6, UMR CNRS 7609, Paris, France.
*Corresponding author. Tel: +33 1 44 27 36 30, Fax: +33 1 44 27 60 33, e-mail: cthomas@ccr.jussieu.fr
Background
Despite numerous studies performed on the CH 4 -SCR of NO x , the development of more efficient and durable catalytic formulations is still of the utmost interest
to meet the ever more drastic regulations on the emissions from stationary sources. Apart from zeolite-supported materials [1], Pd supported on acidic sulphatedor
tungstated-zirconia has also shown interesting capabilities for the CH 4 -SCR of NO x [2,3]. In these studies [3], however, various Pd precursors were used which
made difficult to draw definite conclusions about the influence of the nature of the Pd precursor on the CH 4 -SCR of NO x for Pd/WO x -ZrO 2 catalysts.
Results
For this purpose, Pd(NO 3 ) 2 and PdCl 2 precursors (Johnson Matthey) have been impregnated (0.25 wt% Pd) on WO x -ZrO 2 (WZ: 12 wt% W) prepared by refluxing
a commercial zirconium oxyhydroxide (MEL Chemicals, XZO880/01) and ammonium metatungstate (Fluka) at 110 °C for 20 h. After drying, the samples were
calcined at 650 °C for 3 h under static air. The catalysts were then characterised by XRD, Raman spectroscopy and adsorption of CO followed by FTIR. The
CH 4 -SCR of NO x (1500 ppm CH 4 , 7 % O 2 and 500 ppm NO x ), was studied in a quartz μ-reactor coupled to a set of specific detectors [4].
For both catalysts, a maximum in the NO x conversions is observed at 500 °C with CH 4 conversions close to 40 %. Yet, PdCl 2 /WZ exhibits a much greater (+ 63
%) yield in N 2 than that found for Pd(NO 3 ) 2 /WZ, despite the fact that elemental analysis of PdCl 2 /WZ shows that Cl - are fully removed after calcination. XRD
patterns do not show any significant difference between both catalysts, in which the tetragonal zirconia phase is mainly (~ 90 %) stabilised. In contrast, the
Raman measurements clearly reveal that the use of PdCl 2 limits the sintering of W, since only polytungstate species (WO x ) are observed with W=O and W-O-W
contributions at 1021 and 825 cm -1 , respectively, whereas that of Pd(NO 3 ) 2 shows the additional presence of WO 3 ( W-O-W at 809 cm -1 ). In agreement with the
greater dispersion of W on PdCl 2 /WZ, the adsorption of CO at
77 K followed by FTIR shows a greater Brønsted acidity of this material, both in terms of number (contributions O=C .. HO at 2177 cm -1 and O-H .. CO at 3480 cm -1 )
and strength ( OH ) of acid sites, than that of Pd(NO 3 ) 2 /WZ. The involvement of the Brønsted acid sites in the CH 4 -SCR of NO x will be discussed.
Justification for acceptance
In most cases, the use of chlorinated precursors is avoided, as the deposition of Cl - on the support may influence negatively the catalytic properties of the asprepared
materials. This study shows that overcoming such a prejudice may lead to the preparation of materials with improved efficiencies for environmental
concern.
References
[1] C. Montes de Correa, F. Córdoba Castrillón, J. Mol. Catal. A: Chemical 228 (2005) 267.
[2] E.M. Holmgreen, M.M. Yung, U.S. Ozkan, J. Mol. Catal. A: Chem. 270 (2007) 101.
[3] Resasco and co-workers, Catal. Today. 62 (2000) 291, Niwa and co-workers, Appl. Catal. B: Env. 41 (2003) 137.
[4] C. Thomas, C. Fontaine, J.M. Krafft, F. Villain, G. Djéga-Mariadassou, Appl. Catal. B: Env. 63 (2006) 201.
239 Unambiguous evidence for the formation of RNO x compounds on WO x -ZrO 2 -based catalysts:
active or spectator species in the C 3 H 6 -SCR of NO x ?
N. El Kolli, C. Potvin and C. Thomas*
Laboratoire de Réactivité de Surface, Université Pierre et Marie Curie-Paris6, UMR CNRS 7609, Paris, France.
*Corresponding author. Tel: +33 1 44 27 36 30, Fax: +33 1 44 27 60 33, e-mail: cthomas@ccr.jussieu.fr
Background
The HC-assisted catalytic reduction of NO x from diesel exhausts is still of the greatest interest, as no catalyst satisfies the severe environmental regulations yet.
Despite the promising results reported by Chen et al. [1], Pd/WO x -ZrO 2 (Pd/WZ) has not been further studied in the C 3 H 6 -SCR of NO x . Weingand et al. reported
that nitrates adsorbed on WZ interact with C 3 H 6 to form RNO x species which decompose and react with NO+O 2 to produce N 2 [2]. These species are not
described quantitatively and their reactivity at high temperatures does not imply that N 2 production at lower temperatures occurs mainly through such a pathway
on Pd/WZ.
Results
Pd(0.19 wt%)/W(12 wt%)Z and WZ samples were prepared by refluxing a commercial zirconium oxyhydroxide (MEL Chemicals, XZO880/01), ammonium
metatungstate and Pd(NO 3 ) 2 at 110 °C for 20 h. After drying, the samples were calcined at 650 °C for 3 h. Adsorption of NO x followed by temperatureprogrammed
experiments using various gas feeds or steady-state C 3 H 6 -SCR of NO x (500 ppm C 3 H 6 , 7 % O 2 and 400 ppm NO x ) were performed in a quartz μ-
reactor coupled to a set of specific detectors [3].
After RT-adsorption of NO-O 2 -He on Pd/WZ, a broad (RT-250 °C) desorption NO x (NO + NO 2 ) profile peaking at 80 °C is observed in the TPD in O 2 -He, in
which NO 2 is the major desorbed species. In contrast, in the TPD in C 3 H 6 -O 2 -He, the intensity of this low-temperature desorption peak decreases drastically,
whereas a broad (260-500 °C) NO x desorption profile appears, NO being the major species in this case. Concomitantly, an excess of CO x species is measured in
the gas phase. This demonstrates unambiguously that various RNO x species form by reaction of C 3 H 6 with the ad-NO x species and decompose at high
temperatures. From transients in which C 3 H 6 was removed from the feed at various temperatures, a C to NO molar ratio of about 3 is determined in the formed
RNO x . The decomposition of the RNO x species occurs, however, at temperatures greater than those at which NO x are reduced in the steady-state C 3 H 6 -SCR,
suggesting that RNO x species are spectators on Pd/WZ. A comparison will be made with a Pd/Ce 0.68 Zr 0.32 O 2 catalyst [3], for which RNO x species decompose at
temperatures that closely correspond to those of the C 3 H 6 -SCR of NO x . A particular emphasis will be put on the oxidation state of Pd.
Justification for acceptance
This work provides a methodology which may allow for the involvement of RNO x as intermediates in the HC-SCR of NO x . As far as the decomposition of RNO x
is a prerequisite in the HC-SCR process, this methodology may help in the prediction of the operating temperature window of the synthesised catalysts.
References
[1] Y.-H. Chin, W.E. Alvarez, D.E. Resasco, Catal. Today. 62 (2000) 291.
[2] T. Weingand, S. Kuba, K. Hadjiivanov, H. Knözinger, J. Catal. 209 (2002) 539.
[3] C. Thomas, C. Fontaine, J.M. Krafft, F. Villain, G. Djéga-Mariadassou, Appl. Catal. B: Env. 63 (2006) 201.

242 Effect of physical mixing of metal oxide with Ir-Ba/WO 3 -SiO 2 on CO-SCR activity
T. Nanba,* K. Wada, S. Masukawa, J. Uchisawa, A. Obuchi
National Institute of Advanced Industrial Science and Technology (AIST), Research Center for New Fuels and Vehicle Technology, 16-1 Onogawa, Tsukuba 305-8569, Japan
*Corresponding author. Tel: +81-29-861-8288, Fax: +81-29-861-8259, e-mail: tty-namba@aist.go.jp
Background: NOx reduction from diesel engines by using a reducing component in the exhaust, such as CO and hydrocarbon, is a promising way. Ir-Ba/WO 3 -
SiO 2 is known to be an active catalyst for the selective catalytic reduction of NOx with CO (CO-SCR) and Ir is its active component [1,2]. We have found that a
physical mixture of the Ir catalyst and metal oxides that has no CO-SCR activity alone, improved CO-SCR activity. In this paper, we propose a reaction
mechanism involving an intermediate migration from Ir to the metal oxide surfaces.
Results: Table 1 lists CO-SCR activities of Ir-Ba/WO 3 -SiO 2 , which was composed of 3 wt% Ir, 2.1 wt% Ba (same molar as Ir)
and 10 wt% WO 3 , and its physical mixtures with metal oxides. CO-SCR activities for all the physical mixtures were higher
than the Ir catalyst alone. We examined byproducts formation in the CO-SCR for these catalyst systems with a low
concentration of O 2 (0.5% O 2 ). With Ir-Ba/WO 3 -SiO 2 , no nitrogen-containing by-product was observed. HNCO was formed
for a physical mixture with SiO 2 , the concentration of which increased and then decreased with increasing the contact time.
The HNCO formation was extrapolated to the original point, suggesting that HNCO was an intermediate. It is known that
isocyanate (–NCO) easily migrate onto SiO 2 surfaces[3], so that the migration of isocyanate from Ir to SiO2 is expected to
occur and make vacancies of active sites on Ir surfaces, which may promote the reaction. For the physical mixture with ZrO 2 ,
NH 3 but no HNCO were formed, suggesting that HNCO was hydrolyzed on ZrO 2 . DRIFT measurements with the physical
Table 1. CO-SCR activity.
Mixture max NO x conv (%)
non
66 (245°C)
SiO 2 80 (250°C)
ZrO 2 87 (230°C)
HZSM5 79 (240°C)
Cat. Weight: 20mg (mixture:
0.2g), Flow rate: 400 ml/min,
Feed: 200ppm NO, 3000ppm
CO, 10% O 2 , and 7% H 2 O.
mixture with HZMS-5, which had a much higher capacity of NH 3 adsorption than ZrO 2 , revealed that adsorbed NH 3 increased in the absence of O 2 and
diminished in the presence of O 2 . Since NH 3 is known to react with O 2 on H-ZSM-5 to form N 2 with a high selectivity[4], NH 3 is supposed to subsequently react
with O 2 or NO+O 2 in this case. It is concluded that the enhancement of CO-SCR activity by physical mixtures with metal oxides was due to clearance of active
sites of Ir by the migration of isocyanate and its subsequent reaction to form N 2 .
Justification for acceptance: Increasing an active component is an ordinary way for increasing the rate of a catalytic NOx reduction. However, reducing the
amount of noble metals used in the catalyst is an important issue. We emphasize that addition of materials which has no active component for SCR but are active
for intermediate reactions of SCR, can increase the total reaction rate.
References
[1] A. Takahashi, T. Fujitani, I. Nakamura, Y. Katsuta, M. Haneda, H. Hamada, Chem. Lett., 35 (2006) 420.
[2] M. Haneda, Pursparatu, Y. Kintaichi, I. Nakamura, M. Sasaki, T. Fujitani, H. Hamada, J. Catal., 229 (2005) 197.
[3] F. Solymosi, J. Raskó, Appl. Catal., 10 (1984) 19.
[4] M. Richter, H. Berndt, R. Eckelt, M. Schneider, R. Fricke, Catal. Today 54 (1999) 531.
246 DeNO x with CO over Pd catalysts under simulated post Euro- diesel exhaust conditions
Li Yinghua a , Dae-Won Lee b , Young-Chul Ko a , Yoon-Ki Hong a , Young-San Yoo c , Hyun-Sik Han c and Kwan-Young Lee a, *
a Department of Chemical & Biological Engineering, Korea University, Seoul 136-701, South Korea
b Research Institute of Clean Chemical Engineering, Korea University, Seoul 136-701, South Korea
c Heesung Catalysts Corporation, 507-1 Da, 1251-6, Tungwang-Dong, Shiheung City, Kyungki-Do, South Korea
* Corresponding author. Tel: +82-2-3290-3299, Fax: +82-2-926-6102, e-mail: kylee@korea.ac.kr
Background
The concentration of CO in the diesel exhaust increased whilst NO x decreased with the development of engine tuning strategies to match the post Euro- emission standards. So
it will be promising if a catalytic reduction of NO x by CO in passive system can be carried out effectively, which means NO x removal without external reductant feeding in. As
far as we know, there’s still no report about that. Even if most works studied in active system can get high catalytic activity [1], more research about passive deNO x system needs
to be done in the CO-rich conditions.
Results
Here the simulated post Euro- diesel exhausts (500 ppm NO, 8,000 ppm CO, 8% O 2 and 10% H 2 O) were utilized to test the deNO x performance over Pd/Al 2 O 3 and
Pd/TiO 2 /Al 2 O 3 catalysts. Metallic Pd, after pretreatment in 10 vol.% H 2 , was well dispersed on the supports surface when its amount is less than 2% (XPS and XRD). The
average Pd particle size of 2 wt.% Pd/10 wt.% TiO 2 /Al 2 O 3 was 6 nm (TEM). More Pd loading would cause severe aggregation. Seen in the SEM images, when TiO 2 loading
increased to 15 wt.%, the surface of Al 2 O 3 particles was over-coated by TiO 2 , and then particles adhered together badly. That caused the decrease of catalytic activity. An
optimized catalyst with 2wt.% Pd and 10wt.% TiO 2 loading was selected and showed NO x conversion of 26 51% without water in range of 100 250. While TiO 2 /Al 2 O 3
itself did not show good activity to NO x reduction, the presence of TiO 2 promoted catalytic activity of Pd/Al 2 O 3 obviously. Even if H 2 O showed negative influence, 25 33% of
NO x could still be decomposed. Small amount of H 2 , which exists in the actual exhausts with a ratio of about 1:3 to CO, resulted in a visible synergetic effect. That is the NO x
conversion increased to 45% at 150 200.
Justification for acceptance
Since no study has reported the application of passive deNO x catalysis into diesel exhaust only using carbon monoxide as reductant, our work looks innovative and meaningful.
Moreover, we found newly optimized Pd/TiO 2 /Al 2 O 3 catalyst targeting post Euro- exhaust conditions.
References
[1] A.M. Arias, A.B. Hungría, M.F. García, A.I. Juez, J.A. Anderson, J.C. Conesa, J. Catal., 221, 85 (2004).

247 Reduction of NO by C 3 H 6 over Rh/CeO 2 -ZrO 2
M. Haneda, a, * K. Shinoda b , A. Nagane b , O. Houshito b , H. Takagi b , Y. Nakahara b , K. Hiroe b , T. Fujitani a and
H. Hamada a
a National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba Central 5,
1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
b Mitsui Mining and Smelting co., ltd, 1332-2 Haraichi, Ageo, Saitama 362-0021, Japan
*Corresponding author: Tel: +81-29-861-9326, Fax +81-29-861-4647, E-mail: m.haneda@aist.go.jp
Background
Recently, the total demand of precious metals for automotive catalysts is increasing year after year because of a global increase of environmental
consciousness. Therefore, the studies to minimize the usage of precious metals have been received extensive attention. In this study, we investigated in detail the
influence of Ce/Zr composition on the catalytic activity of Rh/CeO 2 -ZrO 2 for NO reduction by C 3 H 6 in a stoichiometric condition, in order to get information
leading to a decrease of Rh usage in three-way catalyst.
Results
The catalytic activity of Rh/CeO 2 -ZrO 2 with different Ce/Zr compositions for NO reduction with C 3 H 6
was measured, by passing a reaction gas containing 500 ppm NO, 1167 ppm C 3 H 6 , 0.5% O 2 and 10% H 2 O
balanced by N 2 through a catalyst (0.1 g) at a flow rate of 1 L min -1 . As shown in Fig.1, the catalytic activity
strongly depended upon the Ce/Zr composition. The Rh/CeO 2 -ZrO 2 with Ce/Zr ratio of 58/42 (Rh/CZ-58/42)
showed the highest activity while that with Ce/Zr=80/20 (Rh/CZ-80/20) was the least active catalyst. On the
other hand, when the NO reduction by C 3 H 6 (NO+C 3 H 6 reaction) was carried out in the absence of O 2 , the
Rh/CZ-80/20 was found to effectively catalyze NO reduction, suggesting a significant retarding effect of O 2
on the activity of Rh/CZ-80/20 catalyst. The surface species formed during the NO+C 3 H 6 +O 2 reaction over
Rh/CZ-80/20 was measured by in-situ diffuse reflectance FT-IR spectroscopy. Although Rh-NO species,
which is proposed as a reaction intermediate, was observed, main species formed on the surface was carbonate
and formate species. Among them, formate species was found to be very stable under the reaction condition,
and was considered to behave as poisoning species by blocking the catalytically active site, resulting in the
low activity of Rh/CZ-80/20.
Justification for acceptance
The reduction of precious metal usage in three-way catalyst is a very important issue. This work was
performed with the aim to obtain information for the improvement of intrinsic activity of active precious metal species.
NO conversion / %
100
80
60
40
20
0
-10
: Rh/CZ-0/100
: Rh/CZ-20/80
: Rh/CZ-40/60
: Rh/CZ-58/42
: Rh/CZ-80/20
: Rh/CZ-100/0
80100 200 300 400 500 600
Temperature / C
Fig.1. NO conversion vs. temperature for
NO+C 3 H 6 +O 2 reaction in a stoichiometric
condition over Rh/CeO 2 -ZrO 2 catalysts.
248 CeO 2 -Y 2 O 3 and CeO 2 -ZrO 2 -Y 2 O 3 mixed oxide catalysts for diesel soot combustion.
I. Atribak, A. Bueno-López, A. García-García * .
MCMA Group. Inorganic Chemistry Department. University of Alicante, Ap-99, E-03080 Alicante, Spain.
*Corresponding author. Tel: +34 965909419, Fax : +34 965903454, e-mail: a.garcia@ua.es
Background
Catalysed soot oxidation seems to be a proper strategy to decrease the soot burn-off temperature in a controlled fashion, and, thereby, increasing the overall fuel
efficiency of the diesel engines. Ceria and ceria-based catalysts play important roles as diesel soot oxidation catalysts. The modification of CeO 2 with certain
cations can improve the stability towards sintering and also the oxidation activity of the resulting catalysts. The choice of the dopant and its amount as well as the
synthesis route used is critical in determining the properties of the final catalysts prepared. The scarcity of the data in the literature does not allow a rationale for
the role of the dopants, because, very often, their influence can be masked by the fact that samples with different textural properties are compared [1]. Therefore,
the aim of this contribution was to investigate the effect of the amount of yttrium (chosen as dopant) on the final properties of ceria-yttria and ceria-zirconia-yttria
catalysts for soot combustion.
Results
Ce 1-x Y x O 2 and Ce 0.85-x Zr 0.15 Y x O 2 samples (x = 0, 0.01, 0.05 and 0.10) were prepared by calcination of nitrate precursor mixtures at 1000°C. The textural, structural
and redox behaviour characterisation of the two series of catalysts was performed by N 2 adsorption at -196ºC, XRD, Raman Spectroscopy, XPS and H 2 -TPR. The
catalytic activity was measured in loose and tight contact mode by thermogravimetry with a 5%O 2 flow and Printex-U as model soot. The characterisation reveals
that the doping with yttrium does not avoid the ceria sintering, all the Ce 1-x Y x O 2 samples showing a BET surface area of 2-3 m 2 /g, and does not change
significantly the bulk reduction of these catalysts with H 2 (surface reduction is not observed). However, Ce 1-x Y x O 2 catalysts are more active than bare CeO 2 .The
Ce 0.99 Y 0.01 O 2 catalyst is the most active of the Ce 1-x Y x O 2 series for soot combustion, decreasing the T50% temperature from 575ºC for bare CeO 2 to 540°C (for
tight contact experiments). XPS showed Y accumulation on the catalyst surface, suggesting that a very low yttrium dosage (x=0.01) slightly improves the
catalytic activity of cerium (the really active component) while higher yttrium loading diminishes the amount of surface cerium. Concerning the Ce 0.85-x Zr 0.15 Y x O 2
samples, the presence of zirconia partially prevents ceria sintering (BET surface area of Ce 0.85 Zr 0.15 O 2 is 11 m 2 /g), and this value remains more or less unchanged
for the ceria-zirconia-yttria samples. All the Ce 0.85-x Zr 0.15 Y x O 2 catalysts present a low-temperature surface reduction peak (since 500°C) in H 2 -TPR experiments,
absent for the other series. The synergism between higher surface areas and improved surface reduction would explain the enhanced activity of zirconiumcontaining
catalysts (T50% among 456-471°C, for tight contact). Even though, a 0.01 yttrium loading is also the optimum composition for the ternary series, but
the improvement in catalytic activity is not as important as for the binary series is.
Justification for acceptance
This work forms part of one of the most significant topics of this Conference on Environmental Catalysis: the Automotive Emission Control. In particular, the
removal of soot from diesel exhausts, which is one of the most challenging issues of current scientific and technological research.
References
A. Trovarelli. “Catalysis by Ceria and Related Materials”. Catalytic Science Series, Vol.2 (2002).

251 Direct decomposition of NO on Ba catalysts supported on Ce-Fe mixed oxides
W.-J. Hong, S. Iwamoto * , and M. Inoue
Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan
*Corresponding author. Tel: +81 75 3832481, Fax: +81 75 3832479, e-mail: iwamoto@scl.kyoto-u.ac.jp
Background
Emission of nitrogen oxides (NO x ) causes severe environmental problems, and effective methods to decrease NO x emissions are sought. Among various
deNO x strategies, direct decomposition of NO is the most desirable method because this reaction is thermodynamically favorable and does not need any
reductants. Previously, we reported that Ba catalysts supported on Ce-Mn mixed oxides showed markedly high activities for this reaction [1]. In this study, CeO 2
samples modified with Fe, less toxic than Mn, were prepared and NO decomposition activities of the Ba catalysts supported on them were examined.
Results
Barium catalysts (7wt% BaO) were prepared by impregnating Ba(NO 3 ) 2 on Ce-Fe mixed oxides with
various Ce/Fe ratios (designated as Ce-Fe(x); x = Fe/(Ce+Fe)). After calcination at 800 °C in air for 1 h, NO
decomposition activities were examined. Figure 1 shows the NO decomposition at 800 ºC over Ce-Fe(x) and
7wt%BaO/ Ce-Fe(x). While the Ce-Fe(x) mixed oxides exhibited quite low activities, Ba-loading catalysts
showed significant activities. As compared with the Ba catalysts supported on CeO 2 and Fe 2 O 3 , which exhibited
18 % and 5 % NO conversions, respectively, the catalysts supported on Ce-Fe mixed oxides showed enhanced
activities. Among the catalysts examined, 7wt%BaO/Ce-Fe(0.02) showed the highest NO conversion. These
catalysts were characterized by XRD, XPS, XAFS, and TPD, and the results will be presented.
Justification for acceptance
Development of deNOx catalysts is one of the most important subjects in emission control technologies.
This paper reports a novel catalyst active for direct NO decomposition. The catalyst components are relatively
inexpensive and harmless, indicating a potential for practical applications. Therefore, we think this presentation
will provide significant contribution in the ICEC.
NO conversion to N 2 (%)
60
50
40
30
20
10
7wt%BaO/Ce-Fe(x)
Ce-Fe(x)
0
0.0 0.2 0.4 0.6 0.8 1.0
Fe/(Ce+Fe)
Fig. 1. NO conversion to N2 on Ce-Fe(x) and
7wt%BaO/Ce-Fe(x) as a function of Fe content. Catalyst,
0.5 g; reaction gas, 6000 ppm NO in He; flow rate, 30
ml/min; W/F = 1.0 g·s·ml -1 ; reaction temperature, 800 °C.
Reference
[1] S. Iwamoto, R. Takahashi, M. Inoue, Appl. Catal. B: Environmental, 70 (2007) 46.
259 SCR on Fe/BEA zeolite catalysts in diesel exhaust
P. Balle, B. Geiger, S. Kureti*
University of Karlsruhe, Institute of Technical Chemistry and Polymer Chemistry, Germany
*Corresponding author. Tel: +49 721 608 8090, Fax : +49 721 608 2816, e-mail: Kureti@ict.uni-karlsruhe.de
Background
The selective catalytic reduction (SCR) and NO x storage reduction catalysts (NSR) are actually the favoured techniques to remove nitrogen oxides from the
exhaust of diesel vehicles. However, a serious disadvantage of the SCR technology is the toxicological concern of the V 2 O 5 catalyst that can sublimate or melt at
high exhaust temperatures. Such temperatures are achieved in diesel passenger cars if the SCR catalyst is placed downstream to a diesel particulate filter
operating with active regeneration. Contrary, it is known that Fe containing catalysts exhibit significant SCR activity without toxicological relevance, for instance
Fe-ZSM5 zeolite [1, 2]. Hence, the present contribution deals with the development of novel vanadium free catalysts based on the active component Fe including
detailed physical-chemical characterisation of the resulting Fe x O y species.
Results
Our catalyst development led to a new Fe/BEA zeolite system which shows higher SCR performance as compared to commercially available Fe-exchanged BEA
as well as classical V 2 O 5 /WO 3 /TiO 2 systems [3]. At 200 and 250°C the Turnover Frequency of NO x is almost one order of magnitude higher for the Fe/BEA
catalyst than for V 2 O 5 /WO 3 /TiO 2 (feed composition: 500 ppm NO, 500 ppm NH 3 , 5% O 2 , N 2 balance, 50’000 h -1 ) indicating high low temperature activity.
Additionally, the poster presentation provides a knowledge-based argument for the outstanding SCR performance of the Fe/BEA zeolite. Systematic DR UV-VIS,
HTPR and HRTEM characterisation studies show that the superior SCR activity is associated with a high proportion of isolated Fe oxo species, whereas
oligomeric Fe x O y clusters and Fe 2 O 3 particles reveal minor SCR kinetics. Moreover, the latter species support the NH 3 oxidation leading to decreased SCR
performance above 400°C.
Furthermore, our contribution demonstrates the supporting effect of NO 2 in low-temperature deNO x and it also states the advanced hydrothermal stability of
Fe/BEA (450 and 750°C) as compared to the classical vanadia based system. Finally, we report on the very promising transfer of performance from the powder to
the industrially relevant honeycomb level.
Justification for acceptance
Present contribution reports on a highly active Fe/BEA SCR zeolite catalyst which reveals superior activity as compared to the classical V 2 O 5 /WO 3 /TiO 2 pattern.
Furthermore, it shows advanced hydrothermal stability up to elevated temperatures being of high importance for practice. Extensive characterization of the active
Fe species provides detailed understanding of the outstanding SCR activity of the Fe/BEA catalyst.
References
[1] R.Q. Long, R.T. Yang, J. Catal. 188 (1999) 332.
[2] K.M. Santhosh, M. Schwidder, W. Grünert, A. Brückner, J. Catal. 227 (2004) 384.
[3] P. Balle, B. Geiger, S. Kureti, paper in preparation.

260 The possibilities of hydrotalcites as NO x Storage/Reduction catalysts.
A.E. Palomares * , A.Uzcátegui, A. Corma
Instituto de Tecnología Química, Departamento Ingeniería Química y Nuclear, Universidad Politécnica de Valencia, UPV-CSIC, Avenida de los Naranjos s/n, 46022
Valencia, Spain.
*Corresponding author. Tel: +34963879632, fax +34963877639, e-mail: apalomar@iqn.upv.es
Background
The NO x storage/reduction (NSR) catalysts are catalysts for the NO x control in lean-burn engines. In these catalysts the NO x are stored as nitrates under lean
(oxidizing) conditions and they are reduced in the short, rich (reducing) excursions. NSR catalysts are typically composed of a basic compound and at least one
precious-metal component, as Pt and Ba supported on Al 2 O 3 . This material is quite active, but it shows some problems as its price, the fast poisoning by sulfur
compounds and its low activity at low temperature. In this work we study the possibilities of using calcined hydrotalcites as active NSR catalysts.
Results
Cu or Co/Mg/Al hydrotalcites were prepared by a standard co-precipitating procedure. Some samples were impregnated with different transition metal salts and
calcined at 650ºC. In the experiments 1g of catalyst, was contacted with a 650 ml.min -1 feed of a mixture composed by NO, C 3 H 8 , oxygen and balanced with
nitrogen. The O 2 :C 3 H 8 ratio was changed in order to perform a lean cycle (oxidizing) and a rich cycle (reducing) and the experiments were carried out at different
temperatures. It was observed that hydrotalcites remove the NO quite efficiently during the lean period, adsorbing the NO x as nitrates, but the activity falls during
the rich period. In all range of the temperatures tested (100, 200, 300 and 450ºC) the activity of the catalysts based in cobalt was better than that of the copper
hydrotalcite. Hydrotalcites with different cobalt content were tested observing that the samples with 10-15% of cobalt show the best activity. The maximum
conversion was obtained at the beginning of the reaction, decreasing during the reaction and without recovering the initial activity after the rich cycle. This shows
that in this cycle it is no possible to desorb/reduce the NO stored in the lean cycle. An additional increase in the cobalt content results in the formation of different
phases in the material leading to a decrease in their activity. The activity of the samples could be further improved by activating the material with hydrogen and
by adding 1 wt % Pd, if the catalytic tests are made at low temperatures, or with 1% wt Pt, if they are carried out at higher temperatures. It was also checked the
possibilities of using another non-noble metals with redox properties. It was observed that doping the hydrotalcite with Na-V or Na-Ru leads to better results that
those catalysts using noble-metals The resistance of the cobalt hydrotalcites to water and sulphur was tested, observing that there was no any important change in
the catalysts activity of the hydrotalcite with 15% cobalt in presence of 15% water and 30 ppm of SO 2 .
Justification for acceptance
This research fits in the topic of automotive emissions control. The results show the possibilities of using a material with basic properties, as hydrotalcites, doped
with a non noble metal with redox properties as an active NSR catalyst. This could be very interesting because the activity and the low-price of the material.
264 A comparison of transport models for the simulation of three-way catalysts
N. Mladenov * , J. Koop, O. Deutschmann
Institute for Chemical Technology and Polymer Chemistry, University of Karlsruhe, 76128 Karlsruhe, Germany
* Corresponding author: Tel: +49 721 608-6716, Fax: -4805, E-mail: mladenov@ict.uni-karlsruhe.de
Background: Today, environmental protection is a worldwide problem enforcing stringent legislation for exhaust gas emissions. In order to meet the prescribed
limits, three-way catalytic converters (TWC) have become standard for gasoline cars. Their content of precious metals (Pt, Rh) has a direct impact on the costs.
Hence, investigating the complex interaction between chemical reactions and transport inside the catalyst is imminent in order to improve its performance.
Numerical simulations represent a powerful tool for development and optimization of TWC. Understanding the physical and computational accuracy of the
various numerical models is an important aspect in the analysis of the catalyst’s performance [1]. Depending on the complexity of the applied model,
computational times can vary from few seconds to several days.
Results: The current study presents a comparison of various models for the simulation of a steady-state flow in a single channel of a honeycomb TWC operated
under isothermal conditions. The simplest one is the 1D plug-flow model neglecting axial and radial diffusion. The 2D boundary-layer model accounts for the
diffusion in radial direction. Finally, both axial and radial diffusion through solving the complete Navier-Stokes equations are considered. The plug and the
boundary-layer models assume cylindrical channel geometry; the calculations were carried out with the DETCHEM software package. The detailed Navier-
Stokes models also take the influence of the channel geometry into account by comparing cylindrical geometry (2D) and rectangular geometries with straight and
rounded corners (3D). They were simulated in FLUENT. Furthermore, the effect of washcoat on the conversion of hydrocarbons and nitric oxide is included. For
this purpose, simplified and detailed porous media models are introduced. The diffusion coefficients in the porous media are determined based on a modified Fick
diffusion coefficient considering the molecular and Knudsen diffusion. The calculations are carried out for 250ºC and 350ºC with a lean gas-mixture entering the
channel’s inlet. A detailed surface chemistry mechanism consisting of 73 elementary reactions is applied in all simulations [2,3], gas-phase reactions are not
taken into account. The calculated concentrations of hydrocarbons and NOx along the channel are compared with experimental data.
Justification for Acceptance: The current study aims to give a detailed overview of the various models for simulating a single channel of a TWC. A wide
spectrum of reacting flow models is covered, ranging from simple one-dimensional models without any mass-transport limitation to complex three-dimensional
models with mass-transport limitation in both channel and washcoat. Thus, we can evaluate the applicability of the different models for TWC simulations.
[1] L. Raja, R. Kee, O. Deutschmann, J. Warnatz, Catalysis Today 59 (2000) 47-60.
[2] D. Chatterjee, O. Deutschmann, J. Warnatz, Faraday Discussions 119 (2001) 371-384.
[3] J. Koop, PhD thesis, University of Karlsruhe (2008).

265 Investigation and calibration of a global kinetic model of today's 3 way catalytic converters
Background
C.N. Millet * , S. Benramdhane, E. Jeudy
IFP-Lyon, BP3, 69360 Solaize, France.
*Corresponding author. Tel: +33 (0) 478022187, Fax : +33 (0) 478022014, e-mail: c-noelle.millet@ifp.fr
The increasingly tighter automotive emission standards demand rapid light-off and excellent conversion in the hot 3 way catalytic converter (3WCC) despite the
deviations from stoichiometric composition. Today's catalysts have a particularly large efficiency window. This is partly due to the activation of reactions
involving water. Experimental kinetic studies conducted together with numerical investigations allow to get a thorough understanding of the reaction mechanism
that takes place in the 3WCC [1,2,3].
Results
A 3 way catalytic converter (3WCC) global kinetic model was developed and validated against laboratory scale and engine test bench experiments. Laboratory
scale experiments were first used to characterize the reaction mechanism during light-off and calibrate the kinetic constants. These constants were then adapted to
simulate a real scale 3WCC as investigated on an engine test bench, yielding predictive results.
The combination of the experimental kinetic study and the model calibration highlighted the importance of considering the whole set of global reactions that
occur around stoichiometry. The way reduction and oxidation reactions begin and compete with each other could be investigated as a function of temperature and
air to fuel ratio. Among others, this work also showed that water action is essential at high temperature in rich conditions, so as to ensure a high HC conversion
despite the lack of oxygen. It emphasized the role of H 2 at low temperature.
Justification for acceptance
The reaction mechanism and global kinetics involved in a 3WCC are investigated by combining experimental and numerical works. This research
also demonstrates how a kinetic model established after laboratory scale experiments can be successfully adapted and used to simulate the light-off
and the conversion efficiency of a real scale catalyst mounted on an engine test bench.
References
[1] A. Chow, M.L. Wyszynski, Proc.of the IMECHE Part D-Journal of automobile engineering 214 (D8) (2000) 905
[2] L.S. Mukadi, R.E. Hayes, Computers and Chemical Engineering 26 (2002) 439
[3] A. Onorati, G. Ferrari, G. D'Errico, SAE Paper, 2003-01-0366 (2003)
268 Improved detailed reaction mechanisms for three-way catalysts
S. Tischer * , L. Maier, O. Deutschmann
Institute for Chemical Technology and Polymer Chemistry, University of Karlsruhe, 76128 Karlsruhe, Germany
* Corresponding author: Tel: +49 721 608-2114, Fax: -4805, E-mail: tischer@ict.uni-karlsruhe.de
Background: Three-way catalytic converters (TWC) are well-established devices for the reduction of emissions of gasoline cars. Despite their wide-spread
application, predictive simulations of TWC under real driving conditions are still challenging. Frequently, global-step reaction mechanisms are used, that need to
be adjusted individually for each catalyst composition. This is a suitable approach for monitoring the performance of existing catalysts. For an optimization of the
catalyst design and composition we depend on more detailed models [1]. The aim of this study was to develop and improve mechanisms of the TWC reactions on
platinum, palladium and rhodium.
Results: For each catalytic active component, Pt, Pd and Rh, an elementary-step reaction mechanism has been set up in analogy to the Pt/Rh mechanism of
Chatterjee [2]. Data from test bench experiments with exhaust gas recirculation under isothermal conditions for three different synthetic gas mixtures
(stoichiometric, lean and rich) was used for mechanism development [1]. The initial activation energies have been chosen in consistency with literature data. For
the fine-tuning of the reaction coefficients a genetic algorithm with random-walk variations has been applied. For each set of parameters, a thermodynamic
consistent reaction mechanism is generated. Experimental data is then compared to numerical simulations using the model of a continuously stirred tank reactor.
Thus, in an iterative process the mechanisms have been improved until agreement with experimental data was achieved.
In a second step, numerical simulations using DETCHEM [3] with the improved reaction mechanisms are compared to transient measurements of European
standard driving cycles featuring realistic exhaust gas compositions. The mechanisms show good agreement, but the scaling of the lambda value of the fuel/air
mixture was found to influence the simulation significantly. The measured lambda value needs to be re-scaled for the model inlet gas mixture, because only
propylene has been selected as representative of the hydrocarbon mixture. Therefore, a correlation between the oxygen concentration of the model mixture and
the lambda value has to be presumed. Finally, the simulation results for catalysts of arbitrary composition are used as target data in the same random-walk
procedure to generate reliable global-step reaction mechanisms.
Justification for Acceptance: Improving TWC design by numerical simulation depends on reliable reaction mechanisms that are valid over a wide range of
catalyst compositions. This can be achieved by the presented method that is suitable for the parameter fine-tuning of elementary-step and global reaction
mechanisms.
[1] S. Tischer et al., 4 th International Conference on Environmental Catalysis (2005).
[2] D. Chatterjee et al., Faraday Discussions 119 (2001), 371-384.
[3] O. Deutschmann et al., DETCHEM software package, Version 2.1, www.detchem.com (2007).

273 PCHs obtained from various cationic layered clays as base of DeNOx catalysts
L. Chmielarz * , P. Kustrowski, Z. Piwowarska, B. Dudek, R. Dziembaj
Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Krakow, Poland
*Corresponding author. Tel: +48 126632006, Fax : +48 126340515, e-mail: chmielar@chemia.uj.edu.pl
Background
Porous clay heterostructures (PCH) are very interesting materials for catalysis due to high surface area, uniform porosity, thermal and hydrothermal stability,
surface acidity and ion-exchange properties [1]. The synthesis of PCHs is based on a surfactant-directed assembly of open-framework silica in the galleries of
cationic layered clays. PCH materials obtained from various cationic layered clays were tested in the role of supports of DeNOx catalysts.
Results
Cationic layered clays (montmorillonite, saponite, vermiculite) were used as starting materials for the PCH preparation. The synthesis procedure consisted of the
following steps: i) cationic template (hexadecyltrimethylammonium or dodecyltrimetylammonium chloride) and neutral amine co-templates (hexadecylamine or
dodecylamine) were intercalated in the interlayer space of host clays forming micelle structures; (ii) the silica pillars were created by in-situ hydrolysis and
polymerization of a silica source (tetraethylorthosilicate) around micelles; (iii) the organic templates were removed from the material by calcination (550°C/6h).
Transition metal ions (Cu and Fe) were introduced onto PCHs by an ion-exchange method using solutions of suitable metal nitrates. Detailed description of the
synthesis procedure was presented in our previous papers [2, 3].
The PCH samples were characterized with respect to textural parameters (BET), structure (XRD, FT-IR), composition (EDX), surface acidity (NH 3 -TPD, FT-IR)
and coordination of transition metals (UV-vis-DRS). Finally, the samples were tested as catalysts for the selective reduction of NO with ammonia.
The PCH based samples have been found to be active, selective and stable catalysts of NO reduction with ammonia. Both the kind of parent clays used for the
PCHs synthesis as well as deposited transition metals strongly influenced the catalytic performance of the samples. The Cu-containing catalysts were active at
temperatures significantly lower than those modified with iron. A very high selectivity to nitrogen in a broad temperature range as well as resistance for
poisoning by water vapor and SO 2 are the other very promising properties of the PCH based catalysts.
Justification for acceptance
The contribution presents a group of relatively new materials (PCH) and their pioneer application in the role of the DeNOx catalysts. The results of preliminary
tests are very promising due to high activity, selectivity and stability of the PCH based catalysts.
[1] A. Galarneau, A. Barodawalla, T.J. Pinnavaia, Nature 374 (1995) 529.
[2] L. Chmielarz, P. Kustrowski, M. Drozdek, R. Dziembaj, P. Cool, E.F. Vansant, Catal. Today 114 (2006) 319.
[3] L. Chmielarz, P. Kustrowski, M. Drozdek, R. Dziembaj, P. Cool, E.F. Vansant, Catal. Today 119 (2007) 181.
274 Cu perovskite catalysts for soot combustion: effect of copper loading method
F. E. López-Suárez a , A. Bueno-López a , M.J. Illán-Gómez a * , B. Ura b , J. Trawczynski b , A. Adamski c
a
Inorganic Chemistry Department, University of Alicante. Ap. 99, E-03080 Alicante (Spain),
b Division of Chemistry of Technology Fuels, Wroclaw University of Technology (Poland)
c Faculty of Chemistry Jagiellonian University (Poland)
*Corresponding author. Tel: +34 96 5903975, Fax : +34 96 590 3454, e-mail: illan@ua.es
Background
Diesel engines are significant contributors to air pollution by NO x and particulate matter (soot). Nowadays, the most promising after–treatment technique for soot
removal is based on the soot capture and subsequent catalytic oxidation. Cu-containing perovskites have demonstrated to be active for soot oxidation [1]. In this
work, copper-containing perovskite catalysts, obtained by substitution of Cu in the mixed oxide structure (MgTi 0.9 Cu 0.1 O 3 and SrTi 0. 9 Cu 0.1 O 3 ) or by impregnation
of the parent perovskites with a Cu precursor (Cu/MgTiO 3 and Cu/SrTiO 3 ), have been prepared, characterized and tested for catalytic soot combustion. .
Results
The substituted catalysts were prepared by sol-gel method using H 2 O 2 , citrid acid, titanium (IV) isopropylate and aqueous solutions of Sr/Mg and Cu nitrates,
with final calcination at 750ºC. For impregnated catalysts synthesis, copper-free perovskites were prepared following the procedure described and the copper was
added afterwards by excess solution impregnation with copper nitrate, which is finally decomposed by 500ºC calcination. In all the catalysts, the copper loading
is similar (4 wt %). The catalysts were characterised by N 2 adsorption at 77 K, XRD, XPS and H 2 -TPR. Catalytic activity for soot combustion reaction was
determined using a commercial carbon black (Vulcan XC72) as model diesel soot. Activity tests were performed in a fixed-bed reactor at atmospheric pressure
under synthetic air and NOx/O 2 (500 ppm/5% in N 2 ).
In the presence of catalyst, the onset temperature for soot oxidation is decreased both in air and in NOx/O 2 mixture, and a higher soot combustion rate is found.
The different methods used for copper loading affect the catalysts surface properties and the activity for soot oxidation. The results reveal that the impregnated
catalysts are the most active because the copper surface species are more easily reduced in reaction conditions than those within the mixed oxide lattice. On the
other hand, all the catalysts tested improve the selectivity towards CO 2 as soot oxidation product, the impregnated catalysts being the most selective.
Justification for acceptance
The upcoming diesel emissions standards for particulate matter (PM) and NOx being implemented from 2007 to 2010 required the development of aftertreatment
technologies such as diesel particulate filters and NOx aftertreatment devices. This work is framed in the “automotive emission control.”.
References:
[1] F.E. Lopez Suárez, A. Bueno López, M.J. Illán Gómez, B. Ura, J. Trawczynski, Catalysis for Environment: Depollution, Renewable Energy and Clean Fuels.
/ Ed. P. Da Costa, G. Djéga Mariadassou, A. Krzton / Polish Academy of Sciences - Institute of Coal Chemistry PAS – Gliwice (2007), 143-148.

275 Characteristics and catalytic reactivity of soot from biodiesel
F. E. López-Suárez a , A. Bueno-López a , M.J. Illán-Gómez a * , C.A.Cardona b , O. H. Giraldo b C. E. Orrego b
a
Inorganic Chemistry Department, University of Alicante. Ap. 99, E-03080 Alicante (Spain),
b Departamento de Ingeniería Química, Universidad Nacional de Colombia sede Manizales
*Corresponding author. Tel: +34 96 5903975, Fax : +34 96 590 3454, e-mail: illan@ua.es
Background
The use of biodiesel is rapidly expanding around the world and, consequently, it is imperative to fully understand the impacts of biodiesel on the diesel
combustion process, pollutant formation and exhaust after treatment methodology. In this work, we analyze the impact that biodiesel has on the characteristics of
soot in relation with the regeneration of diesel particulate filter by catalytic oxidation.
Results
A direct injection turbodiesel engine (NISSAN -2000) was used to obtain the soot from biodiesel (100%) and from conventional diesel. In addition, and as
references, two commercial carbon blacks (Printex U and Vulcan XC72) were studied.
The catalytic tests for soot oxidation were performed in a fixed-bed reactor at atmospheric pressure under synthetic air and NOx/O 2 (500 ppm/5% in N 2 ) and the
products composition was determined by specific NDIR-UV gas analyzers. For soot characterization the following techniques were used: elemental analysis,
immediate analysis, BET surface are, TEM, Raman, XRD and DRIFTS.
The amount of soot produced decreases with biodiesel fuel in comparison to conventional diesel. In addition, the biodiesel soot shows significant changes in the
nanostructure with regard to conventional diesel soot: less ordered structure and smaller particle size. As consequence of these differences, a higher reactivity is
observed for biodiesel soot compared to conventional diesel soot. Both diesel and biodiesel soot show a higher reactivity than model soot (commercial carbon
blacks). In the presence of a selected catalyst (Cu/Perovskite) [1], the onset temperature for soot oxidation is decreased, both in air and in NOx/O 2 mixture, and a
higher soot combustion rate is also found. The enhancement of oxidation rate observed for biodiesel soot implies a reduction in the temperature required to
initiate the regeneration by oxidation in the diesel particulate filter (DPF).
References:
[1] F.E. Lopez Suárez, A. Bueno López, M.J. Illán Gómez, B. Ura, J. Trawczynski, Catalysis for Environment: Depollution, Renewable Energy and Clean Fuels.
/ Ed. P. Da Costa, G. Djéga Mariadassou, A. Krzton / Polish Academy of Sciences - Institute of Coal Chemistry PAS – Gliwice (2007), 143-148.
276 Cu/BaO/La 2 O 3 catalyst for the efficient simultaneous removal of NOx and carbon particulate
Hiromi YAMASHITA*, Yoshiro IWATA, Akihiko MIYAUCHI, Kohsuke MORI
*Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University
2-1 Yamada-oka, Suita, Osaka 565-0871, JAPAN
*Corresponding author. Tel: +81-6-6879-7457, Fax: +81-6-6879-7457
e-mail: yamashita@mat.eng.osaka-u.ac.jp
Background
NOx and carbon particulates have been causing severe environmental and health damages. The potential technique that can efficiently remove NOx and carbon
particulate is particularly desired . Since the simultaneous removal of NOx and carbon particulate can not be accomplished by either engine modification or fuel
pretreatment, catalytic removal of both harmful emissions should be developed. In this study, the simultanious removal of NOx and combustion of carbon
particulate over Cu/BaO/La 2 O 3 catalyst was carried out. It was found that the carbon particulate efficiently act as a solid reductant for the NOx reduction on
Cu/BaO/La 2 O 3 catalyst.
Results
Ba-based binary oxide (BaO/La 2 O 3 and BaO/Al 2 O 3 ) were prepared from Ba(NO 3 ) 2 , La 2 O 3 and Al 2 O 3
powders by the impregnation, followed by calcination at 900 °C . Cu loading was carried out by the
impregnating nitrate salts on the binary oxide. The catalyst/carbon mixture was placed in a quarts-tube
reactor and heated at 400 °C in a gaseous mixture of NO (400 ppm), O 2 (5 %), and He (balance) (total flow
rate: 100 ml/min). The NO conversion was continuously monitored by a NOx meter.
XRD patterns of Cu/BaO/La 2 O 3 showed distinct peaks due to the BaO and La 2 O 3 phases, while no peaks
attributable to the Cu phase was observed. TG analysis of Cu/BaO/La 2 O 3 under O 2 atmosphere showed the
significant increase in the weight of catalyst at around 300 °C, suggesting that Cu/BaO/La 2 O 3 has oxygen
storage ability. Carbon combustion began at around 300 °C in the presence of Cu/BaO/La 2 O 3 catalyst,
which was much lower than those of Cu/BaO/Al 2 O 3 and other metal loaded BaO/La 2 O 3 catalysts. The
results of the simultaneous removal of NOx and carbon are shown in Figure 1. Among the catalysts the
Cu/BaO/La 2 O 3 exhibited highest reactivity at 400 °C. In this reaction, carbon act as a solid reductant for the
NOx reduction.
0
0 50
100
Justification for acceptance
The simultaneous catalytic removal of NOx and carbon particlulate was effectively promoted over the Cu loaded Ba-based catalysts; Cu/BaO/La 2 O 3 . This
Cu/BaO/La 2 O 3 catalyst could exhibit efficient reactivity even at low temperature, because of its high ability for catalytic gasification of carbon particulate.
100
50
Cu
Pd
Co
Pt
400
Ni
Fig. 1. Time profile of NO removal on
metal loaded BaO/La2O3.

285 Influence of the ageing conditions on the structure of commercial three-way catalysts
H. C. Hahn a,b,* , H. Fuess a and C. Heinrich b
a Technical University Darmstadt, Darmstadt, Germany.
b General Motors Powertrain - Germany GmbH, Ruesselsheim, Germany.
*Corresponding author: Tel: +49 6151 16 6003, Fax: +49 6151 16 6023, e-mail: hhahn@st.tu-darmstadt.de
Background Since the early 1970s three-way catalysts (TWCs) are used in vehicles running on gasoline. Up to now great efforts are made to reduce exhaust
emissions and to guarantee estimated endurance limit for the EURO V legislation of 160,000 km. Haaß and Fuess reported on the deactivation mechanism of
model automotive catalysts and their structural characterisation. [1] From a practical point of view, a greater insight into the deactivation processes in TWCs
operating under real ageing conditions is definitely mandatory. [2, 3] In this study commercial TWCs of the same batch were aged under a variation of ageing
duration and temperature both aged on test bench and road. The goal is to elaborate a model for the ageing mechanism of TWCs. Furthermore the status of real
road aged catalysts has to be related to results of test bench in order to predict their ageing status.
Results Aged TWCs were tested on a chassis dynamometer using the MVEG-B drive-cycle. They show a linear increase of the emissions with duration
and an exponential increase with temperature. The road aged catalysts are comparable to the engine test bench in terms of the emission test results. The light-off
(LO) temperature and the oxygen storage capacity (OSC) of the road and test bench aged catalysts were tested on an engine test bench and in comparison in
laboratory equipment. As described in the literature for model catalysts, the LO temperature increases systematically as a function of temperature and duration. [4]
The OSC decreases by about 50 % for an engine test bench aged catalyst equivalent to 100,000 km in comparison with a fresh sample for the whole canned
catalytic converter.
Both test bench and road aged catalysts were characterised by XRD, XRF and nitrogen adsorption. For this purpose, sections from different parts of the monolith
(inlet, middle, outlet) were taken. During a 100,000 km equivalent test bench ageing the first results for the surface area of a catalyst diluted with cordierite
dramatically decreases by nearly 48 %. The XRF analysis shows a dramatical increase of about 1 wt-% of Zn on the catalyst inlet. In XRD profiles no peaks
assigned to Zn compounds could be observed because of the small fraction of these components. TEM and EPMA analysis are currently performed. They should
show the agglomerisation rate of the precious metal and the resolution of contamination on the catalyst. Progress along these lines, including structural
investigations and results of the catalytic activity, will be presented.
Justification for acceptance The aim of this work is to correlate the ageing behaviour of an engine test bench aged with road aged catalysts in MVEG-B tests,
LO and OSC tests. In addition a correlation between these results to structural results from XRF, XRD, surface area, EPMA and TEM analysis will be aspire. An
extensive understanding of the operating mode of commercial TWCs is essential for further improvements and optimisation of new catalytic concepts. The
explanation of the ageing mechanisms and the poisoning on an atomic scale is the key for an advanced and intelligent catalyst development.
References
[1] F. Haaß, H. Fuess, Adv. Eng. Mater. 7 (2005) 899.
[2] J. Hangas, A.E. Chen, Catal. Let. 108 (2006) 103.
[3] D. Meyer Fernandes, A. Alcover Neto, M.J. Baldini Cardoso, F.M. Zanon Zotin Catal. Today (2008) in press.
[4] U Lassi, Doctoral Thesis, University of Oulu (2003).
286 Catalytic Properties of Pr 2 O 2 SO 4 Having a Large Oxygen-storage Capacity:
Unsteady-state NO-CO Reactions under Cycled Feed Stream Conditions
D.J.Zhang, M.Eto, F.Yoshioka, K.Ikeue, M.Machida*
Department of Nano Science and Technology, Graduate School of Science and Engineering,
Kumamoto University, Kumamoto, 860-8555 Japan
e-mail: machida@chem.kumamoto-u.ac.jp
Background
The reduction and reoxidation between Ln 2 O 2 SO 4 (S 6+ ) and Ln 2 O 2 S (S 2- ) achieves the oxygen storage capacity (OSC) of 2 mol-O 2 mol -1 , which is eight times
larger than that of the conventional CeO 2 -ZrO 2 . The Pr system can work at lowest possible temperature of ca.600 °C and the redox cycle can be accelerated by
impregnated metal catalysts. In the present work, we have applied Pr 2 O 2 SO 4 for an unsteady-state NO-CO reaction to evaluate the effect of a large OSC on
catalytic conversions of CO as well as NO under cycled feed stream conditions.
Results
Pr 2 O 2 SO 4 and metal-loaded catalysts were synthesized as reported [1]. Dynamic cycled catalytic
reaction was conducted in a dual-supply flow system. As gas feeds, 1% CO/He and 0.75% NO/He (W/F=
4.0×10 –3 gmincm –3 ) were alternately switched with programmed time intervals. Among metal-loaded
catalysts, 20wt% Ni/Pr 2 O 2 SO 4 exhibited the highest catalyst activity as well as largest OSC at lower
temperatures. Figure 1 shows the typical effluent gas profiles for the cycled CO-NO reactions. During a
CO supply, the conversion to CO 2 was continued even in the absence of O 2 in the gas phase. When the gas
feed was switched to NO, NO conversion to N 2 was detected in the effluent due to O 2 storage. The
observed OSC and the amount of CO/NO converted are indicative of the occurrence of a stoichiometric
CO-NO reaction in stepwise to CO 2 /N 2 .
We compared the rate of NO reduction in CO-NO reaction under steady-state and cycled feed stream
conditions. It should be noted that the cyclic mode achieved much higher rate at 400-800 °C compared to
a steady-state CO-NO reaction, which was performed by using a stoichiometric CO/NO mixture as a gas
feed. In contrast to the steady-state mode, where the reaction takes place only on the surface of Ni
catalyst, the cyclic-mode reaction was determined by solid-gas reactions, where oxygen storage/release
plays a key role. The promoting effect caused by large OSC was also obvious when the CO-NO cycle was
carried out in the presence of O 2 .
Acknowledgement
inlet
outlet
CO NO CO NO CO NO CO NO
This study was supported by Industrial Technology Research Grant Program in ’05 from New Energy and Industrial Technology Development Organization
(NEDO) of Japan.
References
[1] M.Machida, et al. Chem.Commun. (2004) 662; Chem. Mater. 17 (2005) 1487; J. Mater. Chem. 16 (2006) 3084; Chem. Mater. 19 (2007) 46; J. Ceram. Soc.
Jpn. 115 (2007) 597.
Concentration / ppm
10000
8000
6000
4000
2000
CO
NO
CO reacted
NO reacted
CO
NO
0
0 10 20 0 10 20 30 40 50 60 70
Time / min
Fig.1 CO/NO cycle reactions at 400 °C over 20wt% Niloaded
Pr 2 O 2 SO 4 . 1% CO/He and 0.75% NO/He, W/F=
4.0×10 –3 gmincm –3 .

287 On the Reason for High Activity of CeO 2 for Catalytic Soot Combustion
Y.Murata, K.Kishikawa, K.Ikeue, M.Machida*
Department of Nano Science and Technology, Graduate School of Science and Engineering, Kumamoto University, Kumamoto, 860-8555 Japan
e-mail: machida@chem.kumamoto-u.ac.jp
Background
A great number of studies have been devoted to develop the active soot combustion catalyst in the last two decade. It is well-known that CeO 2 -based oxides
have excellent activity for soot combustion at lowest possible temperatures. However, fundamental understanding of the high activity of CeO 2 for the soot
oxidation is not established in the open literature. In this paper, oxygen species and its storage/release property of CeO 2 have been studied with a view to
elucidate the physicochemical factors in the determination of soot oxidation activity.
Results
Four typical fluorite-type oxides, CeO 2 , ZrO 2 , Pr 6 O 11 and a ZrO 2 -ZrO 2 solid solution, have been studied
for catalytic soot combustion in conjunction with the oxygen storage property and reactivity of oxygen
species. It was found that the redox property measured in terms of oxygen storage/release capacity was
not a sole determining factor for the observed activity sequence, CeO 2 >> CeO 2 -ZrO 2 Pr 6 O 11 > ZrO 2 .
The reactivity of oxygen species formed in the redox cycles would rather be important. The ESR
measurement showed that admission of O 2 to the partially reduced CeO 2 surface generated superoxide ions
(O 2 – ) as shown in Fig.1a. Such reactive oxygen species were less abundant on CeO 2 -ZrO 2 and were not
detected on ZrO 2 and Pr 6 O 11 . The O 2 pulse experiment demonstrated that superoxide species on CeO 2
cause a temporal oxidation of soot even at low temperature of 150 °C, compared to more than 300 °C
required for the ignition of soot oxidation. However, the pulse experiment using oxygen isotope ( 18 O 2 )
suggested that more than 80% oxygen of CO 2 formed should be originated from lattice oxide anions, O 2 .
These results imply the two possible soot oxidation routes over reduced CeO 2 as can be illustrated in
Fig.1b. In the route I, negatively adsorbed oxygen yields superoxide anions, which react directly with
soot. Another fate of superoxide anions is to yield lattice oxide anions (O 2 ), which would be
accompanied by simultaneous reaction between soot and O 2 at the tightly-contacting interface (route II).
Silver loading onto CeO 2 enhanced the generation of superoxide and thus the catalytic soot combustion.
The combination of Ag and CeO 2 seems to favor the activation of O 2 to form reactive superoxide, leading
to an enhanced activity for soot oxidation.
Acknowledgement
This study was supported by Industrial Technology Research Grant Program in ’05 from NEDO of Japan.
References
[1] M.Machida, et al. Catal. Commun. 8 (2004) 2176; J. Ceram. Soc. Jpn. 116 (2008) 230.
(a)
(b)
CeO 2
-1/2O 2
+O O -
2
O e
Ce 4+
Ce 4+ —O 2- —Ce 4+
Ce 3+ —V O —Ce 3+
soot
O 2-
O -
O
Ce 4+
O 2-
Fig.1 Schematic illustration showing (a) formation of
superoxide anion on reduced CeO 2 and (b) two possible
routes for soot oxidation over reduced CeO 2 .
O 2
291 Comparative study of natural gas vehicles commercial catalysts in monolithic form:
On the effect of gas composition and catalyst formulation
M. Salaün a , A. Kouakou a , S. Da Costa b , P. Da Costa a
a U.P.M.C. Paris 6, Laboratoire de Réactivité de Surface, UMR 7609, 4 place jussieu, 75252 Paris cedex 05, France
b Gaz de France, 361 Av. du président Wilson, 93211 Saint-Denis la Plaine Cedex
*corresponding author: Patrick DA COSTA, + 33 1 44 27 55 12, patrick.da_costa@upmc.fr
Background
With growing concern about air quality and increase of city population the interest in transportation sector is renewed. The challenge for governments is to find
and develop cost-effective ways to improve urban air quality without scarifying economy. Natural gas used as a vehicle fuel can be a good alternative in terms of
reduction of local and global pollution. Only few studies deal with TWC catalysts for NGV application. A major limitation of commercial catalysts based on
noble metals is in fact the cost of platinum group metals. The increase of their cost oblige to optimise the catalyst formulation, thus, the role of each metallic
phase has to be good understand.
The aim of this work is to investigate a comparative study of natural gas vehicles commercial catalysts, in order to evaluate their efficiency to reduce emissions of
CO, NO x and CH 4 . We have paid more particularly attention on the role of each metal for each reaction involved in the reduction or oxidation processes.
Results
Two commercial NGV converters, one monometallic and one bimetallic, are tested and compared in CO, NO x and CH 4 reduction using a representative mixture
of NGVs. For all the tests, carrots of catalysts are used (25 cm 3 ), the gas hourly space velocity is equal to 70.000h -1 , except for the homogeneity study in which
the GHSV was 80.000h -1 . During the light off, the temperature ramp is equal to 10°C min -1 . The outlet of the reactor is determined using the combination of four
different detectors. An Eco Physics CLD 700 AL chemiluminescence NO x analyzer allows the simultaneous detection of NO, NO 2 and NO x . Rosemont IR
analyzers were used to monitor N 2 O, CO, CO 2 and CH 4 .
At first, in order to show the impact of the catalyst composition to its catalytic activity, a study with a complete gas mixture is performed. Then, one of the gases
has been removed from the synthetic mixture keeping the equivalence ratio. Secondly, a mixture of two gases (simple gas mixture) has been performed to check
which of them are able to oxidise methane and reduce nitrogen monoxide at low temperature. These experiments are performed on two different catalysts, the
first one is a palladium based catalyst whereas the second one is bimetallic rhodium-palladium catalyst. The global activities are similar for the two tested
catalysts with a low discrepancy of the conversion temperature in the case of complete gas mixture [1]. However, with a simple gas mixture, some differences are
observed. For example, in absence of CO in the feed, the NO reduction is shifted to higher temperatures on the palladium based catalyst whereas no effect is
observed on the bimetallic one.
Justification for acceptance
Nowadays, there are more than 4.7 million NGVs in operation all around the world but there are very few studies on real NGVs converters. In order to develop
new catalytic formulations for these applications, a deep understanding of the reactions mechanism involved in the global reduction and oxidation process is
required.
References
[ 1 ] P. Da Costa, M. Salaün, S. Da Costa, G. Brecq, G. Djéga-Mariadassou, , SAE paper, 2007-01-0039

292 Inverse Hysteresis during NO Oxidation on Platinum: Experiments and Simulation
W. Hauptmann a , A. Drochner a , H. Vogel a , M. Votsmeier b* , J. Gieshoff b
a Technische Universität Darmstadt, Ernst-Berl-Institut, Petersenstr. 20, D-64287 Darmstadt
b Umicore AG & Co. KG, Rodenbacher Chaussee 4, D-63403 Hanau
* Corresponding author. Tel: +49 6181 592311, Fax: +49 6181 594693, e-mail: martin.votsmeier@eu.umicore.com
Background
For high performance modern exhaust gas aftertreatment systems like the NSR-, the NH 3 -SCR as well as the DPF-technology require a certain level of NO 2 . This
level is above the NO 2 amount produced in the engine. Hence the oxidation of NO to NO 2 is an import step in the whole process. The NO oxidation has been
investigated by several groups and elementary (like) mechanisms were proposed. The aim of this work is to use these models to predict experimental results
obtained during steady-state and ignition-extinction-experiments (light-off measurements).
Results
For all experimental investigations a monolithic diesel oxidation catalyst (Pt/Al 2 O 3 ) was used. During the steady-state experiments a loss of activity was
observed, which is consistent with literature results. The catalyst provided a higher activity in the light-off experiments during the heating phase compared to the
cooling phase. This means an inverse hysteresis can be observed during light-off experiments. Adding CO to the gas mixture also results in an inverse hysteresis.
Surprisingly, the CO conversion features an inverse hysteresis too, while a normal hysteresis is found for a CO/O 2 mixture. This behaviour can be explained by
catalyst deactivation. Using the state-of-the-art models [1,2] ignition or extinction can be simulated, although some parameter adjustment is necessary. However,
it is not possible to model the total light-off experiment with one set of parameters. All models show no or only a small normal hysteresis. For the NO/CO/O 2
mixture a wide normal hysteresis is predicted. The CO characteristics dominate the simulated results while the experiments show the opposite behaviour.
Additionally the literature models are not able to forecast the steady-state experiments correctly. Our results show the importance of the implementation of
catalyst deactivation in the mechanisms. Otherwise dynamic behaviour can not be described adequately.
Justification for acceptance
Though NO oxidation is an important step in exhaust gas aftertreatment, an inverse hysteresis has not been reported before. State-of-the-art models fail to predict
the dynamic behaviour of a diesel oxidation catalyst. Therefore catalyst deactivation has to be implemented in the mechanisms.
References
[1] L. Olsson, H. Persson, E. Fridell, M. Skoglundh, B. Andersson, J. Phys. Chem. B 105 (2001) 6895-6909.
[2] M. Crocoll, S. Kureti, W. Weisweiler, J. Catal. 229 (2005) 480-489.
293 NH 3 -SCR: From Mechanistic Understanding to an Improved Ammonia Dosing Scheme
M. Votsmeier a* , A. Schuler b , P. Kiwic c , A. Drochner b , H. Vogel b , C. Onder c , J. Gieshoff a
a Umicore AG & Co. KG, Rodenbacher Chaussee 4, D-63403 Hanau
b Technische Universität Darmstadt, Ernst-Berl-Institut, Petersenstr. 20, D-64287 Darmstadt
c Institute for Measurement and Control, ETH Zürich, Sonneggstr. 3, CH-8092 Zürich
* Corresponding author. Tel: +49 6181 592311, Fax: +49 6181 594693, e-mail: martin.votsmeier@eu.umicore.com
Background
Selective Catalytic Reduction (SCR) of NOx with urea rapidly finds application for heavy duty vehicles and more and more also for passenger cars. Due to some
specific advantages (temperature stability, selectivity) Zeolithe based catalysts in many cases replace the conventional vanadium catalysts for automotive
applications. One of the challenges for the application of urea-SCR DeNOx systems is the urea-dosing.
Results
The contribution covers the following steps:
Kinetic measurements for the reactions of NH 3 with NO and NO 2 on a Fe-Zeolithe catalyst.
Development of a kinetic model.
Validation of the model using model gas measurements with transient inlet concentration- and temperature conditions.
Description of a model based NH 3 control algorithm. This algorithm relies on a 0-dimsional reactor model represented by a set of look-up tables.
Parameterization of the look-up tables based on the detailed reactor model.
Implementation of the catalyst, the NH 3 dosing and the control scheme in a system level (Simulink) model.
Finally, implementation of the NH 3 -controller in a model gas setup and demonstration of its performance.
Justification for acceptance
This is a nice example how numerical models based on detailed chemical understanding can be useful for the system level optimization of exhaust treatment
applications. As an oral, this contribution would work well if combined with a presentation by another group highlighting the recent advances in the mechanistic
understanding of Zeolithe SCR catalysts.
References
[1] D. Chatterjee et al., Society of Automotive Engineers 2005, 2005-01-0965.
[2] M. Devadas et al., Catalysis Today 2007, 119, 137-144.
[3] S. Malmberg et al., Topics in Catalysis 2007, 42–43, 33-36.

304 Nucleation on and stability of -Al 2 O 3 surfaces: the special role of penta-coordinated Al 3+ sites
Ja Hun Kwak, Jian Zhi Hu, Do Heui Kim, Charles H.F. Peden, and János Szanyi *
Institute for Interfacial Catalysis, Pacific Northwest National Laboratory, Richland, WA 99352, USA
* Corresponding author: Tel: 1-509-371-6524; Fax: 1-509-371- e-mail: janos.szanyi@pnl.gov
Background: -Al 2 O 3 is one of the most widely used catalyst support materials due to its high thermal stability, and ability to keep the active
catalytic phases (metals, metal oxides) well dispersed. High dispersion of active catalyst components have been observed in many -Al 2 O 3 -
supported systems, although SMSI, that is thought to be associated with reducible metal oxide supports, was not considered to play a role in these
systems. The formation of penta-coordinate Al 3+ ions have been known to exist on some of the facets of thermally treated -Al 2 O 3 . However, the
possible roles of these under-coordinated Al 3+ ions in correlation to the nucleation of catalytically active materials and to the stability of the alumina
support have not been considered.
Results: The interaction of barium oxide with a -alumina support was investigated by high resolution solid state 27 Al magic angle spinning NMR
at an ultra-high magnetic field of 21.1T and at sample spinning rates of up to 23 kHz. Under these experimental conditions, a peak ~ 23 ppm with
relatively low intensity, assigned to 5-coordinated Al 3+ ions, is clearly distinguished from the two other peaks representing Al 3+ ions in tetra-, and
octahedral coordination. Spin-lattice 27 Al relaxation time measurements clearly show that these penta-coordinated Al 3+ sites are located on the
surface of the -alumina support. BaO deposition onto this -alumina sample resulted in the loss of intensity of the 23 ppm peak that was linearly
proportional to the amount of BaO deposited. The results of this study strongly suggest that, at least for BaO, these penta-coordinated Al 3+ ions are
the nucleation sites. We have also investigated the high temperature structural stability of -Al 2 O 3 using NMR and XRD techniques. When
modifiers (in our case BaO and La 2 O 3 ) were added to the -Al 2 O 3 , its thermal stability increased dramatically. The modifiers coordinatively
saturated the penta-coordinate Al 3+ sites, thus preventing its thermal degradation at elevated temperatures.
Justification for acceptance: These studies clearly demonstrate the special roles penta-coordinate Al 3+ ions play in the nucleation of catalytically active
material, in this example BaO, the active NO x storage material in NSR catalysts. It also provide a clear explanation for the stabilisation of the -Al 2 O 3 phase by
the addition of certain metal oxides (e.g. BaO a,d La 2 O 3 )
References: [1] J.H. Kwak, J.Z. Hu, D.H. Kim, J. Szanyi, C.H.F. Peden, J.Catal. 251 (2007) 189.
[2] J.H. Kwak, J. Hu, A. Lukaski, D.H. Kim, J. Szanyi, C.H.F. Peden, J.Phys.Chem. submitted.
305 Detailed kinetic modeling of NO x storage and reduction with hydrogen - Ammonia formation
Anna Lindholm a , Neal W. Currier b , Junhui Li b , Aleksey Yezerets b and Louise Olsson a,*
a Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
b Cummins Inc., 1900 McKinley Ave, MC 50183, Columbus IN 47201, USA
*Corresponding author. Tel: +46 31 772 4390, Fax : +46 31 772 3035, E-mail: louise.olsson@chalmers.se
Background
NO x storage is a concept for reducing NO x from diesel engines and it is crucial to decrease the emissions of NO x for environmental reasons. When the exhausts
contain oxygen excess (lean period) the NO x is adsorbed on the catalyst's storage component, usually barium. During short pulses of fuel excess (rich conditions)
the NO x is released and reduced to N 2 over the noble metal sites, like platinum and rhodium.
Results
In this study we present a detailed kinetic model of NO x storage and reduction, in the presence of H 2 O and CO 2 , with hydrogen as the reducing agent [1]. This is
the first detailed kinetic model that describes the regeneration with H 2 and the important NH 3 formation in the rich period. The model is used for predictions and
also provides a deep knowledge about the underlying mechanisms on the surface. Flow reactor experiments between 200 and 400°C over a Pt/Ba/Al monolith
sample was used to develop the model [2]. The detailed kinetic model is divided into four sub-models: (i) NO oxidation over Pt [1,3-4], (ii) NO x storage [1,4],
(iii) NO x reduction over Pt [1,3], and (iv) NO x regeneration [1]. The NO x storage model is based on our earlier work [4] and developed to include low temperature
storage and the presence of water and CO 2 [1]. Two storage sites (S2 and S3) were needed in order to describe the experimental features. NO can be stored to
account for the storage occurring at lower temperatures and the NO on S3 can be further oxidized to NO 2 by reacting with oxygen on neighboring Pt sites. The
kinetic model for the NO x reduction on the platinum sites was developed earlier on Pt/SiO 2 [3]. The submodel for the regeneration of stored NO x includes: (i)
reactions between stored NO x and hydrogen on platinum, (ii) NH 3 oxidation on platinum and (iii) reactions between NH 3 and stored nitrates according to SCR
chemistry. The model could describe the experiments adequately. In addition, the model was validated with short lean (60s) and rich (15s) cycles at three
temperatures (200, 300 and 400 C). The model could predict these experiments well.
Justification for acceptance
This is the first detailed kinetic model that describes the regeneration of the storage component with H 2 and the important formation of ammonia in the rich
period. The detailed kinetic model provides a deep fundamental knowledge about the reactions on the surface and the model can also be used for predictions.
References
[1] A. Lindholm, N.W. Currier, J. Li, A. Yezerets and L. Olsson, Submitted 2008.
[2]A. Lindholm, N.W. Currier, E. Fridell, A. Yezerets and L. Olsson, Appl. Catal. B . (2007), 75 (1-2) pp. 78.
[3] A. Lindholm, N.W. Currier, A. Yezerets and L. Olsson, Topics in Catal., (2007), 42-43 (1-4) pp. 83-89.
[4] L. Olsson, H. Persson, E. Fridell, M. Skoglundh, B. Andersson, (2001) J. Phys. Chem. B, 105 6895.

315 Selective catalytic reduction of NO by hydrogen under lean-burn conditions using Pt/Ti-Si-MCM-41 catalysts
Peng Wu, Fuxiang Zhang, Shuang Miao, Wenwen Shen, Yali Yang, Xiaohong Sun, Naijia Guan*
Lab of Functional Polymer Materials, Department of Materials Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, PR China
*Corresponding author. Tel. /Fax: +86-22-2350-0341 E-mail: guannj@nankai.edu.cn
Background
Recently, there are considerable attention for the selective reduction of NO by hydrogen (H 2 -SCR) because of higher activity and less N 2 O formation at low
temperature than NH 3 -SCR and HC-SCR [1-3] . Meanwhile, platinum-based catalysts have been found to be the most active for the NO/H 2 /O 2 lean-burn reaction at
low temperatures (T

328 Catalytic oxidation of Carbon Black over Ru/CeO 2
in the presence of propene or toluene
S. Aouad, E. Saab, E. Abi-Aad* and A. Aboukaïs
Laboratoire de Catalyse et Environnement, E.A. 2598, MREI, Université duLittoral – Côte d’Opale,
145, avenue M. Schumann,59140 Dunkerque, France
*Corresponding author. Tel: +33 3 28658262, Fax: +33 3 28658239, e-mail:abiaad@univ-littoral.fr
Background
Volatile organic compounds contribute to the formation of ground-level ozone and smog. In addition, all by themselves, VOCs can have adverse effects.
Similarly, diesel soot particulates are of a great concern due to theircapacity to damage human health and the environment. In earlier works [1-2], we have
showed that Ru/CeO2 catalysts have a considerable activity for the catalytic oxidation of carbon black (CB) (~350°C “tight contact” mixtures and ~490°C “loose
contact” mixtures) and VOCs (T50%=175°C for propene,T50%=215°C for toluene and T50%=230°C for ortho-xylene).
Results
In the present work, we investigate the oxidation of carbon black in the presence of propene (6000ppm) or toluene (2000ppm). The elimination of an important
part of CB was observed at relatively low temperatures comparing to its elimination under air flow. Carbon black total elimination was also investigated under
isotherm conditions in the presence and in the absence of propene. Total elimination occurred during shorter times when combustion was performed under
propene. EPR and TPR analysis showed that ruthenium species present in the catalysts after activation reduces atrelatively low temperatures (100°C) and less active in oxidation reactions.
Justification for acceptance
This is a novel work investigating the simultaneous elimination of soot and VOCs over Ru based catalysts. The results show the relevant contribution of
Ru/CeO 2
solids for the elimination of air pollutants. They are promising to consider the use of these catalysts in industrial and automobiles applications.
References
[1] S. Aouad, E. Saab, E. Abi-Aad, A. Antoine, Catalysis Today 119 (1-4) (2007) 273
[2] S. Aouad, E. Saab, E. Abi-Aad, A. Antoine, Kinetics and Catalysis 48 (6) (2007) 835
331 DRIFTS Investigation of Sulfation of Model Lean NO x Trap
J.A. Pihl and T.J. Toops*
Fuels, Engines and Emissions Research Center, Oak Ridge National Laboratory, Knoxville, TN 37932, USA
*Corresponding author. Tel:+1 865 946 1207, Fax: +1 865 946 1354, e-mail: toopstj@ornl.gov
Background: A candidate for mitigating the NOx portion of diesel emissions is the Lean NOx Trap (LNT); however, fuel-borne sulfur and its removal currently
limit LNT implementation. This study investigates the impact of SO 2 on a model LNT (1% Pt/8%K 2 CO 3 /Al 2 O 3 ) during typical diesel exhaust conditions, i.e. in
the presence of H 2 O and CO 2 , between 200 and 500°C, and while cycling between lean and rich conditions. The primary technique employed is Diffuse
Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS); however, the results will also be discussed in relation to a recent microreactor study [1].
Results: DRIFTS measurements show that cycling between lean and rich conditions at 200°C leads to an LNT surface that is nearly saturated with nitrates, but
only a small fraction of these stored nitrates are actively removed during the rich phase regeneration. Therefore, the effective NOx storage capacity during low
temperature cycling is only a small fraction of the total nitrate storage capacity. The introduction of SO 2 leads to sulfate formation and a decrease in the overall
nitrates stored, but has a minimal impact on the effective NOx storage capacity, i.e. the amount of nitrates removed during the rich regeneration. At 300°C, a
greater percentage of the total nitrates stored are capable of being regenerated, so SO 2 impacts NOx conversion at a faster rate than at 200°C; this has been
corroborated in a recent microreactor study [1]. At 400°C, nearly all of the sites capable of storing nitrates are active, so the inclusion of SO 2 into the feed stream
has an immediate impact on the effective NOx storage capacity.
Heating the catalyst sulfated at 200°C to 500°C in the absence of SO 2 leads to an additional decrease in the total nitrates stored, but still does not impact
the effective NOx storage capacity. This suggests that some of the sulfur was stored on non-potassium sites, probably alumina. Upon heating, this sulfur was
desorbed and then readsorbed on the potassium-phase or diffused along the surface to the more stable potassium-based sites. Heating the catalyst sulfated at either
300 or 400°C to 500°C only leads to a minor reduction in the total nitrates stored. These observations suggests that alumina is able to store sulfates at low
temperatures and offer some level of protection to the effective NOx storage capacity on K; however, upon heating it is clear that this supposed protection fails
and the potassium adsorbs the released sulfur. A quantitative analysis of sulfur’s impact on the LNT at these three temperatures shows that after heating to 500°C
the number of nitrates displaced is relatively consistent regardless of sulfation temperature.
Justification for acceptance: Understanding the fate of sulfur on the LNT surface during cyclical operation is a critical for development of accurate models and
catalyst formulations. This study offers evidence of which phases of a heterogeneous LNT adsorb sulfur and the relative stability of the sulfur under typical
operating temperatures.
[1] T.J. Toops and J.A. Pihl, Catal. Today, in press (doi: 10.1016/j.cattod.2008.02.007).

337
Enhancement of catalytic activity of Pt-mesoporous silica for HC-SCR through change in pore structures and addition of cerium
Akiko Koga, Chika Saito and Masakazu Iwamoto*
Chemical Resources Laboratory, Tokyo Institute of Technology,4259-R1-5 Nagatsuta, Midori-ku, Yokohama 226-8503, JAPAN.
*Corresponding author. Tel: +81-45 924 5225, Fax: +81-45 924 5228, e-mail: iwamoto@res.titech.ac.jp
Background
Various Pt-loaded mesoporous catalysts have recently been studied for the HC-SCR of NO in the presence of
excess oxygen 1-2) but the activity is not greatly improved in comparison with the previously reported ones 3) .
Lowering of the reaction temperature and increase in the N 2 selectivity still remain to be solved.
Results
Various mesoporous materials and silica were employed as the support of Pt; HMS, MCM-41, MCM-48,
SBA-15, MPS 2) , silicalite-1, fumed silica, and Zr-P 4) . Cerium and other metal ions were loaded by the
template ion-exchange method 5) and 2 wt% Pt was impregnated by using an H 2 PtCl 6 solution. The mixture
of 0.1% NO, 0.3% C 2 H 4 , 14% O 2 , and He as balance was flowed into the catalyst bed at GHSV of 10,000-
100,000 h -1 .
All of the Pt-loaded mesoporous materials showed the maximum activity at 473-493 K (Fig. 1) and the NO
conversions of ca. 65-90%, indicating somewhat effect of the pore structures and the pore diameters on the
activity. HMS and MCM-41 gave the high and similar activity. In contrast, the selectivity to N 2 was greatly
dependent on the supports. The order was HMS > MCM-48 > MCM-41 > SBA-15 > Zr-P > MPS. The
Pt/fumed silica did not yield any N 2 . The N 2 selectivity was changed with the loading of cerium ion onto
MCM-41. The results are shown in Fig. 2. The addition of 6.3wt% Ce on the Pt/MCM-41 catalyst resulted
in the increments in the NO conversion and the N 2 selectivity. The addition also induced the oscillation
phenomenon of NO conversion at 463-478 K, which would be due to change in the amount of oxygen
activated on Ce ion. The dependences of N 2 selectivity on the pore structures and the additives indicate the
possibility that the formation of harmful N 2 O would be able to be decreased by improvement of the catalyst.
It should be noted that the Pt-mesoporous silica showed long-time stability in the presence of water and
could be used repeatedly at the temperature range 373-873 K.
References
[1] A. Jentys, et al., Catal. Today, 59(2000), 313. J. Y. Jeon, et al., Appl. Catal. B, 44(2003), 311. J. Jang, et al., Appl.
Catal. A, 286(2005) 36. [2] T. Komatsu, et al., Catal. Today, 116(2006), 244. [3] M. Iwamoto, et al., Chem. Lett.,
1992, 2235; Catal. Today, 26(1995), 13. R. Burch, et al., Catal. Today, 26(1995) 185. [4] P. Wu, et al., Chem. Mater.,
17 (2005) 3921. [5] M. Iwamoto, et al., Catal. Surv. Jpn., 5 (2001), 25.
NO conversion /%
100
80
60
40
20
0
373
HMS
MCM-41
SBA-15
Zr-P
SV=10,000h -1
Pt=2wt%
473 573 673 773
Temperature / K
873
Fig. 1. Conversions to N 2 + N 2 O on
various Pt-loaded mesoporous
materials.
NO conv. , N 2 yield / %
100
80
60
40
20
0
373
MCM-41
MCM-41
Ce-MCM-41
Ce-MCM-41
SV=10,000 h -1
Pt=2wt%
473 573 673 773
Temperature / K
873
Fig. 2. Effect of Ce-loading on the
NO conversions (closed symbols)
and N 2 yields (open symbols).
340 A Reactivity of SOF on Various Oxygen Condition and De-NOx by producted syn-gas
J. W. Kim a , H. K. Kim a and Y. S. Yoo b , S. J. Choung a*
a
Department of Chemical Engineering, Kyung Hee University College of Environment & Applied Chemistry, Yongin-City, Gyeonggi-Do, 449-701,
Korea
b R&D Center of HeeSung Catalysis, Shihwa #507-1Da, 1251-6, Jungwang-Dong, Shihung-City, Kyungki-Do, Korea
*Corresponding author. Tel: +82 31 201 2533, Fax: +82 31 202 5946, e-mail: sjchoung@khu.ac.kr
Background
To fulfill future emission standards for diesel engines, after-treatment systems with the simultaneous removal of NOx and PM are necessary. [1]. Diesel engines
have low hydrocarbon (HC) and CO emissions but, on the downside, then have high emissions of NOx and PM without after-treatment systems[2,3]. HC-SCR of
De-NOx technology has a merit which passive type. However, diesel emissions include very low HC concentration. For that reason, HC from SOF component of
PM will give an additional reducing agent source for the S.C.R. of NOx. This paper describes the possibilities for the solutions to handle the complexity of
systems including selective catalytic reduction of NOx and de-particulate matter simultaneously through the reforming reactions on catalysts.
Results
Soxhlet extraction of SOF from the PM which filtered from actual diesel exhaust, analyzing their extracts using GC-MS showed the presence of phenol, n-hexane
and 1-hexene as major components. Temperature-dependent activity of SOF reforming on various catalysts performance was studied using varying O 2 levels (0,
5, 10 and 15 vol. %). It was found that the Rh loaded catalyst showed the most highest activity among tested catalysts : at high O 2 contents, the reforming activity
shows sensitively at 400 ~ 500 o C.
Temperature-dependent activity of NO reduction on various samples was obtained in this study. The conversion performance of NO over various catalysts in lean
conditions were found to be good in syn-gas SCR when used for phenol reforming on Rh/r-Al 2 O 3 at 400 o C. Pt/Al 2 O 3 was also used as the catalyst in SCR in this
study.
As a result, the production of syn-gas from SOF reforming gave good performance with NO reduction. Specially, adsorpted phenol on the Rh(1wt. %)/r-Al 2 O 3
play an important role in SOF-reforming. Also, the alcohol group among other functional group in phenol has an effect on adsorption. Acid amount of noble
metal and adsorption amount of SOF were found to have linear relationship and the results are reported in detail here.
Justification for acceptance
SOF in PM has been discussed as a removal object in diesel engine exhaust. In this study, SOF renewed is focused with different view by removing NOx with
produced syn-gas.
References
[1] Schindler, K –P, SAE paper (1997) 972684
[2] Dieselnet, August 20th, 2007 http://www.dieselnet.com/tech/cat diesel.html
[3] B Nakane T., Ikeda M., Hori M., Bailey O., SAE paper (2005) 2005-01-1759

346 Engine bench tests for continuous HC-SCR over a Ag/Al 2 O 3 converter under lean conditions using
a 3.3 liters common rail turbo diesel off-road engine
K. Arve a *, K. Eränen a , J. Perus b , M. Lauren b , S. Niemi b , D. Yu. Murzin a
a Åbo Akademi University, Biskopsgatan, FIN-20500 Turku, Finland.
b Turku University of Applied Sciences, FIN-20700 Turku. Finland
*Corresponding author: Tel: +358 2 215 4437, Fax: +358 2 215 4479, e-mail: karve@abo.fi,
Background
Selective catalytic reduction of NO with hydrocarbons (HC-SCR) has received much attention as one of the most promising methods for removing NO x
emissions from vehicles. Since the pioneering work [1, 2] a variety of different materials have been proposed. Among these, Ag/alumina has shown high activity
both in laboratory and full-scale tests when applied in a passenger vehicle [3]. In practice, all engines for heavy duty and off-road purpose are diesel engines and
emission regulations for these engines are also becoming more stringent [4]. In this study we have investigated activity of a Ag/alumina converter in NO
reduction in engine bench tests using a 3.3 liters common rail turbo charged off-road diesel engine.
Results
Selected results from the engine bench runs are shown in Table 1. As it can be seen, the highest NO x conversion, 70%, was recorded at engine speed 1200 rpm
using 50% load. Depending on the engine speed the optimal post injection timing was found to be either 120° or 150° after top dead centre (ATDC).
Table 1. Data from engine bench runs at 50% engine load.
Speed (rpm) Load (%) NO x conversion (%) Injection (°) HC 1 /NO SFC (g/kWh) Fuel penalty (%)
1200 50 70 120 8.3 230.4 12.8
1600 50 58 150 10 241.2 7.8
2200 50 31 150 7 272.9 4.9
Despite the late post injection timing (120° or 150°) part of the injected hydrocarbons is burned before reaching the catalyst thus increasing the fuel penalty. Thus
the fuel penalty can be decreased in the future by optimising the injection system. It should be mentioned that the break specific particulate matter (BSPM)
decreased using the HC-SCR system compared to EGR in the whole measured range (20-800 nm).
Justification for acceptance
The results from this study are of highest industrial importance as it shows that HC-SCR technique has the potential for reducing NO and BSPM from an off road
engine to meet the coming legislation for these applications.
References
[1] W. Held, A. Koenig, T. Richter, L. Puppe, SAE Paper (1990) 900496.
[2] M. Iwamoto, H. Yahiro, S. Shundo, Y. Yu-u, N. Mizuno, Appl. Catal. (1991) 69.
[3] F. Klingstedt, K. Arve, K. Eränen, D. Yu. Murzin, Acc. Chem. Rev. (2006) 39.
[4] www.DieselNet.com.
347 Kinetics of the reduction of NO by a model paraffinic second generation bio-diesel compound
over Ag/Al 2 O 3 under excess of oxygen
K. Arve*, J. Hernández, K. Eränen, D. Yu. Murzin
Åbo Akademi University, Biskopsgatan 8, FIN-20500 Turku/Åbo, Finland.
*Corresponding author: Tel: +358 2 215 4437, Fax: +358 2 215 4479, e-mail: karve@abo.fi
Background
The effect of longer paraffins on the mechanism of the HC-SCR reaction over a 1.91 wt.% Ag/alumina catalyst was investigated by kinetic studies. Hexadecane
(C 16 H 34 ) was chosen as a model compound as it is also a representative molecule for the second generation biodiesel consisting of long chained paraffins
produced for instance by the NesteOil process NexBTL. The kinetic behaviour of the catalytic reduction of NO x was examined at steady state at 250-550 °C (50
°C ramping) and by using following gas concentration: P NO = 250, 500 and 1000 ppm, P hexadecane = 93.75, 187.5 and 375 ppm and P
O 2
= 1.5, 3 and 6 vol.%.
Results
The results from kinetic experiments are shown in Table 1. They demonstrated that in the temperature range 250-350 °C the oxidation of the hydrocarbon
decreased with increasing HC concentration resulting in a decreased NO to N 2 reduction rate. The activation energy of C 16 H 34 oxidation varied (27 - 71 kJ/mol)
with increasing HC concentration indicating complexity of the reaction mechanism. Reaction orders for C 16 H 34 depicted the inhibiting effect of the hydrocarbon
at this temperature range (Table 1). On the other hand, in the temperature range 450-550 °C the hydrocarbon concentration has a clear enhancing effect on the NO
reduction similar to that earlier reported for C 8 H 18 -SCR [1]. The reduction activity at low temperatures is clearly connected to the catalysts ability to oxidise the
reductant, which in the case of Ag/Al 2 O 3 is the limiting factor in the lower temperature range as we have previously documented [1, 2].
Table 1. Reaction orders for HC and NO at different temperatures and activation energies for HC oxidation.
Temp °C order HC in HC order NO in NO
250 -0.81 0.51
300 -0.55 0.46
350 0.37 0.7
Experiments with varying NO concentration revealed an apparent inhibiting effect of increasing NO concentration and the recorded reaction orders indicated
relatively high surface coverage at all examined temperatures.
Justification for acceptance
For HC-SCR with higher hydrocarbons there are only few papers in the literature describing kinetics and thus this study brings new information
about the possible reaction mechanism of this important reaction.
References
[1] K. Arve, F. Klingstedt, K. Eränen, J. Wärnå, L.-E. Lindfors, D. Yu. Murzin, Chem. Eng. J. 107 (2005)
[2] K. Arve, H. Backman, F. Klingstedt, K. Eränen, D. Yu. Murzin, Appl. Catal. A 303 (2006) 96.

355 The importance of zeolite synthesis on the stability of Cu-ZSM-5
M. Berggrund * , H Härelind Ingelsten, M Skoglundh and A. Palmqvist
Competence Centre for Catalysis, Chalmers University of Technology, 41296 Göteborg, Sweden
* Corresponding author. Tel +46 31 7722976, Fax : +46 317722967, e-mail: malberg@chalmers.se
Background
Recent calculations and experimental work indicate that the aluminum distribution of zeolite ZSM-5, the copper coordination, and the lean NO x activity of Cu-
ZSM-5 are affected by changing the synthesis conditions of the ZSM-5 [1-3]. Density functional theory calculations indicate that the interaction strength between
copper ions and the ZSM-5 framework in the presence of water depends on the locus of the copper and aluminum atoms [1]. In addition, experiments imply that
the aluminum distribution in the ZSM-5 is affected by the choice of aluminum source in the zeolite synthesis [2]. Further, the choice of aluminum source and the
addition of calcium hydroxide in the ZSM-5 synthesis affect the lean NO x reduction of the Cu-ZSM-5 [3].
Results
ZSM-5 syntheses were performed with two different aluminum sources, which have been reported to give different aluminum distribution [2]. In addition to the
two different aluminum sources, calcium hydroxide was included in varied amounts in some of the ZSM-5 synthesis mixtures. The samples were ion-exchanged
to Cu-ZSM-5 and washcoated onto monolith supports. Lean NO x reduction activity was evaluated in flow reactor studies before and after hydrothermal treatment
to access differences in stability between the samples. It was found that the hydrothermal stability of Cu-ZSM-5 samples was affected both by choice of
aluminum source and by the presence of calcium hydroxide in the ZSM-5 synthesis mixture. The stability of a Cu-ZSM-5 sample where the ZSM-5 was
synthesised with aluminum nitrate, supposedly resulting in unpaired aluminum sites [2], was far inferior to a sample synthesised with aluminum chloride,
resulting in paired or close unpaired aluminum atoms [2]. This lower stability was counteracted by addition of calcium hydroxide in the synthesis mixture.
Further, the aging experiments performed indicate that disparate sites are active for the different reactions; NO oxidation, propene oxidation and NO reduction
with propene. While propene oxidation remains unaffected and NO oxidation changes slightly, a significant decrease in NO reduction with propene is noted for
the samples with the largest decrease in NO x reduction. The stability of the sites used for NO reduction with propene seems to be more dependent on the
aluminum distribution of ZSM-5.
Justification for acceptance
This study experimentally illustrates the importance of the ZSM-5 synthesis procedure for the stability of active sites in Cu-ZSM-5. This is expected to have a
direct impact on the possibility to use Cu-ZSM-5 in lean NO x reduction applications.
References
[1] M. Davidová, J. Sauer, M. Sierka, and P. Nachtigall, Abstracts of the 14th International Zeolite Conference, Cape Town, South Africa, (2004) 857.
[2] V. Gábová, J. Ddeek, and J. ejka, Chem. Comm., (2003) 1196.
[3] M. Berggrund, M. Skoglundh, A. E. C. Palmqvist, Topics in Catalysis 42/43 (2007) 153
367 Screening of palladium-containing modified ceria-zirconia catalysts for the Selective Catalytic Reduction (SCR) of NOx by methane
B. Azambre* a , L. Zenboury a , P. Burg a , P. Da Costa b
a Laboratoire de Chimie et Méthodologies pour l’Environnement (LCME), Université Paul Verlaine de Metz, Rue Victor Demange, 57500 Saint Avold, France
Laboratoire de Réactivité des Surfaces, case 178 - T 54-55 - 4, place Jussieu, 75252 Paris Cedex 05, France
*corresponding author. Tel : +33387939106. Fax:+33387939101.e-mail:bazambre@univ-metz.fr
Background
The use of hydrocarbons as substitute for ammonia in the SCR of NO has drawn much attention. Methane is theoretically the most preferable one because natural
gas is readily available from many electrical utilities and stationary combustion engines. However, owing to its intrinsic chemical stability, methane is only little
selective for NOx reduction in oxygen-rich streams and the mechanistic pathways leading to DeNOx still remain unclear. In this study, the DeNOx performances
of Pd/acidic ceria-zirconia catalysts are investigated according to the acidity and composition of the support, the noble metal content, the nature of the metallic
precursor and the presence of water.
Results
Acidic ceria-zirconia (SCZ) were prepared by direct sulfation of high specific surface area commercial CZ powders of compositions Ce 0.21 Zr 0.79 O 2 and
Ce 0.69 Zr 0.31 O 2 . In comparison with other sulfated metal oxides, sulfate species generated on CZ were characterized by a higher thermal stability, even under
reactive atmospheres. TPD-IR analyses of adsorbed pyridine reveal an overall increase of surface acidity after sulfation and the (reversible) conversion of some
Brönsted to Lewis acid sites above 200-300°C in absence of water. The testing of Pd-SCZ and Pd-CZ catalysts was carried out under a mixture of 150 ppm NO,
1500 ppm CH 4 , 7% O 2 in TPSR (ramp) or isothermal mode (steady state experiments). Whereas Pd-CZ were found to be not selective for SCR in presence of O 2 ,
the palladium catalysts supported on acidic ceria-zirconia exhibit a significant activity. The optimal catalytic performances of these Pd-SCZ catalysts were
obtained for a Pd loading of 0.25-0.5% wt with 35% conversion of NO to N 2 at 370°C. Under these conditions, the catalyst did not show any deactivation with
time. TEM-EDX, XRD and IR of adsorbed CO revealed that the active phase for SCR at low Pd loadings consists in well-dispersed acidic palladium Pd x+ cations
exhibiting weak reducibility. The decrease of SCR activity observed for higher Pd loadings has to be related to the promotion of the non-selective methane
combustion by PdOx clusters. Analysis of TPSR profiles revealed that the addition of water to the feed is detrimental for SCR activity due to competitive
adsorption with NOx on Pd sites.
Justification for acceptance
This presentation summarizes the results obtained by Laila Zenboury, 3 rd year PhD student at the LCME, (University of Metz) within the Eureka project
“Stationocat” 2005-2008 (EU n°3230). This project was funded through a ADEME-Gaz de France grant and is also part of the international research group
(GDRI) “Catalyst for environment: depollution, renewable energy and clean fuels” (CNRS-PAN).
Part of the work presented has already been accepted as 2 publications in Catalysis Today.

372 Toward Three-way Nanocatalyst with High Performance and Low Noble Metals Loading
Zhimei Li, , Xiao Guan, Licheng Liu, Hongxing Dai, Xuehong Zi and Hong He*
Laboratory of Catalysis Chemistry and Nanoscience, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing
University of Technology, Beijing 100022, P.R. China
*Corresponding author. Tel: 8610-67396588, Fax : 8610-67391983, e-mail: hehongr@bjut.edu.cn
Background It is a great challenge for us to find a way to reduce manufacturing cost for three-way catalyst (TWC). If the size, shape and composition of noble
metal nanoparticles deposited on a carrier are precisely controlled, the activities of TWC will be increased largely and the loading of noble metals will be
reduced. Recently, a promising method [1, 2] , i.e. ultrasound-assisted membrane reaction (UAMR), has been developed in our laboratory for fabricating supported
metal nanocatalysts, which is benefit to control the nucleation and growth process of metal nanoparticles on carries.
Results The 0.5 wt %Rh/-Al 2 O 3 and 0.5 wt %Rh 0.5 Au 0.5 /-Al 2 O 3 nanocatalysts were prepared by the UAMR method, which showed better catalytic
performance in TWC model reactions (CO and HC oxidations as well as the reaction of CO + NO) than the 0.5 wt %Rh/-Al 2 O 3 catalyst prepared by
impregnation method. For example, the light-off temperatures of CO oxidation were 168 and 190 °C over the 0.5 wt %Rh/-Al 2 O 3 and 0.5 wt %Rh 0.5 Au 0.5 /-
Al 2 O 3 nanocatalysts prepared by UAMR method, respectively, which were lower than that (315 °C) over the ordinary 0.5 wt %Rh/-Al 2 O catalyst. If the
Rh 0.5 Au 0.5 bimetallic nanoparticles are used to substitute Rh employed in TWC, the consumption of Rh will be cut down 66% in comparison with commercial
TWC. The TEM images of Rh 0.5 Au 0.5 /-Al 2 O 3 and Rh/-Al 2 O 3 nanocatalysts are presented in Figure 1. The sizes of the Rh 0.5 Au 0.5 and Rh nanoparticles with
A
B
uniform size distribution deposited on -Al 2 O 3 are ca. 5 and 3 nm, respectively. Possibly, it is
accountable for the high performance of 0.5 wt %Rh/-Al 2 O 3 and 0.5 wt %Rh 0.5 Au 0.5 /-Al 2 O 3
nanocatalysts.
Justification for acceptance The grand challenge faced by the researchers in the field of catalysis is
5 nm 5 nm
“to control the composition and structure of catalytic materials over length scales from 1 nanometer to 1
micron to provide catalytic materials that accurately and efficiently control reaction pathways” [3] . The
novel method of UAMR provides an exciting and promising way to meet the grand challenge. Also, it
will make a big contribution to the automobile emission control by reducing the high cost of TWC
Figure 1 TEM images of 0.5 wt %Rh 0.5 Au 0.5 /- manufacture.
Al 2 O 3 (A), and 0.5 wt %Rh/-Al 2 O (B)
nanocatalysts prepared by UAMR method
References
[1] Hong He, Hongxing Dai, Xuehong Zi, Chinese Patent CN1907556
[2] Hong He, Hongxing Dai, Xuehong Zi, US patent Application No. 11/777,090
[3] NSF Workshop Report on “Future Directions in Catalysis: Structures that Function on the Nanoscale” NSF Headquarters, Arlington, VA June 19-20, 2003.
5 nm
381 Synthesis of CeO 2 -ZrO 2 solid solution by glycothermal method and its oxygen release capacity
S. Hosokawa, S. Imamura, S. Iwamoto and M. Inoue*
Graduate School of Engineering, Kyoto University, Katsura, Kyoto, 615-8510, JAPAN
*Corresponding author. Tel : +81 75 3832481, Fax : +81 75 3832479, e-mail : inoue@scl.kyoto-u.ac.jp
Background
The CeO 2 -ZrO 2 solid solution is an important oxygen-storage component for use in automobile catalysts. We have been exploring the methods for
synthesizing inorganic materials in organic media at elevated temperatures. Various mixed oxides are directly crystallized when two suitable starting materials in
the forms of alkoxide, acetylacetonate, acetate, etc. are allowed to react in 1,4-butanediol at 200–300 ºC (glycothermal [GT] reaction) [1].
In this work, CeO 2 -ZrO 2 solid solutions were prepared by the GT method, and its oxygen release capacity was investigated by a repetitive reduction-oxidation
technique.
Results
The CeO 2 -ZrO 2 solid solutions were synthesized by the GT method and co-precipitation (CP) method. In
the repetitive reduction-oxidation experiment, the solid solution was reduced with H 2 up to 950 ºC (the first
TPR), and it was re-oxidized with O 2 (20 vol % in He) at 500 ºC for 1 h, followed by the second TPR
procedure. Figure 1 shows the TPR profiles in the repetitive reduction-oxidation experiment. The hydrogen
consumption of the GT sample was 1.5 times as much as that of the CP sample. Re-oxidation of the GT sample
at 500 ºC after the first TPR procedure resulted in a large decrease in the reduction temperature (300–600 ºC)
in the second TPR. On the other hand, only a slight shift of the main peak occurred for the CP sample, and a
small broad peak appeared in the lower temperature region. The CeO 2 -ZrO 2 solid solution synthesized by the
GT method had unique oxygen release property as compared with the CP sample.
Justification for acceptance
The CeO 2 -ZrO 2 solid solution with high oxygen release property has a merit for the use in the automobile
catalysts. This paper reports a novel preparation method (GT method) for the CeO 2 -ZrO 2 solid solution. The
CeO 2 -ZrO 2 solid solution synthesized by the GT method has a high oxygen release capacity and unique
reduction behavior. Therefore, we think this presentation will provide a significant contribution to the ICEC.
Reference
[1] M. Inoue, J. Phys. Condens. Mater., 16 (2004) S1291.
H 2-consumed (a.u.)
(a)
Third
Second
First
150 300 450 600 750 900
Temperature ()
H 2 -consumed (a.u.)
(b)
Third
Second
First
150 300 450 600 750 900
Temperature ()
Fig. 1 TPR profiles of CeO 2 (20 mol%)-
ZrO 2 obtained by calcination at 1100 ºC
of the product synthesized by the
glycothermal method (a) and the co-

382 DRIFTS-SSITKA analysis of H 2 -assisted NH 3 SCR on Ag-alumina
J. Sjöblom a , * , D. Creaser a and J.P. Breen b , R. Burch b
a Chemical Reaction Engineering, Department of Chemical and Biological Engineering, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
b CenTACat, School of Chemistry, Queen’s University Belfast, Belfast, BT9 5AG, Northern Ireland.
*Corresponding author. Tel: +46 31 772 3039, Fax : +46 31 772 3035, e-mail: jonas.sjoblom@chalmers.se
Background
Ag-alumina is a promising candidate for selective catalytic reduction (SCR) of NO X for automotive applications. Numerous papers have been published trying to
reveal the mechanism and also try to elucidate the role of hydrogen which can act as a SCR promoter especially at lower temperatures [1]. This study aims at
clarifying the reaction mechanism of H 2 -assisted NH 3 -SCR and the role of adsorbed NO X as potential reaction intermediates.
Results
Atmospheric reactor experiments using fast switching and isotopic labelled 15 NO analyzed by both Diffuse Reflectance Fourier Transform Infrared Spectroscopy
(DRIFTS) and mass spectrometry (MS) was performed. The experiments were performed using 2%w/w Ag-alumina. The gases used were 1000 ppm NO (as
14 NO or 15 NO), 1000ppm NH 3 , 5% O 2 and 1% H 2 (when in use) and the switching were made using a high speed 4-valve switch. The MS signals were converted
into concentration using an experimental design taking into account both fragmentation patterns as well as secondary effects. The spectral matrices were deconvoluted
using ALS [2] into two matrices representing concentration and pure spectra respectively.
By analysing the relative amounts of N 2 as 14 N 2 , 14 N 15 N and 15 N 2 , it was confirmed that during H 2 -assisted NH 3 -SCR the dominating product was 14 N 15 N, whereas
for NH 3 -SCR without H 2 at high temperatures, all combinations were formed indicating other reaction pathways. For the H 2 -assisted NH 3 -SCR the time evolution
of the isotopic combinations of N 2 and the spectra obtained from the ALS analysis was compared. Most of the surface species were considered to be spectators.
However, the change in N 2 signal (from 14 N 2 to 14 N 15 N) was equally fast as one of the surface species, indicating that a reaction intermediate may be visible using
DRIFTS. These results contribute to our understanding about reaction intermediates and spectators.
Justification for acceptance
This study uses several complementary techniques. The choice of NH 3 -SCR at atmospheric conditions is one way to elucidate one part of the complex HC-SRC
mechanism [3]. The use of MS calibration for quantification of gas phase species, the use of ALS for spectral deconvolution and the use of DFT for peak
assignment of the resulting spectra shows clearly interdisciplinary benefits and improves the subsequent analysis, i.e. the combination of fast switches and
DRIFTS for mechanistic study.
References
[1] E.V. Kondratenko, V.A. Kondratenko, M. Richter and R. Fricke, J. Catal., 239 (2006) 23-33.
[2] R. Tauler, Chemom. Intell. Lab. Syst., 30 (1995) 133-146.
[3] J.P. Breen, R. Burch, C. Hardacre, C.J. Hill and C. Rioche, J. Catal., 246 (2007) 1-9.
384 Performance of alumina and silica-supported copper oxide catalysts for simultaneous removal of NO x and SO 2
from combustion flue gases
M. A. Goula, a,* , O. Bereketidou a,b , C. Economopoulos a , H. Latsios a , G. Grigoropoulou a
a Pollution Control Technologies Department, Technological Educational Institute of Western Macedonia, Koila, Kozani, 50100, Greece,
b Department of Engineering and Management of Energy Resources, University of Western Macedonia, Bakola & Sialvera, Kozani, 50100, Greece
*Corresponding author. Tel: +302461068296, Fax : +302461039682, e-mail: mgoula@kozani.teikoz.gr
It has been recognized that NOx and SO 2 emissions, being produced by fuel combustion from stationary sources, as power stations, industrial heaters or
cogeneration plants may cause major environmental problems. Selective catalytic reduction (SCR) has been well established and applied world-wide for NOx
emissions control mainly due to its efficiency, selectivity and economics. Copper oxide deposited on a porous supporting material has been used as a highly stable
and active catalyst for the SCR reaction, while presence of SO 2 in the feed causes copper sulphate (CuS0 4 ) formation at a temperature range between 300-450°C.
Reductive regeneration of the sulphated catalysts has commonly carried out by using NH 3 gas streams. The tolerance to SO 2 presence and the effectiveness of the
regeneration process to CuO supported on alumina and silica catalysts are presented in this study.
Catalysts were synthesized by using different impregnation methods and characterized by techniques as Inductively Coupled Plasma Atomic Emission
Spectroscopy (ICP-AES), Nitrogen Adsorption-Desorption and X-ray Powder Diffraction (XRD). Testing experiments were carried out in a fixed-bed reactor
using a controlled gas mixture. The effect of reaction temperature, weight hour space velocity (WHSV) and sulphur oxide concentration on SCR activity, life
time and regeneration capability of the catalysts were studied. Denitrification (DeNOx) seems to decrease at lower temperatures, but it increases at higher
temperatures with increasing SO 2 concentration. Moreover, side reactions as catalytic ammonia oxidation and N 2 O formation occurring mainly at higher
temperatures were taken into consideration, as well.
The development of innovative or improved techniques for combustion flue gases removal is one of the principal topics in environmental catalysis, particularly
after stricter legislation being induced from European Union. Simultaneous SO 2 and NO x removal, using a regenerative fixed bed catalytic reactor, seems to be
one of the most promising applying technologies and research focusing in new catalytic materials performance is in any case needed.
References
[1] Guo Yan-Xia, Lia Zhen-Yu, Li Yun-Mei1, Liu Qing-Ya, J Fuel Chem Technol, 35(3), (2007),344348
[2] Guoyong Xie, Zhenyu Liu, Zhenping Zhu, Qingya Liu, Jun Ge, and Zhanggeng Huang, J. Catal., 224, (2004), 42-49
[3] Guido Buscaa, Luca Liettib, Gianguido Ramisa, Francesco Bertic, Appl.Catal.B:Environmental, 18, (1998), 1-36
Acknowledgments:
The presented work is financially supported by the 3 th PEP OF WESTERN MACEDONIA, REGION OF WESTERN MACEDONIA, PROJECTTITLE ‘Development and
Application of an Operational Forecasting Model for Atmospheric Pollution and Tackling Actions in the Region of Kozani - Ptolemaida’, 06-08

389 Metal substrate SCR catalysts for NO x reduction in mobile applications
T. Maunula a* , K. Rahkamaa-Tolonen a , A. Viitanen b , M. Kärkkäinen a , A. Lievonen b and T. Kinnunen a
a
Ecocat, Product development, Typpitie 1, Fi-90650 Oulu, Finland.
b Ecocat, Product development, P.O. Box 20, FI-41331 Vihtavuori, Finland.
*Corresponding author. Tel: +358-10-6535586, Fax, +358-10-6535700, e-mail: teuvo.maunula@ecocat.com
Background
The future NO x emission limits for on- and off-road applications are becoming so demanding that efficient combustion modification and after treatment methods
are needed. The use of urea-SCR enables to minimize fuel consumption (lower CO 2 emissions) of diesel engines. Since 2005, the new heavy-duty trucks have
been equipped with urea-SCR catalysts in Europe covered by urea distribution network. The metallic substrates have advantages like low pressure drop,
mechanical durability, packaging without assembly mats and high cell-density substrates. The improvements, designs and utilization of V 2 O 5 /WO 3 -TiO 2 based
SCR catalysts have been reported in this work.
Results
Catalyst composition and design were developed by laboratory and engine bench (6.9L MAN) experiments. SCR catalyst coatings were prepared both on open
foil (500-900 cpsi) and brazed (500 cpsi) substrates. The high cell density substrates have a high coating amount and geometric surface area which are important
for SCR reactions. The latest concept showed improved NO x reduction activity and good durability (500-1000 h) in diesel exhaust gases. NO x reduction at low
temperatures below 230°C was clearly improved and was competitive with commercial extruded and coated SCR catalysts. NO 2 formed in DOC upstream SCR
catalysts improved the performance at low temperatures and with a small SCR catalyst. The NH 3 slip catalyst (PostOxicat) was developed to have higher SCR
activity and selectivity for N 2 formation instead of NH 3 decomposition or oxidation. The NO x conversion in engine experiments was over 90% at 220°C with the
combination of SCR (12.8 dm 3 ) and NH 3 slip (6.4 dm 3 ) catalysts. The NO x after treatment designs were optimized by catalyst amount, pressure drop and
durability requirements in comparison to emission limits (US, EU, Japan). The importance of kinetic and mass transfer limitations were analyzed in concepts. The
NO x conversions were estimated by NH 3 and N 2 O slip criteria. The concept design of SCR catalysts with DOC, catalytic hydrolysis units, catalyzed particle
filters (CPF) and POC was also discussed.
Justification for acceptance
SCR catalysts with metallic substrates have a commercial importance in fast growing mobile applications, especially in heavy duty and off-road applications. The
coming EuroV/VI and US2010 legislations require the optimization of concepts to fulfill simultaneously NO x , PM and CO 2 emission targets. The coating
methods on metal surfaces were developed to have both good adhesion and performance. Most of publications are related to extruded and ceramic concepts but
new aspects and benefits are found by applying metallic substrates. The results with new coatings are very competitive, especially at low temperature, and the
integration of SCR activity on NH 3 slip catalyst showed also a new level of performance compared to baseline.
390 H-ZSM-5 as promising catalyst for selective catalytic reduction of NO x with dimethyl ether
Stefanie Tamm a,b,* , Hanna H. Ingelsten a,b and Anders E.C. Palmqvist a,b
a Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
b Applied Surface Chemistry, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
*Corresponding author. Tel: + 46 31 772 2977, Fax: + 46 31 16 00 62, e-mail: stamm@chalmers.se
Background: As a consequence of increasing atmospheric CO 2 concentrations and increasing oil prices, attention is currently drawn to the use of dimethyl ether
(DME) as alternative fuel in diesel engines. Despite the comparably clean exhaust from lean DME combustion, an aftertreatment system will most likely be
needed to meet the most stringent upcoming legislation for NO x emissions. DME-SCR would be the simplest choice for such an aftertreatment system. However,
silver/alumina and Cu-ZSM-5, two of the most promising materials for HC-SCR, are not particularly active with DME as reductant in the presence of water [1,
2].
Results: In this study, we show that zeolite H-ZSM-5 is a promising and stable low-cost catalyst for DME-SCR in the presence of water, giving NO x reduction of
50 % with high selectivity to N 2 . In more detail, flow reactor experiments were carried out where NO x , NO and DME conversion and formation of CO 2 , CO,
methanol, formaldehyde, acetaldehyde and NO 2 were evaluated as a function of temperature, acidity of the zeolite, the HC/NO x -ratio and the absolute NO x and
DME concentrations at a fixed HC/NO x -ratio. We find that the H-ZSM-5 catalyst with the lowest SiO/Al 2 O 3 -ratio, being at the same time the most acidic one, is
most active for NO x reduction. Moreover, NO x reduction increases with decreasing space velocity, increasing HC/NO x -ratio, and, at a fixed HC/NO x -ratio, with
increasing absolute NO x and DME concentrations. Methanol is formed at lower temperatures, with a maximum yield at 300 °C. At higher temperatures,
formaldehyde, acetaldehyde and considerable amounts of NO 2 are observed. The yields of CO 2 , CO, methanol, formaldehyde and acetaldehyde are only
dependent on the temperature but not on the other four evaluated parameters. In contrast, the concentrations of NO and NO 2 are sensitive to all these parameters.
Furthermore, NO x reduction is only observed when NO 2 is formed, indicating a connection between NO x conversion and NO 2 formation.
Justification for acceptance: For DME-SCR only moderate NO x conversion has previously been reported in literature. Here, we report 50 % NO x conversion in
the presence of water over H-ZSM-5. These results are expected to have an impact on the application of lean NO x catalysts in DME-fuelled vehicles.
References:
[1] S. Erkfeldt, A. E. C. Palmqvist, E. Jobson, Top. Catal. 42-43 (2007) 149.
[2] K. Masuda, K. Tsujimura, K. Shinoda, T. Kato, Appl. Catal. B 8 (1996) 33.

394 Mechanistic aspects of the “Fast” SCR reaction over Fe-ZSM5 catalysts
Isabella Nova a* , Antonio Grossale a , Enrico Tronconi a , Daniel Chatterjee b , Michel Weibel b
a
Dipartimento di Energia, Politecnico di Milano, I-20133 Milano, Italy
b Daimler AG, HPC: E220, 70546 Stuttgart, Germany
*Corresponding author: Tel: +39 0223993228, Fax: +390223993318, e-mail: isabella.nova@polimi.it
Background
The “Fast” SCR reaction, 2 NH 3 + NO + NO 2 2 N 2 + 3 H 2 O, is required to enhance the low-T DeNOx activity of new generation urea-SCR converters for
Diesel vehicles [1,2]. Herein we report a systematic study of the elementary steps in the Fast SCR chemistry over a commercial Fe-ZSM5 catalyst.
Results
Available observations for stoichiometry, selectivity and kinetics of the Fast SCR reaction at low temperature over V-based catalysts 1 and over zeolites 2,3 have
been rationalised in the literature according to a sequential scheme formally involving NH 4 NO 3 as intermediate:
2 NO 2 + 2 NH 3 N 2 + NH 4 NO 3 + H 2 O (1); NO + NH 4 NO 3 NO 2 + N 2 + 2 H 2 O (2)
On the basis of dedicated transient reactive experiments performed under realistic conditions we show herein that the Fast SCR reaction over Fe-ZSM5 proceeds
via: 1) NH 3 adsorption–desorption; 2) NO 2 disproportion and heterolytic chemisorption in the form of surface nitrites and nitrates; 3) reversible oxidation of
nitrites by NO 2 to form nitrates and NO; 4) thermal decomposition of nitrates to NO 2 and oxygen; 5) reaction of nitrites with NH 3 to form N 2 via decomposition
of unstable ammonium nitrite. Accordingly, the role of NO 2 in the Fast SCR over the Fe-promoted zeolite is to form surface nitrites and nitrates, the role of NO is
to reduce nitrates to nitrites, and the role of NH 3 is to facilitate decomposition of nitrites to nitrogen via the formation of unstable ammonium nitrite.
Justification for acceptance
The results of the dedicated transient experiments herein presented provide a conclusive and exhaustive summary of the Fast SCR catalytic chemistry, which is
directly proven to be identical over V-based and zeolite catalysts. The identification of the Fast SCR reactions is preliminary to the development of mechanistic
reaction kinetics and eventually of a chemically and physically–based, fully transient mathematical model of SCR honeycomb monolithic converters.
References
[1] I.Nova, C. Ciardelli, E. Tronconi, D. Chatterjee and B. Bandl-Konrad, Catal. Today 114 (2006) 3
[2] O. Krocher, M. Devadas, M. Elsener, A. Wokaun, N. Söger, M. Pfeifer, Y. Demel, L. Mussmann, App. Catal. B: Environ. 66 (2006) 208.
[3] Y.H. Yeom, J. Henao, M. Jun Li, W.M.H. Sachtler and E. Weitz, J. Catal. 231 (2005) 181
395 The highly active catalysts of nmCeO 2 -supported CoO x for soot combustion
Jian Liu, Zhen Zhao*, Chunming Xu, Aijun Duan, Guiyuan Jiang
(State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, 102248, China)
*Corresponding author. Tel:+86 10 89731586, Fax: +86 10 69724721, e-mail:zhenzhao@cup.edu.cn
Background The soot particulate matter emitted from diesel engines is one of the most serious pollutants in urban areas. The combination of traps and
oxidation catalysts appears to be the best after-treatment technique. Exhaust gases of the typical diesel vehicle have a temperature ranging from 150 to 400 o C [1-
2]. Thus, the active catalysts must be developed in such temperature levels. In this work, the new nanometric CeO 2 -supported CoO x catalysts were prepared, and
the highly catalytic performances were obtained for soot combustion under the loose contact between soot and catalysts.
Results Nanometric CeO 2 powder were prepared by the auto-combustion method assisted by rotating evaporation [3]. Nanometric CeO 2 -supported cobalt
oxide catalysts were prepared by the method of ultrasonic-assisted incipient-wetness impregnation. Spectroscopic techniques (XRD, XPS, Raman, FT-IR and
UV-Vis DRS) were utilized to determine the structures of Co m /nmCeO 2 samples. The catalytic performances were investigated with temperature-programmed
oxidation reaction (TPO).
The XRD results show that the samples possessed a face-centred cubic fluorite structures. The particle sizes of Co m /nmCeO 2 catalysts were in the range of 6~9
nm. The Raman, XPS, IR and DRS results indicated that the structures of Co m /nmCeO 2 catalysts were altered with the loading amount of Co. At low Co
loading, cobalt oxide existed as CoO or cobalt-cerium oxide solid solution, and the medium or high Co loading resulted in the presence of spinel Co 3 O 4 . While
higher Co loading amount caused the conglomeration of the Co 3 O 4 crystalline, leading to the lower activity.
The results of NO adsorption in-situ DRIFT spectra, and in-situ mass spectra indicate that NO can be adsorbed and oxidized on the Co m /nmCeO 2 catalysts.
Thus, NO 2 can be generated from nitrates decomposition or the directly catalytic oxidation of NO to NO 2 in the gas phase on Co m /nmCeO 2 catalysts. The
nanometric Co m /nmCeO 2 oxides have good catalytic activities for soot combustion under loose contact conditions between soot and the catalyst. The best
catalytic activity was obtained over Co 20 /nmCeO 2 catalyst (T 50 =368 o C). This catalytic activity is as good as supported Pt catalysts, which is the best catalyst
system so far reported for soot combustion under loose contact conditions [4].
Acknowledgements This work was supported by the National Natural Science Foundation of China (No. 20773163, 20473053 and 20525621), the Beijing
Natural Science Foundation in China (No. 2062020), and the 863 program of China (No.2006AA06Z346).
References [1] Z.P. Liu, S.J. Jenkins, D.A. King, J.Am. Chem. Soc. 126 (2004) 10746.
[2] J. Liu, Z. Zhao, C. Xu,, et al., Appl. Catal. B 61 (2005) 39; Appl. Catal. B 78 (2008) 61.
[3] J. Liu, Zhao, C. Xu, A. Duan, L. Wang, S. Zhang, Catal. Commun. 8 (2007) 220.
[4] J. Oi-Uichisawa, S. Wang, T. Nanba, A. Ohi, A. Obuchi, Appl. Catal. B 44 (2003) 207.

398 Mesoporous oxides with ceria for the purification catalysts of automotive emission
V. Parvulescu a* , S. Somacescu a , I. Sandulescu b , I. Popescu b , S. Todorova c and G. Kadinov c
a Institute of Physical Chemistry, Spl. Independentei 202,060021 Bucharest, Romania
b University of Bucharest, Faculty of Chemistry, B-dul Regina Elisabeta 4-12, Bucharest 70346, Romania
c Institute of Catalysis, Bulgarian Academy, Acad. G. Bonchev St., Block 11, Sofia, Bulgaria
*Corresponding author. Tel: +40 21 3115892, Fax: +40 21 312.11.47, e-mail: vpirvulescu@chimfiz.icf.ro
Background
A new tendency in the last years is in the development and use of nanostructured mesoporous oxides with high surface area and uniform pore distribution in the
emission control catalysts. In order to obtain new active materials in catalytic conversion of hydrocarbons we used ceria as support for praseodymium or for
doping of yttria stabilized zirconia. The mesostructured mixed oxides were synthesized by hydrothermal treatment with surfactants.
Results
Ce 1-x Pr x O 2 oxides (were x are 0.1, 0.5 or 0.9) and xCeO 2 -ZrO 2 – 8%Y 2 O 3 powders with x = 5, 10, 15, 20 and 30 molar content were synthesized by hydrothermal
treatment using CTAB as surfactant and urea as the hydrolyzing agent. The obtained materials were characterized by X-ray diffraction, SEM microscopy, N 2
adsorption-desorption, IR, UV-Vis spectroscopy. The catalytic conversion of hydrocarbons (methane, propane, and hexane) was performed under atmospheric
pressure with a quartz-made tubular reactor. Temperature was varied between 50-550 o C. A very homogeneous mesoporous materials with spherical morphology
and an insignificantly variation of lattice parameter were evidenced by SEM microscopy, N 2 adsorption-desorption and XRD. X-ray diffraction peaks of the
calcined CeZrY and CePr samples correspond to the face-centered cubic fluorite structure. The small-angle XRD patterns (2 in the range 0.5-5) showed a
relatively intensive peak in this region for CeZrY oxides. The activity of oxides was very low until 350 o C. The unexpected increasing of the conversion was
evidenced after 450 o C in case of methane oxidation on CePr catalysts and after 350 o C for CeZrY samples in oxidation of propane and hexane. The highest
catalytic potential for total oxidation was obtained for CePr samples (C CH4 =98%) at 530 o C and for CeZrY (15% molar percent of CeO 2 ) sample (C C3H8 =98%,
C C6H14 =90%) at 450 o C, respectively 500 o C.The activity of CeZrY catalysts was influenced by cerium content and presents a maximum for 15% molar percent of
CeO 2 . The treatment of the gels during of synthesis process plays a key role in migration on the uniformity of Pr 4+ : Pr 3+ ratio and oxygen vacancy in these
materials.
Justification for acceptance
The obtained mesostructured oxides have a high catalytic activity and stability in total oxidation of hydrocarbons. These performances offer the possibility to be
used as sensor materials or catalysts for purification in automotive emission control and anode materials for SOFC applications.
410 Transient effective diffusivity studies on a catalytic converter under non reacting conditions
S.T. Kolaczkowski a *, K.Robinson b , S. Awdry a and Y.H. Yap a .
a Catalysis & Reaction Engineering, Department of Chemical Engineering, University of Bath, Bath, BA2 7AY, UK
b Department of Mechanical Engineering, University of Bath, Bath, BA2 7AY, UK
*Corresponding author. Tel: +44 1225 386440, Fax: + 44 1225 385713, email: cesstk@bath.ac.uk
Background
When developing a mathematical model of a catalytic converter, in order to use it as a design tool, it is essential to include a term for the effectiveness factor of
the catalyst. This means, that a value for the effective diffusivity in the catalyst/washcoat layer needs to be calculated/assigned. Although the need for this term is
generally well understood, there is a lack of experimental data in the literature to provide confidence in the method/values to be used. In a review paper [1] on
‘Measurement of effective diffusivity in catalyst coated monoliths’, a novel approach using an established transient technique (or chromatographic method) is
described, which was shown in a theoretical simulation to be viable. However, a longer length of monolith was required in order to ensure that changes as a result
of diffusion in the thin layer of the washcoat could be experimentally detected.
Results
The experiments are performed using a Ford 4 cylinder turbocharged and after-cooled diesel engine. This type of engine is currently fitted in production vehicles
e.g. Mondeo. The engine is set to operate at a constant speed, and the hot exhaust is fed into a specially fabricated housing consisting of a number of catalytic
converters mounted in series (to amplify the output signal).
By injecting a known quantity of species (e.g. 10,000 ppm of CO) in the form of a pulse (e.g. duration 3s), directly into the exhaust stream from the engine, then
the response of the output signal at the outlet of the converter may be analysed, and the effective diffusivity calculated. Results are presented of experiments
using a monolith that has been coated with a washcoat, but without any catalyst (to minimize the initiation of chemical reactions which would consume the
injected CO). These are compared with experiments for a catalyst coated monolith, where the gas inlet temperature is below that at which the catalyst is
considered to be active (e.g. 100 ºC ). In these experiments, the effect of gas inlet temperature and operating characteristics of the engine can be assessed. The
transient thermal response of the converter is also carefully monitored to detect the initiation of any chemical reactions. Blank/baseline experiments (without
washcoat) are also performed to quantify dispersion characteristics of the channels and gas inlet/outlet ports.
Justification for acceptance
To reduce emissions, the design of catalytic converters and the way in which they are used needs to be improved. The first phase of work on ‘effective diffusivity
aspects’ is described, that forms the start of a 3 year project (2007-2010) on: ‘On-line and on-engine catalyst characterisation – a diagnostic technique to design
better catalysts’, supported by the EPSRC (some of the converters are supplied by Johnson Matthey).
References
[1] S.T. Kolaczkowski, Catalysis Today 83 (2003) 85-95.

411 Transient heat transfer studies on a catalytic converter under non reacting conditions
S.T. Kolaczkowski a *, K.Robinson b , S. Awdry a and S. Ye b .
a Catalysis & Reaction Engineering, Department of Chemical Engineering, University of Bath, Bath, BA2 7AY, UK
b Department of Mechanical Engineering, University of Bath, Bath, BA2 7AY, UK
*Corresponding author. Tel: +44 1225 386440, Fax: + 44 1225 385713, email: cesstk@bath.ac.uk
Background
Although there are many papers that describe the construction of mathematical models of catalytic converters for the control of emissions from vehicles, very few
of them show any comparison with real experimental data. The models vary in complexity, and some have many tuneable parameters – hence the link between
cause and effect is not transparent. When a mathematical model is constructed of a converter, it is essential to ensure that the method used to model the basic heat
transfer aspects is appropriate. Otherwise, as reactions are exponentially dependent on temperature, small errors in temperature can have a significant effect on
the method of calculating reaction rates - especially under transient conditions. It is also well recognized [1] that pulsations from the engine will affect catalyst
warm-up.
Results
The novelty in our approach arises from the use of a commercial catalytic converter as an experimental reactor (connected to a live engine). This creates a sense
of realism and provides opportunities, however, this also create many challenges. The experiments are performed using a Ford 4 cylinder turbocharged and aftercooled
diesel engine. This type of engine is currently fitted in production vehicles e.g. Mondeo. The hot exhaust from the engine is then fed into a catalytic
converter, which contains a monolith that has been coated with a washcoat, but without any catalyst (to minimize the initiation of reactions which would affect
the thermal response). First, the engine is set to operate at a constant speed, producing a constant set of conditions to the converter e.g. 300 ºC. Then, cold air is
suddenly added directly into the exhaust, such that the inlet of the converter is exposed to a downward step change in temperature e.g. 170 ºC (note: a change in
the total mass flow of gas also occurs). The transient response of the converter is then carefully monitored. Inlet and outlet gas temperatures, and monolith wall
temperatures are recorded using 0.5 mm thermocouples that are positioned at regular intervals along the centre line axis of the monolith. The composition of the
exhaust gas in and out of the converter is monitored, using a fast analyzer. In the poster, the technique is illustrated, and experimental results are compared with
modelled data using different forms of expression for the heat transfer coefficient. Entrance effects and pulsations are clearly important.
Justification for acceptance
To reduce emissions, the design of catalytic converters and the way in which they are used needs to be improved. The first phase of work on ‘heat transfer
aspects’ is described, that forms the start of a 3 year project (2007-2010) on: ‘On-line and on-engine catalyst characterisation – a diagnostic technique to design
better catalysts’, supported by the EPSRC (some of the converters are supplied by Johnson Matthey).
References
[1] S.F. Benjamin and C.A. Roberts, Proc. Instn. Mech. Engrs. Vol 215 Part D (2005) 891-910.
421 Pt-induced distribution of Ba-sites activity towards regeneration stage on NO x storage-reduction catalysts
U. Elizundia, R. López-Fonseca*, M.A. Gutiérrez-Ortiz, J.R. González-Velasco
Chemical Technologies for Environmental Sustainability Group, Department of Chemical Engineering,
Faculty of Science and Technology, Universidad del País Vasco/EHU, P.O. Box 644, E-48080 Bilbao, Spain.
*Corresponding author. Tel: +34 946015985, Fax: +34 946015963, e-mail: ruben.lopez@ehu.es
Background
The development of NO x storage-reduction (NSR) catalysts was impelled by the introduction of lean-burn engine technologies. The presence of different Basorption
sites over model Ba/Pt-Al 2 O 3 NSR catalysts have been already evidenced. Indeed, the influence on the chemical nature of the sorption sites activity has
been addressed [1], along with the effect of the relative position between sorption sites and noble metal [2]. Moreover, a Pt-catalysed surface reaction during
regeneration stage has been proposed [3]. In this study, the later effect has been analysed as a function of Pt-loading and its incorporation order.
Results
The NO x storage-reduction behaviour of a series of Ba(15)/Pt(x)-Al 2 O 3 (with Pt-loadings up to 1.8 %wt), prepared
by wet impregnation of Pt/Al 2 O 3 with Ba(Ac) 2 has been investigated. Calcination process, followed by TG-MS, Pt00
was indicative of the dependence of Ba(Ac) 2 stability on the surrounding amount of Pt. Moreover, after storage
sites saturation at 350 ºC, NO x ad-species stability (also followed by TG-MS) under reducing (H 2 ) conditions was
also altered by the surrounding amount of Pt. Starting from Pt absence, an increased loading led to a progressive
Pt03
Pt05
decay on nitrate stability, Figure 1. A different picture was observed, when Ba-precursor preceded Pt
incorporation, resulting in a less noticeable influence of the noble metal. These results were also correlated to those
obtained under realistic NSR operation conditions (no imposed delays between rich and lean events, tuned cycle
timing in order to prevent reductant slip, presence of CO 2 and H 2 O). It was observed that a higher Pt content
Pt07
Pt14
Pt18
promoted NSR performance especially at low temperatures.
Justification for acceptance
2·10 -3 NO x adsorption
Due to the relatively high cost, noble metal loading and its incorporation procedure must be optimised on
temperature
the high-demanding automotive catalyst industry.
0 100 200 300 400
References
Temperature, ºC
500 600
[1] L. Lietti, P. Forzatti, I. Nova, E. Tronconi. J. Catal. 204 (2001) 175-191.
[2] W.S. Epling, J.E. Parks, G.C. Campbell A. Yezerets, N.W. Currier, L.E. Campbell. Catal. Today 96 (2004) 21-30.
Figure 1. Normalised dTG signal during H 2 -TPD
[3] I. Nova, L. Lietti, L. Castoldi, E. Tronconi, P. Forzatti. J. Catal. 239 (2006) 244-254.
runs as a function of Pt-loading
dTG N , (mg min -1 )/mg T

423 0D modelling : a promising way for exhaust after-treatment issues in automotive application
G. Mauviot, F. Le Berr
IFP, 1 & 4 Avenue du Bois Préau, 92852 Rueil-Malmaison Cedex, FRANCE
Corresponding author. Tel: +33 1 47 52 73 34, Fax: +33 1 47 52 70 68, e-mail: gilles.mauviot@ifp.fr
Background
For modern automotive applications, after-treatment systems become mandatory to respect the new emission standards. As a result, requirements on
after-treatment issues are more and more significant on the cost of the whole engine and vehicle development process. For example, a classical
Diesel after-treatment line is now composed of several catalysts often associated with a particulate filter. This complex architecture implies to
develop advanced tools to help the exhaust line conception and also the design of associated control strategies indispensable to manage so
sophisticated system.
Results
The present paper demonstrates that 0D simulation can be an accurate and low cost approach to develop exhaust line simulators and deals with
complex compromises between accuracy and CPU performances. This paper proposes an original zero-dimensional model of monolith. This
approach is based on resistive and capacitive elements according to the bond-graph theory. The dynamic model described in this paper takes into
account the pneumatic flow and the thermal behaviour of the monolith. Models of several catalysts are built plugging this monolith model with
some well known simplified chemical reaction scheme [1]. To split a model of monolith into several elementary zero-dimensional blocks in series
allows to have a good representation of the specific internal dynamic of one catalyst and to access to some local information as in conventional well
known one-dimensional model [2]. Such an approach is first used as a phenomenological understanding means of the catalytic system which is
known to be more than only a chemical reactor. It is also used as a simulation tool for engine emission control. First, some validations on synthetic
gas bench results of several catalysts from literature are performed in order to discuss the approach validity and relevance. Then, a concrete
automotive application is described to illustrate the use of 0D simulation tools. The application is based on Diesel engine test bed results. The aftertreatment
system is only composed of one Diesel oxidation catalyst. In this context, 0D modelling shows a promising way to help control strategy
development by providing accurate simulators which can be used as virtual after-treatment systems.
Justification for acceptance
In the automotive context, catalysis concentrates all the attention because it is the only way to reach the future standards. With the increase of
exhaust system complexity, the development of accurate simulators become indispensable during the whole process of exhaust line design.
References
[1] G.C. Koltsakis, P.A. Konstantinidis, A.M. Stamatelos, Applied Cat. B: Env. 12 (1997),161-191.
[2] C. Depcik, D. Assanis, Prog. in Energy and Combustion Science 31 (2005), 308-369.
445 Novel NO x reduction method combining NO x storing materials with electrochemical reduction of nitrogen oxides
U. Röder * , K. Sahner, R. Moos
Bayreuth Engine Research Center, Department of Functional Materials, University of Bayreuth, 95440 Bayreuth, Germany
*Corresponding author. Tel: +49 921 55 7425, Fax: +49 921 55 7405, e-mail: ulla.roeder@uni-bayreuth.de
Background
Lean-burn engines, for example diesel engines that provide oxygen in excess during combustion, are excellent in terms of energy efficiency but emit a large
quantity of nitrogen oxides (NO x ) due to their operating principle. Since oxygen is present in excess in the lean exhaust, NO x cannot be completely reduced by
conventional three-way-catalysts. In an alternative electrochemical approach, NO x is reduced electrochemically by pumping a current through a ceramic ionic
conducting membrane. However, the effectiveness of these principles in presence of excess oxygen is low.
Results
In this contribution, a modified method for electrochemical NO x reduction in lean exhausts is presented. Two different types of ionic conductors were used,
oxygen ion conductors and proton conductors. To increase the efficiency of the NO x reduction in oxygen containing exhaust gases, we added a NO x storing
material. Possible candidates are barium or potassium carbonate, materials known from NO x storage catalysts.[1] NO x reduction then proceeds in a two-step
process. During the first step, NOx is stored by the storing material. When no more nitrogen oxide can be stored, a pumping voltage is applied to the ion
conductor, thus reducing the stored NO x . The presence of the storage material in direct contact to the ion conductor limits the oxygen access and increases the
NO x partial pressure compared to the oxygen partial pressure. As a consequence, the parasite reactions related to excess oxygen, eg., oxygen pumping or
formation of water, are limited. The main challenge of this concept is to identify the optimum trade-off in operating temperatures. While an optimum temperature
around 350 °C exists for storing NO x , ionic conductors present a better performance, i.e., conductivity, at considerably higher temperatures. Our study aimed at
demonstrating feasibility of this concept by finding an appropriate combination of materials and operating conditionsto solve this problem.
Justification for acceptance
This study proposes a novel aftertreatment method for lean automotive exhausts and fits therefore well within the scope of the automotive emission control
section of the ICEC. In particular, the NOx reduction in lean exhaust treated herein is a highly significant, up-to-date issue that is closely related to the discussion
on climate warming by CO 2 emission.
References
[1] W. Strehlau, J. Leyer, E.S. Lox, T. Kreuzer, M. Hori, M. Hoffmann, SAE Paper 962047 (1996)

450 Continuous monitoring and measurements for N 2 O emissions from NH 3 -SCR DeNO x reaction
on commercial V 2 O 5 /TiO 2 -based catalysts
Ki-Hwan Kim a , Young-Hyun Lee a , Moon Hyeon Kim a,* , Sung-Won Ham b , Seung Min Lee c , Jeong-Bin Lee c
a Department of Environmental Engineering, Daegu University, 15 Naeri, Jillyang, Gyeongsan 712-714, Korea
b Department of Display and Chemical Engineering, Kyungil University, 33 Buho, Hayang, Gyeongsan 712-701, Korea
c Korea Electric Power Research Institute (KEPRI), 103-16 Moonji, Daejon 305-308, Korea
*Corresponding author. Tel: (+82-53) 850-6693, Fax: (+82-53) 850-6699, E-mail: moonkim@daegu.ac.kr
Background
Nitrous oxide (N 2 O) would be significantly produced from NH 3 -SCR DeNO x (selective catalytic reduction of NO x by NH 3 ) processes [1] that are widely used for
abating NO x from fossil fuel-fired power plants. The use of grab sampling for N 2 O analysis gives its secondary formation in the sample during transport and
storage [2]. Thus, an on-line analysis technique is required to quantitatively determine the extent of the production of N 2 O at on-site SCR units.
Results
A commercially available infrared (IR) spectrophotometer equipped with a gas cell having an optical path of 10 meters was connected directly to the downstream
of a laboratory-designed SCR reactor. The whole wall surface inside the gas cell was coated with Ni and finally Au to prevent undesired reactions between
reactants on the wall surface. Ultrahigh purity N 2 O, NH 3 , O 2 , He (99.999%), and NO (99.99%) were employed here, but a level of impurities, such as H 2 O, CO 2 ,
CO, CH 4 , and other trace species, present in each cylinder gas was determined to acquire possible interference to direct on-line measurements for the N 2 O
formation. The IR system was calibrated with a flowing mixture of N 2 O/He to yield 0-230 ppm N 2 O, and had a detection limit of 1 ppm for N 2 O based on the
most intense peak at 2242 cm -1 . When directly measuring N 2 O concentrations during the course of SCR reaction, the extent of the N 2 O formation depended
significantly on amounts of V 2 O 5 in the catalysts, which was in excellent agreement with earlier studies [3].
Justification for acceptance
Our study has been devoted to develop a continuous IR-based analysis system for directly monitoring and measuring N 2 O concentrations formed during NH 3 -
SCR DeNO x reaction over commercial V 2 O 5 /TiO 2 -based catalysts. The direct N 2 O measurements represented the strong need of optimization of V 2 O 5 contents in
frequently-used commercial SCR catalysts without any loss of DeNO x performances.
[1] J.A. Martin, M. Yates, P. Avila, S. Suarez, J. Blanco, Appl. Catal. B 70 (2007) 330.
[2] T. Hulgaard, K. Dam-Johansen, Environ. Prog. 11 (1992) 302.
[3] G. Madia, M. Elsener, M. Koebel, F. Raimondi, A. Wokaun, Appl. Catal. 39 (2002) 181.
455 Chemical Deactivation of SCR catalysts
P. Kern, M. Klimczak, M. Lucas, P. Claus*
Department of Chemistry, Technical Chemistry II, Darmstadt University of Technology,
Petersenstrasse 20, D-64287, Germany
claus@ct.chemie.tu-darmstadt.de
Background
Selective Catalytic Reduction with ammonia (NH 3 -SCR) is a technology which is able to meet the strict limit values for emissions over the running time of an
automobile. Thermal and in particular chemical deactivation caused by deposition of several inorganic poisons result in a reduced catalytic performance. By
applying high throughput techniques we screen the effects of 15 potential catalyst poisons and their combinations to the catalysts V 2 O 5 /WO 3 /TiO 2 , Fe zeolite and
Pt/Al 2 O 3 (for NO-oxidation). A selection of poisons is further investigated by poisoning with corresponding aerosols.
Results
Poisoning: For the HT-screening, 72-cpsi gas prove monolithic honeycomb catalysts are poisoned by an automated channel by channel impregnation procedure
using a pipetting robot [1] . Furthermore 400-cpsi honeycomb catalysts are poisoned by aerosols at 500 °C and a space velocity of 50000 h -1 (95% air, 5% H 2 O). All
unpoisoned catalysts are provided by industrial partners and are close to commercial products.
Testing conditions: The feed consists of NO, NH 3 , CO, O 2 , CO 2 , H 2 O and nitrogen. Experiments are carried out
V 2
O 5
-catalyst
at temperatures ranging from 200 to 450 °C and a space velocity of 50000h -1 100
unpoisened catalyst
. The reaction gases are analyzed by
90 poisoning by aerosol, catalyst poison: KNO 3 , 3 mmol K
80 poisoning by aerosol, catalyst poison: NaNO
FTIR-spectroscopy (Nicolet Anataris IGS).
3 , 3 mmol Na
70
HTS is carried out in a High-Throughput test rig with a 3D-positioning system and a Sampling/Dosing-System,
60
which allows the testing of single channels of the monolith [1] 50
.
40
The experiments show a strong poisoning effect of alkaline-and alkaline earth metals and phosphorous to the
30
20
catalysts. The deposition of transition metals results in a decrease of N 2 -selectivity. The results from HTS are in
10
good agreement with results from aerosol poisoning in most cases.
0
200 250 300 350 400 450
Justification for acceptance
temperature [°C]
The causes for deactivation of modern SCR aftertreatment systems are of high interest to catalyst suppliers and
Fig. 1: Effect of K and Na on DeNOx activity,
the
Aerosol Poisoning
identification of poisons may lead to counter measures and the improvement of the catalyst lifetimes.
The characterization of poisoned catalysts, among the comparison between impregnation- and aerosol
poisoned samples, leads the way to our final goal, the development of a rapid aging protocol covering
thermal as well as chemical deactivation.
References
[1] M. Lucas, P. Claus, Appl. Catal. A: General 254 (2003) 35.
DeNOx [%]

461 New catalysts for reduction of nitric oxides by carbon monoxide
R.B.Akverdiyev a , V.L.Baghiyev b*
a Institute of Petrochemical Processes ANAS, Baku, Azerbaijan
b Azerbaijan State Oil Academy, Baku, Azerbaijan
* Corresponding author. Tel: (+99450) 3280059, Fax: (+99412) 5140349, e-mail: vagif_bagiev@yahoo.com
Background
The greatest amount of pollution to atmosphere of the Earth is produced by traffic and consists mainly from carbon and nitric oxides. One of the perspective
methods for their cleaning is catalytic reduction of nitric oxides by carbon monoxide as both toxic compounds simultaneously leave from gas emissions.
Replacement well known catalytic systems on the basis of metals of platinum group by rather cheaper and accessible catalysts at preservation of demanded level of
efficiency is an important problem. From this point of view, the choice of the catalysts received on the basis of activated aluminum alloys is expedient.
Results
The studied catalysts have been synthesized by interaction of alloys Cu(Ni, Co)InGaAl with water and the further drying of a deposit at 120 0 and treatment at
550 0 in air atmosphere. Spectrophotometric researches have shown, that on the reaction conditions on a surfaces of catalysts there is a set of ions of copper in
different conditions: Cu 2+ , Cu + and Cu 0 . It is shown that reaction proceeds through intermediate carbonyl and isocyanate complexes over synthesized catalysts.
Atoms of copper participate in formation of isocyanate complexes and ions of Cu + participate in formation of carbonyl complexes. On a basis kinetic researches
of reaction of oxidation of CO and reduction of NO on copper containing catalysts it is established, that at a rather low temperatures and ratio :NO 1 a degree of surfaces reduction increases, in other words the quantity of
atoms Cu 0 increases. On these atoms becomes possible dissociation of NO. Atoms of nitrogen, co-operating with the adsorbed molecules of CO form isocyanate
complexes, which, reacting with NO ads , discharge nitrogen molecules on a gas phase. It is shown, that molecules NO and CO participate in processes of oxidation
and reduction of a surface of the catalyst, and they compete among themselves for adsorption places on a surface. At oxidation of a surface by molecules NO
there can be a transition of ions Cu + to Cu 2+ . At the same time molecules NO still contact with ions of oxygen of a surface, leaving ions Cu 2 + uncombined. At
temperatures of reaction adsorption CO on ions Cu 2+ does not occur. Simultaneously with reaction of reduction of NO, oxidation of CO by oxygen proceeds in
reactionary system. There are, at least, two sources for CO oxidation - the oxygen which is present as admixture in initial reaction mixture, and oxygen of
blankets of the catalyst.
Justification for acceptance
Thus the developed catalysts synthesized by us show high activity in reaction of CO oxidation and simultaneous NO reduction. Most activity in the studied
reaction shows copper containing samples. This catalyst may be used for the further investigations in pilot scale.
462 Experimental investigation of the reduction mechanisms over Pt-Ba/Al 2 O 3 Lean NO x Trap systems
Isabella Nova a,* , Luca Lietti a , Pio Forzatti a F. Prinetto b , F. Frola b , G. Ghiotti b
a Dipartimento di Energia, Politecnico di Milano, I-20133 Milano, Italy
b Dipartimento di Chimica IFM and NIS, centre of excellence, Università di Torino,
via P. Giuria 7, 10125 Torino, Italy
*Corresponding author: Tel: +39 0223993228, Fax: +390223993318, e-mail: isabella.nova@polimi.it
Background
The so-called Lean NO x Traps (LNT) represent a viable solution for the abatement of NO x emissions from lean–burn engines [1]. Several studies were published
on the mechanisms of both the NO x storage [1] and reduction [2] steps, but a complete understanding of these processes is still lacking.
Results
In previous studies [2] we showed that on Pt-Ba/Al 2 O 3 catalysts the reduction process is not initiated by the thermal decomposition of the stored NO x ad-species,
but a catalytic pathway involving Pt is instead operating. New results are herein presented, which prove that such catalytic pathway is constituted of 2 consecutive
steps in which NH 3 is formed as intermediate upon reaction of nitrates with H 2, and further reacts with nitrates to produce selectively N 2 . Water favours the first
step process but has no significant impact on step 2, whereas CO 2 has a strong inhibition effect on both steps due to poisoning of Pt by carbonyls, shown FT-IR
spectroscopy.
A parallel study showed that CO is a much weaker reducing agent than hydrogen, and leads to formation of isocyanates as potential reaction intermediates,
identified by FTIR spectroscopy. However, in the presence of water the CO reactivity is significantly enhanced, due to the occurrence of the water gas shift
reaction that produces H 2 , the actual reducing agent also in this case.
Justification for acceptance
The optimization of the operating conditions and the rationalization of the catalyst formulation of LNT systems are required for their commercialization on a
large scale. To achieve such objective key factors are the detailed comprehension of the mechanisms involved in the “NO X storage/reduction” systems and in
particular of the parameters that determine the selectivity of the reduction process.
References
[1] W.S.Epling, L.E.Campbell, A.Yezerets, N.W.Currier and J.E.Park II, Catal. Reviews, 46 (2004) 163
[2] I.Nova, L.Lietti, L.Castoldi, E.Tronconi, P.Forzatti, Journal of Catalysis, 239 (2006) 244

463 NO x storage on Pt-K/Al 2 O 3 NSR catalyst
F.Frola a ,S.Morandi a ,F.Prinetto a ,G.Ghiotti a,* ,L.Castoldi b ,L.Lietti b ,P.Forzatti b
b Dipartimento di Energia, P.zza L. Da Vinci 32, 20133 Milano, Italy
*Corresponding author. Tel: +39 116707539, Fax : +39 116707855, e-mail: giovanna.ghiotti@unito.it
Background
Pt-Ba/Al 2 O 3 NO x storage reduction catalysts appear nowadays the most promising solution to abate NO x produced by petrol engines [1-2]. However, Potassium is
gaining attention as storage element, and, recently, Park et al. [3] showed that: (i) the co-loading of potassium and barium oxides enhances the thermal stability of
the stored NO x ; (ii) after hydrothermal treatment at 850 °C K/Al 2 O 3 and K-Ba/Al 2 O 3 preserve their storage capacity better than Ba/Al 2 O 3 . Hereafter preliminary
results about the NO x storage-reduction on Pt-K/Al 2 O 3 catalyst are presented and compared with that previously performed in the same conditions on a Pt-
Ba/Al 2 O 3 catalyst [4,5].
Results
The NO x storage at 350°C on homemade Pt-K/-Al 2 O 3 (1/5.4/100 w/w) catalyst was studied by FT-IR in situ and TRM analyses performed under admission of
NO 2 or NO/O 2 mixture. As in the case of Pt-Ba/Al 2 O 3 catalyst [4,5], when NO 2 was stored only nitrates were formed on Pt-K/Al 2 O 3 , both of ionic type (
(NO 3 ) asym at 1370 cm -1 and (NO 3 ) sym at ca.1030 cm -1 ) and bidentate type ((N=O) at 1550 cm -1 , (NO 2 ) asym at 1320cm -1 , (NO 2 ) sym at 1030-1020 cm -1 ).
However, while on Pt-Ba/Al 2 O 3 catalyst ionic nitrates were the predominant species, on Pt-K/Al 2 O 3 the bidentate nitrates were also present in relevant amounts
and the ionic species showed a more pronounced ionic character. Again, as in the case of Pt-Ba/Al 2 O 3 catalyst, by admitting the NO/O 2 mixture an initial
formation of nitrite species was noted, rapidly evolving to nitrates both of ionic and bidentate types. It is worth noting that nitrites formed on Pt-K/Al 2 O 3 at the
beginning of the storage were both of bidentate type ((NO 2 ) sym at 1230 cm -1 ) and linear type ((N=O) at 1500-1550 cm -1 , (N-O) at 1100-1050 cm-1). The
same experiments have been performed at lower temperatures: in this case formation of nitrites, along with nitrates, have been observed upon NO 2 admission, as
opposite to the Pt-Ba/Al 2 O 3 catalyst.
The reduction of the stored NO x species has also been investigated at different temperatures. As suggested in the case of the Pt-Ba/Al 2 O 3 catalysts, the reduction
of the stored NO x species to N 2 occurs also in this case according to a 2-step mechanism which implies at first the formation of ammonia upon reduction of the
stored NO x with H 2 , followed by the subsequent reaction of NH 3 with nitrates to give N 2 . Accordingly NH 3 is an intermediate in the formation of N 2 . Notably,
these two steps are clearly distinguishable in the case of Pt-Ba/Al 2 O 3 in that the reactivity of H 2 in the formation of NH 3 is much higher than N 2 formation upon
NH 3 + nitrates reaction, whereas a similar reactivity of the two steps has been pointed out in the case of the K-containing system. Accordingly higher N 2
selectivity is observed in the case of the Pt-K/Al 2 O 3 catalyst. These aspects are currently under investigation in our labs.
Justification for acceptance
References
[1] H. Shinjoh, N. Takahashi, K. Yokota, M. Sugiura, Appl.Catal.B: Environmental 15 (1998) 189.
[2] R. Burch, Catal. Rev.-Sci. Eng. 46 (2004) 3&4, 271.
[3] S. M. Park, J. W. Park, H-P. Ha, H-S Han, G. Seo, J. Chem. Catal. A: Chemical, 273 (2007) 64.
[4] F. Prinetto, G. Ghiotti, I. Nova, L. Lietti, E. Tronconi, P. Forzatti, J. Phys. Chem.B., 105 (2001) 12732.
[5] F. Prinetto, I. Nova, L. Castoldi, G. Ghiotti, L. Lietti, E.Tronconi, P. Forzatti, J.Catal, 222/2 (2004) 377.
464 Soot combustion: reactivity of alkaline and alkaline-earth metal oxides
Lidia Castoldi, Roberto Matarrese, Luca Lietti*, Pio Forzatti
Dipartimento di Energia, Politecnico di Milano, Milano, Italy
*Corresponding author: Tel.: +39 0223993272, Fax: +39 0270638173, E-mail address: luca.lietti@polimi.it
Background
Over the past decade the use of Diesel engines expanded in sectors traditionally covered by gasoline engines, because of their good driving characteristics and
their higher fuel efficiency. However, high levels of particulate matter (soot) are emitted from Diesel engines. At present, the technology used to reduce soot
emissions consists in the employment of diesel particulate filters (DPF), which must be periodically regenerated. The catalytic regeneration of the filters at lower
temperature is a challenge nowadays. Among the various investigated catalytic systems, alkali promoted ones (i.e. K- and Cs-based catalysts) show interesting
properties.
Results
In the present study a systematic analysis of the reactivity of alkaline (i.e. Na, K and Cs) and alkaline-earth (i.e. Mg, Ca and Ba) catalytic systems in the soot
combustion has been carried out. The oxidation of soot was investigated by means of Temperature Programmed Oxidation and also under isothermal conditions
both in the presence of alumina supported catalysts (loose contact) and after direct impregnation of soot with catalyst precursors as well (full contact). Uncatalysed
soot oxidation was also performed for comparison purposes. It was found that the alkaline-containing samples are very active in the soot oxidation
even under loose contact conditions. As a matter of facts, a decrease of the soot ignition temperature of 100 and 150°C, respectively, was observed for the
K/Al 2 O 3 - and Cs/Al 2 O 3 -soot systems with respect to the uncatalyzed soot combustion. On the other hand the results showed that presence of alkaline-earth metals
does not significantly affects the soot oxidation activity. When an intimate contact was guaranteed between the active elements and the soot (full contact), the
reactivity in the soot combustion was enhanced for both alkaline- and alkaline earth-based samples, as expected. Notably in these conditions the reactivity of the
Ba-containing sample becomes similar to the very active K- and Cs-based systems. The order of reactivity can be correlated with the electronegativity of the
selected metals, which could affect the capacity to weak the C-C bond and start the oxidation process.
Justification for acceptance
The tests performed with full-contact systems allowed the analysis of the intrinsic oxidizing property of alkaline or alkaline earth elements since an intimate
contact between the key-catalyst component and the soot is guaranteed a priori. This led us to the rationalization of the role of such elements in the combustion
of soot.

466 A Novel Method for Automotive NOx depollution : in situ Generation of Ammonia
Sébatien THOMAS, Véronique PITCHON *
LMSPC, UMR 7515 du CNRS 25 rue de Becquerel, 67087 Strasbourg, France, pitchon@chimie.u-strasbg.fr
Background
A possible way to control NO x emission from automotive exhaust is the so called “standard” SCR where the main reaction is between ammonia and NO.
This technology, in process for stack gases from stationery sources, is not transferable to mobile applications. One option would be to generate NH 3 ammonia on
board in order to be consumed in the so-called “fast” SCR reaction, known as the reaction of NH 3 and an equimolar quantity of NO and NO 2 .The presence of
hydrogen is currently observed in an engine with concentration as high as 1%, thus by choosing an appropriate catalyst, the formation of ammonia become
feasible. We have tested a number of supported noble metals on various oxides for the formation of ammonia in an O 2 rich mixture (5000 ppm) in the presence of
3% CO and HC (propene, 600 ppm) with 1000 ppm of NOx and 1% H 2 and a VVH of 60,000 h -1 .
RESULTS
Support influence
After comparison of Pt and Pd, we have selected the latter to be deposited on a large number of supports. Among all the supports, Pd/Al 2 O 3 gave the
higher selectivity and activity and was retained for further examination. On this catalyst, the production of hydrogen resulting from steam reforming and WGS is
obtained, which allows the production of on-board hydrogen, offering the possibility to produce ammonia even in the absence of H 2 in the exhaust.
Effect of Pd loadings
The effect of Pd loadings (0.1 to 2 %) was tested in the presence and in the absence of water. A selectivity of 100% in ammonia is achieved with 1%
Pd/Al 2 O 3 . The presence of water favours the oxidation of isocyanic acid which has been identified as a reaction intermediate.
Influence of HC concentration
The influence of C 3 H 6 concentarion was tested with 750, 600, 400 and 0 ppm. As the concentration increases, the activity decreases. This effect is
directly correlated with a lower reactivity of H 2 ; particularly above 310°C. This is due to a competition of adsorption between C 3 H 6 and H 2 which impedes the
adsorption of the HC.
Effect of O 2 concentration
The effect of O 2 was studied with 0.5, 1.0, 1.4 et 2. There is an optimum for 1% O 2 . Above this concentration the oxidation of H 2 becomes more
favourable than the oxidation of C 3 H 6 and therefore there is less H 2 available for the formation of NH 3 .
Conclusion
We have demonstrated the possibility of generating in situNH 3 for the reduction of NOx in an engine by using a catalyst based on Pd on alumina. The
various mechanistic aspects of the NH 3 formation and reaction will be explained.
471 A Novel Cu-V/Al 2 O 3 Catalyst for Selective Reduction of NO by NH 3 at Low Temperature
Chengjun Wang † , Yuegang Zuo* † and Chen-lu Yang ‡
† Department of Chemistry and Biochemistry and ‡ Advanced Technology and Manufacturing Center, University of Massachusetts Dartmouth, 285 Old Westport Road, North
Dartmouth, MA 02747
E-mail: yzuo@umassd.edu, Phone: 508-999-8959, Fax: 508-999-9167. POSTER
Background
Over the past two decades, catalytic techniques have shown promises for the direct removal of NO and other NO x from emission gases. In principle, the simple
decomposition of NO into N 2 and O 2 , a thermodynamically favorable reaction at low temperature, is desirable. However, the reaction is very slow and sufficiently
active catalysts have not been discovered. As a result, CO, methane, propane and other hydrocarbons have been tested as reductants to reduce NO into N 2 . But
these reactions require the catalysts made of noble metals such as Pt, Pd, and Rh, and high cost of facilities, and still suffer from the low removal efficiencies at
low temperature. More recently, the selective catalytic reduction (SCR), particularly those using NH 3 to selectively reduce NO x under the excessive oxygen
condition, have been extensively studied and applied to eliminate NO x from stationary sources such as power plants, and automotive exhausts. Such technique
offers the advantages of low cost, high selectivity of NH 3 reaction with NO in the presence of oxygen, and the possibility for converting the noxious gas to one or
more innocuous substances such as nitrogen gas and water, which are free of disposal problems. However, the reaction mechanism of selective catalytic reduction
of nitrogen oxides by NH 3 is not well understood yet because reactions are complicated with the different proportions of ammonia, nitric oxide and oxygen at
different temperatures in SCR system. The NH 3 -SCR technique still contains some severe disadvantages such as NH 3 -slip by unreacted and/or excess NH 3 and
high operation temperature and thus high cost of facilities.
Results
In this study, a novel copper-based catalyst has been synthesized and evaluated for its efficiency on the selective catalytic reduction of nitric oxide (NO) using
ammonia (NH 3 ) as a reductant in the temperature range of 50~500 o C. The Brunauer-Emmett-Teller (BET) method, Energy Dispersive X-ray Spectrometry
(EDS) and Scanning Electron Microscopy (SEM) have been used to characterize the catalysts developed. The effects of reaction parameters including
temperature, space velocity, oxygen concentration, and the ratio of ammonia to nitric oxide on the selective catalytic reduction of NO by NH 3 on the synthesized
catalyst, as well as the chemical mechanisms and the side reactions involved have been examined. The catalyst shows high activity for NO conversion (90%) with
a NH 3 /NO ratio of about 1 in the presence of O 2 (~ 3% v/v) at a temperature of 200 o C. At a temperature of 200 o C or below, only selective (desirable) catalytic
reactions occur. At temperatures above 200 o C, ammonia was gradually oxidized to NO and NO 2 , and thus led to a low NO removal efficiency. The NO
conversion also increased with decreasing space velocity between 3600 hr -1 ~7800 hr -1 .
Justification for acceptance
Emission of NO x represents a severe environmental problem because NO x are major contributors to many large atmospheric environmental pollution issues. [1] In
this presentation, we report on development and evaluation of a novel Cu-V/Al 2 O 3 catalyst, which has shown to be very promising for the elimination of NO
using NH 3 as a reductant in flue gases.
Reference
[1] G. Busca, L. Lietti, G. Ramis, F. Berti, Appl. Cat. B: Environ. 18 (1998) 1.

479 NH 3 production and decomposition during regeneration of NO x storage catalyst
P. Koí a,* , J. Štpánek a , F. Plát a , M. Marek a , V. Schmeisser b , D. Chatterjee b and M. Weibel b
a Institute of Chemical Technology, Prague, Department of Chemical Engineering,
Technická 5, CZ 166 28 Prague, Czech Republic
a Daimler AG, Department GR/VPE Combustion and Emission Control,
019-G206, D 705 46 Stuttgart, Germany
* Corresponding author. Tel:+420 220 443 293, fax: +420 220 444 320, e-mail: petr.koci@vscht.cz
Background
Several nitrogen compounds can be produced during the regeneration phase in periodically operated NO x storage and reduction catalyst (NSRC) for conversion of
automobile exhaust gases from lean burn engines. Besides the main product N 2 , also NO, N 2 O, and NH 3 can be formed, depending on the regeneration phase
length, temperature, and gas composition [1]. Main by-product under typical fuel-rich conditions is NH 3 . Ammonia formed under reducing conditions in the front
part of the monolith can be re-oxidised by NO x or oxygen in the rear, yet unreduced part of the monolith, until the reduction front reaches the outlet [2, 3].
Results
We focus on experimental evaluation and kinetic modelling of the NO x reduction dynamics during catalyst regeneration phase with particular focus on the
ammonia by-production. An industrial NSRC monolith sample of PtRh/Ba/CeO 2 /-Al 2 O 3 type is employed in nearly isothermal laboratory micro-reactor [4]. The
NO x storage/reduction experiments are performed in the temperature range 100-500C in the presence of CO 2 and H 2 O. Hydrogen, CO and C 3 H 6 are examined as
primary reducing agents. Transformation of CO and C 3 H 6 to hydrogen via water gas shift and steam reforming reactions is also studied.
In our spatially distributed NSRC model [3] the following ammonia pathway is considered: NH 3 is formed by the reaction of H 2 with NO x under rich conditions
and it can further react with oxygen and NO x producing N 2 . Considering this scheme with ammonia as an active intermediate of the NO x reduction, a good
agreement with experiments is obtained in terms of the NO x reduction dynamics and NH 3 /N 2 selectivity. Under certain operating conditions, a smaller NH 3 peak
is observed experimentally at the reactor outlet just after the beginning of the regeneration phase (before the main NH 3 peak). We show that this more complex,
double NH 3 peak dynamics can be described by the same spatially distributed model with proper values of kinetic parameters governing the rates of NH 3
formation and decomposition. We also examine possible effects of "slow" and "fast" NO x storage sites on the ammonia formation during the catalyst
regeneration.
Justification for acceptance
The topic is of a high interest in environmental catalysis and fits perfectly to the scope of the conference. We extend current understanding of the problem by an
effective combination of experiments and mathematical modelling, considering spatially distributed reaction and transport of reactants and reaction intermediates.
References
[1] Epling W.S., Yezerets A., Currier N.W., The effects of regeneration conditions on NO x and NH 3 release from NO x storage/reduction catalysts, Applied Catalysis B:
Environmental 74 (2007) 117.
[2] Cumaranatunge L., Mulla S.S., Yezerets A., Currier N.W., Delgass W.N., Ribeiro F.H., Ammonia is a hydrogen carrier in the regeneration of Pt/BaO/Al 2 O 3 NO x traps with
H 2 , Journal of Catalysis 246 (2007) 29.
[3] Koí P., Plát F., Štpánek J., Kubíek M., Marek M. Dynamics and selectivity of NO x reduction in NO x storage catalytic monolith, Catalysis Today (2008) in press,
doi:10.1016/j.cattod.2007.11.023
[4] Monolith, http://www.vscht.cz/monolith (2008)
483 Evidence of WGS activity over precious/transition metal DeNO x catalyst during HC-SCR
J.M. Pigos a , C.J. Brooks a *
a Honda Research Institute USA, Inc. 1381 Kinnear Rd., Suite 116, Columbus Ohio, 43212, USA
*Corresponding author: fax: 614-340-6082, cbrooks@honda-ri.com
Background Metal oxides supported on alumina have shown promise for hydrocarbon selective catalytic reduction (HC-SCR) of NO x to N 2 [1-3]. However,
these systems still suffer from limited activity at low temperature as compared to other catalytic DeNO x systems. Platinum metals at lower temperature have
shown NO x reduction activity using such hydrocarbons as propene and propane [1]. By combining the activity of precious metal systems with the selectivity of
metal oxide systems, it is hoped that a catalyst can be developed that will meet both requirements. In an attempt to better understand the reaction pathway of a
newly discovered precious metal mixed oxide DeNO x catalyst a study using isotopic gases was conducted.
Results In initial investigations, we observed a large reduction in NO x concentration (~ 60 % conversion), when using propene (~ 500 to 5000 ppm) as a
reductant gas with carbon monoxide under steady state DeNO x conditions. The addition of propene produced water in situ (mass signal 18) [4], as expected,
however the presence of hydrogen was also detected (mass signal 2). The H 2 formation can be explained by the water produced from combustion reacting with
carbon monoxide to make hydrogen via the water-gas-shift reaction. In order to determine if the NO reduction was due to additional hydrocarbon reductant, the
addition of water or the generation of hydrogen, isotopic labeling studies were conducted.
To note the effect of water directly on NO x reduction, oxygen-18 labeled water was introduced into the gas stream using a saturator. This was to substitute the
in situ formation of water from hydrocarbon combustion. By using H 18 2 O, the CO 2 produced from WGS (mass 46) could be distinguished from CO 2 produced
via CO oxidation (mass 44). However, since NO 2 also has a mass of 46, it was necessary to use 13 CO to further distinguish the WGS product CO 2 (mass 47).
Upon addition of water, the NO level decreased in the MS (as measured by mass 30) as well as the total NO x concentration on the NO x detector. This result
indicates that water is playing a role in the catalytic reaction to favor the NO x reduction pathway. More interesting, we see an increase in the level of tagged CO 2
(mass 47), which are formed from the isotopic constituents of WGS. The presence of H 2 is also noted consistent with WGS, as well. Conversely, the level of
untagged CO 2 (mass 45) is reduced, indicating a reduction in CO combustion, which allows more CO to be available for NO x reduction.
Justification for acceptance With the proper tagging of key constituents involve in HC-NO x reduction, we see evidence of WGS as a side reaction occurring
and being involved with NO x reduction. Continuing with these studies, we hope to gain more insight into the DeNOx mechanism of these precious-metal mixed
oxide DeNOx catalysts. This will help with the design of catalysts with better NOx reduction activity at low temperature in diesel emission.
References
[1] R. Burch, J.P. Breen and F.C. Meunier, Appl. Catal. B: Environ. 39 (2002) 283, and reference therein.
[2] M.C. Kung and H.H. Kung, Topics in Catal. 28 (2004) 105.
[3] D.E. Sparks, P.M. Patterson, G. Jacobs, N. Dogimont, A. Tackett and M. Crocker, Appl. Catal. B: Environ. 65 (2006) 44.
[4] Z. Liu and S. I. Woo, “Recent Advances in Catalytic DeNO x Science and Technology”, Taylor & Francis Group, LLC.

POSTER
ABSTRACTS
Green Chemistry

101 Negative effect of [bmim][PF 6 ] on the catalytic activity of alcohol dehydrogenase: mechanism and prevention
Xirong Huang
Key Laboratory of Colloid Interface Chemistry of the Education Ministry of China,
Shandong University, Jinan 250100, P. R. China.
Tel: +86-531-88365433, Fax: +86-531-88564464, e-mail: xrhuang@sdu.edu.cn
Background
[bmim][PF 6 ] is a hydrophobic ionic liquid which could be considered as an environmentally friendly solvent for biocatalysis. In pure [bmim][PF 6 ], however,
alcohol dehydrogenase from yeast (YADH) has no catalytic activity. The aim of the present work was 1) to quantitatively study the negative effect of
[bmim][PF 6 ] on the catalytic activity of YADH and the related mechanism, and 2) to made an attempt to lessen the negative effect of [bmim][PF 6 ] on YADH by
microemulsifying [bmim][PF 6 ].
Results
The activity of YADH in the homogeneous solution formed by H 2 O, CH 3 CH 2 OH and [bmim][PF 6 ] decreased rapidly with the increase of the molar fraction of
[bmim][PF 6 ]. The inhibitory effect of [bmim][PF 6 ] on YADH was probably caused by the competition of the imidazole group of [bmim][PF 6 ] with the coenzyme
NAD + for the binding sites on YADH. In a water-in-[bmim][PF 6 ] microemulsion, YADH was catalytically active due to the formation of the interfacial membrane
of the nonionic surfactant TritonX-100, which separated YADH from [bmim][PF 6 ] and avoided the direct inactivation of [bmim][PF 6 ] on YADH. Under the
optimum conditions, the activity of YADH was as high as 51 mol·L -1·min -1 .
Justification for acceptance
To the best of my knowledge, this paper is the first report of this kind. It could arouse the interest of a large audience who try to improve the catalytic
performance of YADH in [bmim][PF 6 ].
103 Ullmann coupling reaction of chlorobenzene over a novel nanoporous Pd/SiO 2 -C catalyst in aqueous media
Haiyan Wang and Ying Wan*
Department of Chemistry, Shanghai Normal University, Shanghai 200234, P. R. China
*Corresponding author. Tel: +86 21 64322516, Fax : +86 21 64322511, e-mail: ywan@shnu.edu.cn
Background
Organic reactions in water-containing media have been extensively investigated for the fine and pharmaceutical chemical industries. It is due to the fact that they
offer the possibility of providing environmentally benign reaction conditions by reducing the burden of the organic solvent disposal.[] Therefore, developing new
catalysts that allow the reactions conducted in aqueous media is important for both economical and environmental concerns.
Results
In this paper, we report the use of mesoporous carbon-silica nanocomposite as a novel kind of catalyst supports for organic reactions in water-containing media,
and the comparison with active carbon and mesoporous silica SBA-15. The Ullmann coupling reaction of chlorobenzene to biphenyls is chosen as an example,
which is of significance to produce various agrochemicals and pharmaceuticals. Mesoporous carbon-silica nanocomposites display a unique hybrid nature that is
inherited from the homogenously distributed carbon and silica components, and a uniform pore-size distribution without obvious pore blockage. The carbonsilica
support has the ability to selectively adsorb a large amount of organic molecules containing benzene ring in aqueous solution, and in turn, the
Pd/mesoporous carbon-silica catalyst exhibits high catalytic property in the Ullmann coupling reaction. The yield of biphenyl can reach as high as 56% at 30 ºC.
As such we envision that this kind of unique hybrid inorganic/organic frameworks.
Justification for acceptance
Chlorobenzene is cheaper and more common than iodobenzene and bromobenzene, being more valuable in the coupling reaction. Such reactions are usually
carried out in the organic solvent such as N, N-dimethylformate or toluene. The hybrid mesoporous carbon-silica support shows good catalytic properties for the
Coupling reaction in aqueous solution and is expected to find wide applications in environmental benign catalysis.
References
[1] C. J. Li, Chem. Rev., 105 (2005) 3095.
[2] Y. Wan, D. Q. Zhang, Y. P. Zhai, C. M. Feng, J. Chen, H. X. Li, Chem.-Asian J., 2 (2007) 875.

104 Periodic Mesoporous Organosilicas: A Kind of Hybrid Supports for Water-Mediated Reaction
Ying Wan*
Department of Chemistry, Shanghai Normal University, Shanghai 200234, P. R. China
*Corresponding author. Tel: +86 21 64322516, Fax : +86 21 64322511, e-mail: ywan@shnu.edu.cn
Background
Periodic mesoporous organosilicas (PMOs), which were firstly reported in 1999, are synthesized by replacing the precursor of tetraethoxysilane (TEOS) with
bridged organosilsequioxane through the surfactant self-assembly approach analogous to that used in the preparation of ordered mesoporous silicates. While
much has been known on the synthesis of PMOs, the applications that exploited their hybrid nature are limited.
Results
Hybrid periodic mesoporous organosilicas Ph-PMOs with phenylene moieties embedding inside silica matrix were used as a heterogeneous catalyst for the
Ullmann coupling reaction in water. Mesoporous Ph-PMO supports and Pd/Ph-PMO catalysts possess highly ordered 2D hexagonal mesostructure and covalently
bonded organic-inorganic (all Si atoms are bonded with carbon) hybrid frameworks. In the Ullmann coupling reaction of iodobenzene in water, the yield of
biphenyl is 94%, 74% and 34% for palladium supported Ph-PMO, Ph-MCM-41 and MCM-41 catalysts, respectively. The selectivity to biphenyl can reach 91%
for the coupling of boromobenzene on the palladium supported Ph-PMO catalyst. This data is much higher than that for Pd/Ph-MCM-41 (19%) and Pd/MCM-41
(0%), although the conversion of bromobenzene on the two catalysts is similar to that on Pd/Ph-PMO. The large difference in the selectivity can be attributed to
the surface hydrophobicity which was evaluated by the adsorption isotherms of water and toluene. Ph-PMO has the most hydrophobic surface, and in turn,
selectively adsorbs the reactant haloaryls from the aqueous solution. Water transfer inside the mesochannels is restricted. The coupling reaction of bromobenzene
is improved.
Justification for acceptance
This study is very important for the understanding on the effect of hydrophilic/hydrophobic properties of a support on catalysis, and offer a way to enhance the
catalytic performance in the green process, namely the water-mediated organic process.
References
[1] S. Inagaki, S. Guan, Y. Fukushima, T. Ohsuna, and O. Terasaki, J. Am. Chem. Soc., 121 (1999) 9611.
105 Cycloaddition of carbon dioxide to allyl glycidyl ether using immobilized ionic liquid catalyst on hybrid MCM-41
S. Udayakumar, D. W. Park*, M. K. Lee, H. L. Shim and S. W. Park
Division of Chemical Engineering, Pusan National University, Busan 609-735, Korea
*Corresponding author. Tel : +82 51 5102399, Fax : +82 51 5128563, e-mail : dwpark@pusan.ac.kr
Background
Using CO 2 as an environmentally benign, safe, and cheap C 1 building block in synthetic chemistry is a great challenge in “green chemistry”. The coupling
reaction of CO 2 and epoxides to produce valuable cyclic carbonates is of great importance in industry. Recently, the use of ionic liquids as environmentally
benign media for catalytic processes or chemical extraction has become widely recognized and accepted. In the present study, immobilization of ionic liquid
catalyst on hybrid MCM-41 was reported for CO 2 insertion reaction to allyl glycidyl ether(AGE).
Results
Generation of ionic liquids on chloropropyl containing MCM-41 (CP-MS41) via the immobilization of trialkylamines (R 4 Cl-MS41) was attempted. The first step
was a simple condensation under basic conditions yielding CP-MS41 leading sequentially to R 4 Cl-MS41. Hybrid MCM-41 materials were synthesized in alkaline
medium in the presence of cetyltributylammonium bromide (CTABr) as surfactant by one-pot synthesis technique, with large and more uniform pores, higher
surface area, good long-range order, and well distributed functionality in contrast to post-grafting technique. Moreover, this outcome was achieved under milder
and simpler synthesis conditions utilizing less time and fewer materials. A wide variety of CP-MS41 by manipulating the TEOS to 3-chloropropyltriethoxysilane
(ClPTES) ratios were synthesized and characterized by a number of physico-chemical measurements such as XRD, BET, FT-IR, CP 13 C, 29 Si MAS-NMR and
TG/DTG. 29 Si MAS-NMR and FT-IR spectra reveal adduct formation of ionic liquids with chloropropyl groups tethered to the silica surface. The amount of
ClPTES incorporated in the silica framework increased with the ClPTES concentration in the synthesis gel, while the ordering of the mesoporous structure
gradually decreased. The immobilized ionic liquids (IILs) showed good catalytic activity for the cycloaddition of CO 2 to AGE and the reusability.
Justification for acceptance
The immobilized ionic liquid catalyst on this mesoporous hybrid MCM-41 showed good reactivity in the cycloaddition of carbon dioxide to AGE. The catalyst
can be reused up to four consecutive times without any considerable loss of its initial activity and leaching phenomenon. Therefore, this paper concerns three
important subjects of environmental catalysis: ionic liquid as a catalyst, carbon dioxide utilization, and reuse of heterogenized catalysts.

109 H 3 [PMo 12 O 40 ] immobilized on Ionic liquids: A green and recyclable catalytic system for synthesis of 2,4,5-triarylimidazoles using
microwave irradiation
N. Mobarrez a , A. Mirjafari b *
a Faculty of Chemistry, Islamic Azad University North Tehran Branch, PO Box 19585/936, Tehran, Iran. b Pars Molybden Co., Tehran 14385, Iran.
*Corresponding author. Tel.:+98-21-88063917, Fax:+98-21-88061476, email:a.mirjafari@chem.ui.ac.ir
Background
Recently, room-temperature ionic liquids have been extensively evaluated as environmental-friendly or “green” alternatives to VOCs for broad range of industrial
organic synthetic applications [1]. RTILs are the valuable media for the microwave-promoted organic reaction because of their highly polar nature [2].
Heteropoly acids (HPAs) as solid Brønsted acids have many advantages finding economically and environmentally attractive in industrial significance and have
been widely used as acid and oxidation catalysts for organic synthesis. HPAs are found several industrial applications [3].
Results
We have developed a microwave-promoted multi-component synthesis that provides an efficient rout to diverse arrays of 2,4,5-triarylimidazoles with important
biological behavior such as P38 map kinas inhibitor. The generality of this green methodology was demonstrated by microwave-promoted synthesis of a library
of 2,4,5-triarylimidazole compounds 3. The [3+2] cycloaddition reactions were performed by diverse keto-oximes 1 and aldehydes 2 with the green and
recyclable catalytic system (HPMo immobilized on RTILs) under the microwave irradiation conditions and a library 2,4,5-triarylimidazole compounds 3 were
obtained with excellent yields.
R 1
R 1
R 2
1
O
+R 3 CHO
N 2
OH
HPMo/RTILs
MW (150 W)
NH 4 OAc
R 2
N
H
N
3
R 3 ILs= [C 4 mIm][BF 4 ]and[C 4 mIm][NTf 2 ]
Justification for acceptance
H 3 [PMo 12 O 40 ]/RTILs are economically and environmentally benign catalytic systems which are efficient under the microwave irradiation for above-mentioned
reactions. Two RTILs act as “green” solvents and importantly, increase the activity of the catalytic systems dramatically in contrast to HPMo with molecular
solvents. Thus we believe that it is valuable catalytic system for the green, fast and efficient preparation of 2,4,5-triarylimidazoles in a parallel synthesis format
for pharmaceutical industries.
References
[1] N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev. 37 (2008) 123.
[2] N. E. Leadbeater, M. H. Torenius, H. Tye, Comb. Chem. & High Throughput Screening, 7 (2004) 511.
[3] G. D. Yadav, Catalysis Surveys from Asia 9 (2005) 117.
110 Molybdenum carbide catalysts for CO hydrogenation to alcohols
M. Xiang a,b , D. Li a , H. Xiao a,b , J. Zhang a,b , W. Li a , Y. Sun a, *
a
State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, CAS, Taiyuan 030001, P.R. China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, P.R. China
*Corresponding author. Tel: +86-351-2023638, Fax: +86-351-4041153, e-mail: yhsun@sxicc.ac.cn
Background
Considerable interest remains in CO hydrogenation for either the synthesis of hydrocarbons, methanol or higher alcohols. Molybdenum carbide was
potential catalyst due to the high active and flexible selective for CO-H 2 reactions comparable to the noble metals [1]. In present paper, a series of Mo 2 C-based
model catalysts were prepared to study the correlations between the performances and structure of catalysts for Fischer-Tropsch synthesis.
Results
As a new type of catalyst, Mo 2 C was active for CO hydrogenation with the main products of light hydrocarbons and the promoter of alkali resulted in a
remarkably shifting of the selectivity toward alcohols [2]. Moreover, the addition of transition metals (such as Fe, Co, Ni) was found to be able to improve the
catalytic activity and selectivity of C 2 + alcohols. For K/Mo 2 C catalyst, Fe, Co, Ni showed the similar ability of promoting the carbon chain growth, in particular,
for the step of C 1 to C 2 . However, the promotion effects were different with the sequence: Ni >> Co > Fe for the activity and Ni > Co > Fe for the alcohols
selectivity. The apparent activation energies for the alcohols formation decreased over the Ni or Co modified K/Mo 2 C catalysts, whereas Fe caused a slight
increase for methanol and decrease for C 2 -C 4 alcohols.
XRD analysis demonstrated the fresh and the used catalysts had the same bulk structure. However, evident changes took place in surface of catalysts induced
by different reaction conditions according to the in-situ XPS tests. The correlations between catalytic performances and the valence of surface Mo species
indicated that Mo 4+ was responsible for the production of alcohols, whereas the low value of Mo species such as Mo 0 and/or Mo 2+ might explain the high activity
and selectivity towards hydrocarbons.
Justification for acceptance
As activate catalyst for CO hydrogenation, Mo 2 C-based catalysts maybe potential for FT process due to its similar properties of noble metal, sulfur tolerance
and the flexible for catalyst designing. This paper might offer some useful information for the designing and development of the catalysts.
References
[1] J.S. Lee, M. Boudart, Catal. Lett. 20 (1993) 97.
[2] H.C. Woo, K.Y. Park, Y.G. Kim, I.S. Nam, J.S. Chung, J.S. Lee, Appl. Catal. 75 (1991) 267.

115 Synthesis of 2-Cumaranon in the Presence of Lacunary Keggin Structures, [PW 11 MO 40 ] p- ( M= Co, Ni, Cu, Zn ) as Green Catalysts
A. Gharib a , F. F. Bamoharram a , M. Roshani a , M. Jahangir a
Department of Chemistry ,School of Sciences, Azad University khorasan Branch, Mashhad, Iran
e-mail:aligharib5@yahoo.com
Lactons are of interest because of their applications in building up biologically active compounds which exhibit pharmacologically activity[1] and also can be
used for the synthesis of polyesters[2].Many catalytic methods including heterogeneous liquid phase lactonization of diols lactonization of -,w-diols by use of
the sodium bromate–hydrobromic acid system[3]. Most of these catalysts are expensive and the applications of them cause some drawbacks such as
environmental problems, long reaction times and tedious work up procedure.The Keggin-type heteropolyacids and Dawson-type heteropolyacids are the most
important for catalysis and they have been widely used as acid and oxidation catalysts for organic syntheses[4], while a few studies have been published on the
use of lacunary Keggin catalysts. One of the reasons is related to the dual character of such compounds, since keggin type are strong acids and can also act as
efficient oxidants[5].its acid strength depends on the type of addenda and hetero atom,which can be tuned to a suitable catalyst for the acid-catalyzed reactions.
[6].HPAs are environmentally friendly catalysts for organic reactions and syhtesis reactions with HPAs are green and fine for chemical industries.
The lactones five and larger rings are synthesized from related diols using lacunary Keggin catalysts.Our findings indicate that lacunary keggin catalysts render
effective oxidation of 1,2-benzene dimethanol to 2-cumaranone respectively with high yields and excellent selectivity by using hydrogen peroxide.
Heteropolyacids as solid acid catalysts are green with respect to corrosiveness, safety, quantity of waste, and separability and it is well known that the use of
heteropolyacid catalysts for organic synthesis reactions can give a lot of benefits. Heteropolyacids are widely used in variety of acid catalyzed reactions [7].
CH 2
CH 2
OH
HPAs ([PW 11 MO 40 ] P- ),H 2 O 2
OH
O
O +H 2 O
References
[1] R. A. Raphael, P. Ravenscorft, J. Chem. Soc. Perkin Trans. 1 (1988) 1823.
[2] M.Trollasas, J. L. Hedrick, D. Mecerreyes, P. Dubois, R. Jerome, H. Ihre, A. Hult, Macromolecules. 31 (1998) 2756.
[3].S. Kajigaeshi, T. Nakagawa, N. Nagasaki, H. Yamasaki, Bull. Chem. Soc. Jpn. 59 (1986) 747.
[4] Y. Izumi, K. Urabe, M. Onaka, Zeolite, Clay and Heteropoly Acid in Organic Reactions, Kodansha / VCH, Tokyo, 1992.
[5] A. Corma, Chem. Rev. 95 (1995) 559.
[6] T. Okuhara, C. Hu, M. Hashimoto, M. Misono, Bull. Chem.Soc. Jpn. 67 (1994) 1186
[7] T. Okuhara, A. Kasai, M. Misono, Shokubai (Catalyst) 22 (1980) 226.
116 An eco-friendly catalytic route for Conversion of Alcohols to Nitro and Azido Compounds by
Effect of Ultrasound and Heteropolyacids Catalysts
A. Gharib a , F. F. Bamoharram a , M. Roshani a , M. Jahangir a
a Department of Chemistry ,School of Sciences, Azad University khorasan Branch, Mashhad, Iran
e-mail:aligharib5@yahoo.com
Aliphatic nitro compounds are valuable intermediates in organic synthesis [1] and organic chemists devote a great attention to their preparation.Aliphatic nitro
compounds are often prepared from carbenoids [2], carboxylic acid [3], etc.Catalytic nitration of saturated alkanes using nitric acid under mild conditions was described
recently [4].Very frequent method for preparation of aliphatic nitro compounds is oxidation of primary amines with potassium permanganate [5]. Ultrasonic irradiation of
the reaction mixture ROH/NaNO 2 /Heteropolyacids allowed to shorten the reaction time and increase yields of aliphatic nitro compounds.we used from Heteropolyacid
(HPAs),Preyssler anion catalysts and its silica supported as a solid acid or super acid in conversion of alcohols to nitro and azido compounds.Heteropolyacids (HPAs)
are well defined molecular clusters that are remarkable for their molecular and electronic structural diversity and to use in organic synthesis and for fine chemical
industries pharmaceutical, food and flavours[6].The performance of the Preyssler catalyst as pure, mixed addenda and silica supported was compared against known
classical catalyst: sulfuric acid and HPAs,preyssler catalysts are promising solid acids to replace environmentally harmful liquid acid catalysts such as H 2 SO 4 [7].All
different forms of this green solid catalyst can be easily recovered and recycled with retention of their initial structure and activity.
NaNO 2,CH 3COOH,HPAs Catal
R OH CH 2 Cl 2
R NO 2
OH
NaNO 2,CH 3COOH,HPAs Catal
NO 2
+
CH 2 Cl 2
X
X
X
X
X
References
[1] .Pham-Huu, D. P., Petrušová, M., BeMillar, J. N., and Petruš, L., Tetrahedron Lett. 40, 3053 (1999).
[2] . Sitzmann, M. E., Kaplan, L. A., and Angres, I., J. Org.Chem. 42, 1580 (1977).
[3] T. Okuhara, N. Mizuno, M. Misono, Adv. Catal. 41 (1996)113.
[4] .Shinji, I., Nishiwaki, Y., Sakaguchi, S., and Ishii, Y.,Chem. Commun. 2001, 1352.
[5] . Emmons, W. D., J. Am. Chem. Soc. 79, 5528 (1957).
[6] Heravi, M. M.; Rajabzadeh, G.; Bamoharram, F. F.; Seifi, N.J. Mol. Catal. A: Chem., 2006, 256, 238-241.
[7] I.V. Kozhevnikov, Chem. Rev. 98 (1998) 171.
O
C
H
+
O
C O

121 Investigation of CO 2 adsorption on amine-functionalized nanosized MCM-41 support
Linfang Wang, Aiqin Wang , Lei Ma, Tao Zhang*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, CAS, Dalian 116023, China
*Corresponding author. Tel: +86 411 84379015, Fax: +86 411 84691570, e-mail: taozhang@dicp.ac.cn
Background
Recently, the carbon dioxide issue has become the focus of attention because of its green house effect and increasing impact on the climate change. Reducing CO 2
emissions is therefore attracting more and more research interest. Adsorption is one of the promising methods for separating CO 2 from gas mixtures and the
recovered concentrated CO 2 could be used as the starting material for synthetic chemicals. Various adsorbents have been developed so far [1] . In the present work,
we developed a new adsorbent by grafting amines onto a nanosized mesoporous MCM-41 support.
Results
Nanosized MCM-41 support was synthesized according to literature [2] , and the as-synthesized MCM-41 was added in an ethanol solution containing 3-
aminopropyl-triethoxysilane (APTES) and heated at 50 o C for 24h to obtain the APTES-functionalized MCM-41. BET surface area and pore volume were
decreased from 1056 to 656 m 2 /g and from 1.77 to 0.62 cm 3 /g, respectively, upon the surface functionalization. TEM images showed that the particle size of the
MCM-41 was uniform, around 100 nm. CO 2 adsorption was tested using static adsorption equipment. At an adsorption temperature of 25 o C, the CO 2 adsorption
amount was 41.1 and 80 mg/g at its partial pressure of 0.002 and 0.1 MPa, respectively. This result was better than that on the micrometer-sized MCM-41 or
SBA-15 support. By comparing with other adsorbents, such as activated carbon and zeolites, it is found that the amine-functionalized mesoporous support
presented the unique advantages as a CO 2 adsorbent: a large adsorption capacity even at a high adsorption temperature and a very low CO 2 partial pressure, and
the co-presence of H 2 O has no influence on the CO 2 adsorption capacity.
Justification for acceptance
Utilization of CO 2 has become an important global issue due to the significant and continuous rise in atmospheric CO 2 concentrations, and separating CO 2 from
gas mixtures by adsorption is a feasible way to allow further utilization of CO 2 . In this respect, developing an efficient adsorbent is the key.
References
[1] X. Xu, C. Song, J. M. Andresen, B. G. Miller, A. W. Scaroni, Energy & Fuels, 16 (2002) 1463.
[2] Q. Cai, Z. S. Luo, W. Q. Pang, Y. W. Fan, X. H. Chen, F. Z. Cui, Chem. Mater. 13 (2001) 258.
126 Surface mobility and reactivity of supported copper oxide catalysts: Isopropanol decomposition.
K. Lanasri a , K. Bachari 1,2 , D. Halliche 1 , Z. Rassoul 1 , O. Cherifi 1 and A. Saadi 1, *
1. Laboratoire de Chimie du Gaz Naturel, Faculty of chemistry, USTHB, BP32 El-Alia, 16111 Bab-Ezzouar, Algeria..
2. Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques. BP 248,16004 Algiers, Algeria.
* corresponding authors Fax:+ 213 21 24 73 11, e-mail address: adel_saadi@yahoo.fr
Background
Catalytic hydrogenation and dehydrogenation reactions are commonly used in the chemical industry, and such reactions involving oxygenated
compounds are particularly important in the preparation of pharmaceuticals and fine chemicals [1]. Dehydrogenation reactions are typically endothermic and
conversions can be equilibrium controlled; in addition, low H 2 pressures may enhance deactivation due to coking, and a selectivity consideration of
dehydrogenation versus dehydration as well as hydrogenolysis can become important when oxygenates are the reactants.
Results
In the present study, we report the results obtained in the gas phase decomposition of isopropanol over copper oxide (10%) supported on SiO 2 , TiO 2 ,
CeO 2 , ZrO 2 and Al 2 O 3 catalysts. The catalysts were obtained by impregnation and the resulting precursors were dried at 100°C and calcined in air (350°C/3 h).
The solids were characterized by their BET specific area, XRD and reducibility. The catalytic reactions were carried out in a fixed bed glass reactor with 0.2g
samples at atmospheric pressure and in the temperature range :100°C-250°C ( H 2 per-reduction : 350°C). The specific area of the catalysts increased with that of
the corresponding supports and was in the range of 40–130 m 2 g -1 . However, this range of specific area is lower than that of the supports (60-200 m 2 g -1 ). The XRD
spectra showed the characteristic bands of the nickel phase and support. The pattern for the supports was that of crystallised materials with well defined bands
except for the amorphous SiO 2 support.
As a general trend, Acetone appeared as a low reaction temperature product rather favoured on CuO-CeO 2 and CuO-ZrO 2 (60%- 90% of selectivity). The
CuO-Al 2 O 3 catalyst did not formed the acetone product in the gas phase at this temperature but only from above 110 °C (50% of selectivity) as a consequence of
adsorption phenomena. Propylene product appeared as a product of mean reaction temperature (110°C) favoured on CuO-TiO 2 and CuO-SiO 2 (80% of
selectivity), the CuO-Al 2 O 3 catalyst was the less active in this reaction (10% of selectivity only).
Justification for acceptance
Although studied and utilized to a much lesser extent than hydrogenation reactions, dehydrogenation reactions involving organic compounds can also play an
important role in the production of fine chemicals (Catalysis in a sustainable fine chemical industry).
References
[1] R.M.Rioux, M.A.Vannice, J.Catal. 216 (2003) 362-376.

129 Study of the dimerization of 1-pentene catalyzed by ion-exchange resins
M. Cadenas, R. Bringué, J. Tejero, M. Iborra, C. Fité, J.F. Izquierdo and F. Cunill *
Chemical Engineering Department, University Barcelona, Barcelona 08028, Spain.
*Corresponding author. Tel: +34934021304, Fax : +34 934021291, e-mail: fcunill@ub.edu
Background The ion-exchange resins play a key role in the development of safer and non-waste producing alternatives compared with homogeneous catalysis.
They have been used commercially as solid acid catalysts in many areas. Oligomerización of olefins is an emerging area in this field. Up to date, studies on light
olefins oligomerization have been performed mainly with homogeneous mineral acids and various zeolites as catalysts. However, these catalysts are not very
promising for industrial purpose due to reaction media highly corrosive and low selectivities, respectively. Some references can be found for branched olefins
oligomerization catalyzed by ion exchange resins [1] but only a few ones for linear olefins oligomerization with more than four carbon atoms [2].
Results Dimerization of 1 pentene was carried out successfully catalysed by macroporous acid-exchange resins. 1-pentene conversion was almost complete with
the majority of the tested resins (Amberlyst 15, 16, 35, 36, 39, 46 and Purolite CT-175, CT-252, CT-275, CT-276) at 373 K after 6 h of reaction. Selectivity
values ranged between 76 and 98%, depending on the used resin. Fifteen dimer isomers were detected, 3,4-diethyl-3-hexene, 2-methyl-3ethyl-2-heptene and 2,3-
dimethyl-2-octene being some of the dimers found. By using the same resin weight, the highest selectivity to dimers was showed by Amberlyst 15 and the one
that produced the highest amount of trimers was Purolite CT252. Trimers presence was detected for all the resins, except for Amberlyst 35. Amberlyst 46, which
has the lowest acid capacity but all the active sites are located at the surface, appears to be very promising for dimers production at long reaction time, with low
trimers formation. Temperature effect was tested with Amberlyst 15: dimers selectivity increased at lower temperature. The most plausible reaction mechanism is
the following one: the 1-pentene isomerizated quickly to 2-pentene, and this dimerizated and then, trimerizated.
Justification for acceptance FCC C5 compounds provide the highest contribution of olefins in gasoline and these olefins are responsible for more than 90% of
the total of gasoline’s ozone formation potential [3]. As a result, C5 olefins content has to be reduced and, at the same time, to form higher compounds to be
added to gasoline and diesel fuel of high quality that adapt to the regulations and current environmental legislations. Dimerization and trimerization reactions
catalyzed by macroporous ion exchange resins at mild temperature are an interesting way to obtain these purposes.
References :
[1] N.F. Shah, M.M.Sharma, Reactive Polymers 19 (1993) 181.
[2] M. Marchiona, M.D. Girolamo, R. Patrini, Catal. Today 65 (2001) 397.
[3] K.L.Rock, T.Cardenas, L.T.Fornoff, Fuel Reformulation (November/December) (1992) 42
134 Microwave-enhanced rapid one-pot deprotection, esterification and silylation of MOM- and EOM-ethers in
[Hmim]HSO 4 as a Brönsted acid ionic liquid
A. Mirjafari*, I. Mohammadpoor-Baltork, M. Moghdam, A. R. Khosropour, V. Mirkhani, S. Tangestaninejad
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan 81746-7344, Iran.
*Corresponding author. Tel.:+98-311-7932705, Fax:+98-311-6689732, email:a.mirjafari@chem.ui.ac.ir
Background
Room-temperature ionic liquids are attracting interest as green/sustainable reaction media in many industrial organic synthetic applications [1]. Ionic liquids have
been developed for task-specific purposes and recently there have been increasing efforts to utilize these TSILs as active catalysts for the organic transformations
[2].
Methoxymethyl (MOM) and ethoxymethyl (EOM) ethers, acetates and trimethylsilyl ethers are the most versatile protecting forms of the hydroxyl groups. Onepot
conversion of these acid-sensitive hydroxyl-protective groups into the next one plays the critical role in successful synthesis of multi-functional complex
molecules [3].
Results
An efficient protocol using [hmim]HSO 4 as a cheap and stable Brönsted acid task-specific ionic liquid used as a catalyst and reaction medium for deprotection of
MOM- and EOM-ethers to their alcohols and furthermore, one-pot interconversion of them to their acetates and trimethylsilyl ethers under microwave
irradiations and traditional conditions was developed. A variety of MOM- or EOM-ethers such as substituted benzilic and aliphatic ones were employed to
investigate the scope and generality of these processes. The short reaction time, easy synthetic procedure, free of toxic organic solvent, simple work-up in
isolation of the products in high purity, and importantly, recycability of the catalyst are features of this new procedure.
Justification for acceptance
Use of [Hmim]HSO 4 as a powerful Brönsted acidic room temperature ionic liquid (BARTIL) helps to develop a green system that provides deprotection of
MOM- and EOM-ethers and their transformation to corresponding acetate and TMS-ether groups by one recyclable reagent, without the use of corrosive
substances and eliminating waste formation. Thus, we believe that [Hmim]HSO 4 is an economically and environmentally benign solvo-catalytic system for acidcatalyzed
deprotection and interconversion reactions of MOM- and EOM-ethers.
References
[1] N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev. 37 (2008) 123.
[2] V. I. Pârvulescu, C. Hardacre, Chem. Rev. 107 (2007) 2615.
[3] T. W. Green, P. G. M. Wuts, Protective Groups in Organic Chemistry, John Wiley and Sons: New York, 1999.

138 Preparation, characterisation and activity testing of Gold Catalysts supported on Single Walled Carbon Nanotubes
Anne E Shanahan ab* , James A Sullivan c , Mary McNamara a , Hugh J Byrne b
a
School of Chemical and Pharmaceutical Sciences, Dublin Institute of Technology, Kevin St.
b
FOCAS Institute, Dublin Institute of Technology, Camden Row, Dublin 8.
c School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4.
* Corresponding author. Tel: +353-1-4027905 Fax: +353-1-4027904 Email: anne.shanahan@dit.ie
Due to the inherent reactivity of gold nanoparticles (d Au = 1-10nm), gold catalysts are being considered for reactions of environmental interest such as the
selective oxidation of CO, the synthesis of fine chemicals and also various liquid-phase selective oxidations, e.g. the oxidation of 1-Phenylethanol to
Acetophenone [1] and the oxidation of glycerol to glyceric acid [2, 3].
The catalytic potential of Au/C has been investigated previously in the latter reaction. In this work single walled carbon nanotubes (SWNTs) as well as
amorphous carbon in aqueous suspensions are used as supports for the Au nanoparticles. The catalysts and supports are characterised by XRD, BET, TEM, and
AAS. Their activity and selectivity of the catalysts in promoting the aerobic oxidation of 1-Phenylethanol is monitored using FT-IR analysis.
TEM shows that the untreated SWNTs exist as bundled aggregates with gold nanoparticles (with an average diameter of ~4nm) being clearly visible on the
surface. Comparison of the catalytic activity of Au/SWNT and Au/C in the oxidation of 1-Phenylethanol shows that the % conversion to Acetophenone as a
function of time using SWNTs as supports is significantly higher than in the case of the amorphous C supported material.
The search for clean oxidation processes is currently a topic of some interest because oxidation reactions are generally not “green”, (e.g. using permanganate or
acidified dichromate). One alternative is heterogeneously catalysed aerobic oxidations. O 2 is an ideal reagent as H 2 O is the only by-product in the oxidation of
alcohols to their corresponding aldehydes or ketones.
References:
[1] A. Abad, C. Almela, A. Corma, H. Garcia, Tetrahedron, 62, (2006), 6666-6672
[2] S. Demirel, K. Lehnert, M. Lucas, P. Claus, Appl. Catal. B, 70, (2007), 637-643
[3] F. Porti, L. Prati, J. Catal., 224, (2004), 397-403
165 Sulfonic acid functionalized mesoporous organosilicas as novel solid acid for catalysis
Jian Liu, Jie Yang, Congming Li, Qihua Yang*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
*Corresponding author. Tel: +86 411 84379552, Fax: +86 411 84694447, e-mail: yangqh@dicp.ac.cn
Background
The synthesis of solid acid for catalysis has attracted much research attention nowadays because it can reduce the environmental pollution and the corrosion of
the equipment caused by the homogeneous acid catalyzed process. Mesoporous materials functionalized with sulfonic acid (MM-SO 3 H) are efficient catalysts for
acid-catalyzed reactions because of its high surface area and large pore size. Compared with mesoporous silicas, the periodic mesoporous organosilicas (PMOs)
have unique features, such as the tunable physical/chemical properties by choosing different kinds of organic group bridging in the framework [1]. The PMOs
open new opportunities for the design and synthesis of novel solid catalysts. Here, we report the synthesis of sulfonic acid functionalized PMOs with different
framework compositions and its application as solid acid in the dehydration of 1-butanol and hydration of propylene oxide.
Results
BnT-SO 3 H with different fraction of ethane moiety in the pore wall was synthesized by one step co-condensation of 1,2-bis(trimethoxysilyl)ethane (BTME),
tetramethoxysilane (TMOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) under acidic medium in the presence of triblock copolymer pluronic P123.
Structural characterizations show that all materials have ordered hexagonal mesoporous structure with large pore diameter (7-9 nm). The mesoporous solid acids
can adsorb both water and hexane due to the existence of surface hydroxyl groups, propyl sulfonic acid group, and the ethane moiety. The catalytic data of the
dehydration of 1-butanol over different materials show that all materials containing sulfonic acid group are active for the dehydration of 1-butanol. The catalytic
activity of B 25 T-SO 3 H-24 is comparable to that of Nafion ® NR50 and much higher than B 0 T-SO 3 H-24 (with no ethane moiety in the framework). In the hydration
of propylene oxide (PO), the selectivity of glycol and conversion of PO increases with the content of ethane moiety in the framework increasing. The catalytic
activity is in the following order: B 75 T-SO 3 H-39 B 50 T-SO 3 H-39 B 25 T-SO 3 H-39. Catalytic tests show that the mesoporous organosilicas functionalized with
sulfonic acid are efficient solid acid catalysts and exhibit advantages over conventional solid acids in water involved reaction.
Justification for acceptance
The acid catalyzed reactions are often used in industry for the production of fine chemicals. It is urgent to replace homogeneous process by heterogeneous one in
view of environmental protection. Therefore, this work should be accepted.
References
[1] S. Fujita, S. Inagaki, Chem. Mater. 20 (2008) 891.

167 Molybdenum carbide catalysts for CO hydrogenation to alcohols
M. Xiang a,b , D. Li a , H. Xiao a,b , J. Zhang a,b , W. Li a , Y. Sun a, *
a
State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, CAS, Taiyuan 030001, P.R. China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, P.R. China
*Corresponding author. Tel: +86-351-2023638, Fax: +86-351-4041153, e-mail: yhsun@sxicc.ac.cn
Background
Considerable interest remains in CO hydrogenation for either the synthesis of hydrocarbons, methanol or higher alcohols. Molybdenum carbide was
potential catalyst due to the high active and flexible selective for CO-H 2 reactions comparable to the noble metals [1]. In present paper, a series of Mo 2 C-based
model catalysts were prepared to study the correlations between the performances and structure of catalysts for Fischer-Tropsch synthesis.
Results
As a new type of catalyst, Mo 2 C was active for CO hydrogenation with the main products of light hydrocarbons and the promoter of alkali resulted in a
remarkably shifting of the selectivity toward alcohols [2]. Moreover, the addition of transition metals (such as Fe, Co, Ni) was found to be able to improve the
catalytic activity and selectivity of C + 2 alcohols. For K/Mo 2 C catalyst, Fe, Co, Ni showed the similar ability of promoting the carbon chain growth, in particular,
for the step of C 1 to C 2 . However, the promotion effects were different with the sequence: Ni >> Co > Fe for the activity and Ni > Co > Fe for the alcohols
selectivity. The apparent activation energies for the alcohols formation decreased over the Ni or Co modified K/Mo 2 C catalysts, whereas Fe caused a slight
increase for methanol and decrease for C 2 -C 4 alcohols.
XRD analysis demonstrated the fresh and the used catalysts had the same bulk structure. However, evident changes took place in surface of catalysts induced
by different reaction conditions according to the in-situ XPS tests. The correlations between catalytic performances and the valence of surface Mo species
indicated that Mo 4+ was responsible for the production of alcohols, whereas the low value of Mo species such as Mo 0 and/or Mo 2+ might explain the high activity
and selectivity towards hydrocarbons.
Justification for acceptance
As activate catalyst for CO hydrogenation, Mo 2 C-based catalysts maybe potential for FT process due to its similar properties of noble metal, sulfur tolerance
and the flexible for catalyst designing. This paper might offer some useful information for the designing and development of the catalysts.
References
[1] J.S. Lee, M. Boudart, Catal. Lett. 20 (1993) 97.
[2] H.C. Woo, K.Y. Park, Y.G. Kim, I.S. Nam, J.S. Chung, J.S. Lee, Appl. Catal. 75 (1991) 267.
174 Anion-modified Mg-Al mixed oxides as solid base catalysts for the alcoholysis of propylene oxide
G. Wu a,b , X. Wang a,b , J. Li a , F. Xiao a , W. Wei a, * Y. Sun a, *
a
State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, CAS, Taiyuan 030001, P.R. China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, P.R. China
*Corresponding author. Tel: +86-351-4049612, Fax: +86-351-4041153, e-mail: yhsun@sxicc.ac.cn weiwei@sxicc.ac.cn
Background
In recent years, the Mg–Al mixed oxides calcined from HT-CO 3 were considered as promising solid base catalysts owing to the advantages of high surface
area and tunable basicity. In order to further improve their catalytic performance, the Mg–Al mixed oxides modified by various cations have been developed
since 1991 [1]. However, there are few reports on the anion-modified Mg-Al mixed oxides. Here we reported a now route to the preparation of anion-modified
mixed oxides and their application in the alcoholysis of propylene oxide.
Results
Mg-Al hydrotalcite (HT) intercalated by halogen anions (F - , Cl - , Br - , I - ) and their calcined derivations were prepared and characterized by XRD. It was found
that F - intercalated hydrotalcite (HT-F) was transformed into fluorine-modified Mg-Al mixed oxides (F/Mg x (Al)O) at 673 K, while HT-Cl and HT-Br was
converted into pure Mg-Al mixed oxides. Noticeably, HT-I still retained its lamellar structure before 1073 K. In the reaction of propylene oxide and methanol [2],
the catalytic performance of the above materials was in the following sequence: HT-F > HT-I > HT-Br HT-Cl Mg(Al)O. F/Mg x (Al)O exhibited the optimal
PO conversion of 94.4 % with 86.6% of the selectivity to 1-methoxy-2-propanol (PPM). At the same time, it was found that their catalytic performance was
closely corrected with their acid-base properties, location of the active sites, texture and structure.
Justification for acceptance
As solid base catalysis for the alcoholysis of propylene oxide, the fluorine-modified Mg-Al mixed oxides showed much higher catalytic performance than
the pure Mg-Al mixed oxides duo to the improved basicity. We expect our work could be helpful for the development of high efficient and environmentally
benign catalytic materials for the base-catalytic reactions.
References:
[1] R.J. Davis, E.G. Derouane, Nature 349 (1991) 313-314.
[2] G. Wu, X. Wang, B. Chen, J. Li, N. Zhao, W. Wei, Y. Sun, Appl. Catal. A 329 (2007) 106-111.

175 Efficient selective oxidation of benzyl alcohol with hydrogen peroxide catalyzed
by chromium Schiff base complexes immobilized on MCM-41
Xiaoli Wang a,b , Gongde Wu a,b , Junping Li a , Fukui Xiao a , Wei Wei a , and Yuhan Sun a *
a
State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, CAS, Taiyuan 030001, P.R. China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100049, P.R. China
*Corresponding author. Tel: +86-351-4049612, Fax: +86-351-4041153, e-mail: yhsun@sxicc.ac.cn
Background
Catalytic oxidation of benzyl alcohol (BzOH) with hydrogen peroxide to benzaldehyde (BzH) is a widely investigated reaction as it provides chlorine-free
BzH required in perfumery and pharmaceutical industries. Among the known catalytic methods, heterogenised transition metal Schiff base complexes in
resemblance of enzymatic oxidation are eye-catching for their more accessible synthesis conditions and versatile coordination structures [1]. Here we reported the
efficient selective oxidation of BzOH with 30% H 2 O 2 catalyzed by a series of chromium complexes immobilized on MCM-41. An in-depth study on the catalytic
performance of immobilized complexes and their homogeneous analogues was carried out. Moreover, the roles of different ligands in the structures and
performance of immobilized complexes were also discussed in detail.
Results
Elemental analysis and 1 H MAS NMR, 13 C CP/MAS NMR, FTIR and UV spectra showed that the five typical homogeneous complexes had been
successfully immobilized on MCM-41. The powder XRD patterns and N 2 sorption isotherms displayed that the textural structures of immobilized complexes
were related to the used ligands. These immobilized complexes were effective catalysts and all exhibited much higher catalytic performance than their
corresponding homogeneous analogues. Simultaneously, the catalytic performance of immobilized complexes was also found to depend on the Schiff base
ligands. Under the optimal reaction conditions, the highest conversion of BzOH reached 45.5% with 100% of the selectivity to BzH.
Justification for acceptance
The catalytic performance of immobilized Schiff base complexes in comparison with their corresponding homogeneous analogues has still been
controversial among academia. Moreover, the effect of different Schiff base ligands on the textural structures and catalytic performance of immobilized
complexes was rarely dealt with. This paper discuss detailedly the above two problems which are of significance for high effective heterogeneous catalyst design.
References
[1] X.L. Wang, G.D. Wu, J.P. Li, N. Zhao, W. Wei, Y.H. Sun. J Mol Catal A, 276 (2007) 86.
176 One-Step Method of Direct Synthesis of Dipropylene Glycol over Efficient Super Basic Catalyst
Z. Liu a,b , G. Wu a,b , N. Sun a,b , J. Li a , N. Zhao a F. Xiao a , W.Wei a,* Y. Sun a,*
a
State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, CAS, Taiyuan 030001, P.R. China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100039, P.R. China
*Corresponding author. Tel: +86-351-4049612, Fax: +86-351-4041153, e-mail: yhsun@sxicc.ac.cn weiwei@sxicc.ac.cn
Background
Dipropylene glycol is a component of many commercial products, such as air fresheners, antifreeze, cosmetic products and plastics [1]. The technical-grade
DPG is prepared by the reaction of PO and propylene glycol with 85% sulfuric acid as catalyst. However, homogeneous catalysts give rise to the problems of
products separation and catalysts recycle. Thus, in recent years solid catalysts have attracted extensive attention owning to their less corrosiveness, easy
separation and reuse. In our present work, we firstly use one-step method to prepare DPG from propylene oxide (PO) and deionized water, and found that solid
catalyst Na-ZrO 2 was an efficient catalyst for this reaction.
Results
The catalytic performance and textural properties of many solid bases (Al 2 O 3 , MgO, CaO-ZrO 2 , Na-ZrO 2 ) were investigated [2]. And their base was
characterized by CO 2 -TPD. It was found that both the PO conversion and DPG selectivity were improved with the increased base strength and specific area of
catalysts. Na-ZrO 2 , as a super basic catalyst, exhibited the highest active for the synthesis of dipropylene glycol (DPG) from PO and deionized water. The optimal
PO conversion and DPG selectivity reached 99.9% and 41.3%, respectively. This might be attributed to the higher charge density of O 2- with Na + than that of O 2-
with Ca + , which led to the increase in basic strength of the material.
Justification for acceptance
Solid base catalysts played a decisive role in a number of reactions essential for fine chemical synthesis duo to their advantages of low pollution, easier
separation and recovery. In the present work, we firstly use one-step method to prepare DPG from PO and distilled water over a super solid basic catalyst of Na-
ZrO 2 , which would break a new path for the green production of DPG.
References:
[1] M. J. Hootha, R. A. Herberta, J. K. Hasemana, D. P. Orzecha, J. D. Johnsonb, J. R. Buchera Toxicology. 204 (2004) 123–140.
[2] S. Liu, S. Huang, L. Guan, J. Li, N. Zhao, W. Wei, Y. Sun Micropor. Mesopor.Mat. 102 (2007) 304–309.

178 Development of new Ce/La/Zr Super Acid Catalysts
H. Stephenson a , * , H. Bradshaw a , C. J. Butler a , D. Harris a , R. Brown b and H. Williams b
a
MEL Chemicals, PO Box 6, Lumns Lane, Swinton, Manchester M27 8LS, England.
b
University of Huddersfield, Centre for Applied Catalysis, Huddersfield, HD1 3D, England.
*Tel: +44 161 911 1179, Fax: +44 161 911 1052, e-mail: hazel.stephenson@melchemicals.com
Background
Zirconium oxide doped with sulphate and tungstate are known to be solid acids, however it has recently come to light that ceria and lanthana doped zirconium
oxide may also exhibit strong acid sites as well as the expected basic sites. [1] This work investigates dependence of strong acid sites on calcination and activation
conditions and looks at how this acidity can be used in real applications via catalyst testing, the reactions being specifically chosen to give information to the type
and strength of acid sites.
Results
Oxide with varying Ce:La:Zr were prepared by a range of different commercialised processes. [2] Samples were calcined at temperatures between 300-1200C
using ramp rate 1C/min and dwell of 3hours in static air. The samples were then activated in situ at temperature 200- 825C under dried helium flow at 5ml min -
1 . Small pulses (typically 1 ml) of the probe gas (1%NH 3 in He) were injected at regular intervals into the carrier gas stream. The net amount of ammonia
irreversibly adsorbed from each pulse was determined from the MS signal. This data was combined with the enthalpies of ammonia adsorption for each pulse,
measured in a flow-through calorimeter, to give a H o ads(NH 3 ) vs NH 3 adsorbed profile which could be interpreted in terms of an acid site strength distribution
profile for the catalyst sample.
The reactions chosen for catalyst testing are the gas phase dehydration/dehydrogenation of 2-propanol and 3-methyl-2-pentanol for which product distribution
can give an indication of both acidic and basic sites, and their relative strengths.
Further characterisation including surface area, porosity, XRD and particle size will also be presented. We are making efforts to explain and rationalise the
behavior of the materials in terms of suitable models.
Justification for acceptance
The paper presents evidence of how fine tuning the composition and activation conditions of modified and doped zirconia catalysts can have dramatic effects of
the catalytic properties of the materials. This will be highly significant in the development of both automobile catalysts and industrial catalysts designed for high
temperature operation.
References
[1] M.G. Cutrufello, I. Ferino, R. Monaci, E. Rombi, V. Solinas, Topics in Catalysis, 19 (2002)
[2] Y. Takao, C. Norman, G. Edwards, I. Chisem, WO/03/037506
180 Ceria supported group IB metal catalysts for oxidation reactions of environmental interest
S. Scirè *, C. Crisafulli, P.M. Riccobene
Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, 95125 Catania, Italy.
* Corresponding author. Tel: +390957385112, Fax: +39095580138, e-mail address: sscire@unict.it
Background
Ceria-based catalysts are widely used in redox reactions due to the high oxygen storage capacity of ceria. Au/ceria has been reported to be among the most active systems
for VOC combustion [1] and preferential oxidation of CO (PROX) [2]. Cu/ceria catalysts were also found promising both for PROX [3] and water gas shift [4]. We
report a study on IB metal/ceria catalysts in two reactions of environmental interest, PROX and VOC combustion, focusing on the effect of preparation and pretreatment
methods on catalytic performance.
Results
VOC combustion and PROX were studied on IB metal/ceria catalysts prepared by deposition-precipitation (DP) or coprecipitation (CP). Catalytic runs were carried out
in the gas phase in a flow reactor using a feed of CO, O 2 , H 2 (1:1:98) for PROX and 0.7 vol.% VOC (methanol, 2-propanol, acetone, toluene) and 10 vol.% O 2 , the rest
being He for VOC combustion. Samples were characterized by TPR, TEM, XRD, XPS, FTIR.
The VOC oxidation activity of catalysts was in the order Au/CeO 2 Ag/CeO 2 > Cu/CeO 2 >> CeO 2 . With regard to PROX reaction the order of activity in terms of O 2
conversion was the same as above whereas as CO oxidation to CO 2 was Au/CeO 2 > Cu/CeO 2 >> Ag/CeO 2 > CeO 2 . On Au samples the selectivity (defined as the ratio of
O 2 consumption for CO oxidation to the total O 2 consumption), very high at low temperature, sharply decreased at T>10°C. On Cu samples the selectivity drop occurred
at T>110°C. On Ag samples the selectivity was always low ( Cu/CeO 2 > CeO 2 . It was suggested
that IB metals induce a lattice distorsion causing a decrease in the strength of Ce-O bonds nearby the IB atom, a higher atomic radius of the IB metal resulting in a larger
extent of this effect. Considering that both investigated reactions occur through a Mars-van Krevelen mechanism, the oxygen reactivity explains the activity trend
observed for VOC combustion. The different behaviour found for PROX was justified with the different CO activation ability of the IB metal (Au>Cu>Ag). The
influence of preparation and pretreatment techniques on catalytic performances was rationalized in terms of different particle size and amount of active species located on
the catalytic surface.
References
[1] S. Minicò, S. Scirè, C. Crisafulli, C. Satriano, A. Pistone, Appl. Catal. B 40 (2003) 43.
[2] W. Deng, J. De Jesus, H. Saltsburg, M. Flytzani-Stephanopoulos, Appl. Catal. A 291 (2005) 126.
[3] G. Avgouropoulos, T. Ioannides, Appl. Catal. A 244 (2003)155.
[4] T. Tabakova, F. Boccuzzi, M. Manzoli, J.W. Sobczak, V. Idakiev, A. Andreeva, Appl. Catal. A 298 (2006) 127.

184 Urea obtaining by and ammonia interaction
A.R. Elman* and A.E. Batov
Rostkhim Ltd., 38, Shosse Entuziastov, 111123, Moscow, Russia.
*Corresponding author. Tel: +7(495) 916-60-60, e-mail: alexandr@spektr-ttt.ru
It is well known that the industrial process of urea production is based on 2 and ammonia interaction. Very rigorous conditions (180-230 and 120-
250 at) make the process unacceptable for obtaining of urea small quantities, for example for synthesis of urea labeled by carbon and nitrogen isotopes. However
it is known [1, 2] that urea may be prepared by carbon monoxide and ammonia interaction in the presence of selenium. This reaction runs under very mild
conditions (r.t., 1 at) [1] with stoichiometric selenium quantities but oxygen addition provides catalytic course of the reaction under elevated pressure (up to 50 at)
[2, 3].
14
In the present work the urea formation from and NH 3 has been studied under low pressure in the presence
12
of selenium powder and the reaction conditions have been selected for catalytic course of the process. In the
10
experiments conducted in mild conditions (40 , 14 at ) with Se stoichiometric quantities in THF gas uptake 8
finished during 1 h. The urea yield calculated on Se was increased from 68.6 % up to nearly 100 % by the choice of 6
solvent, reaction conditions and the reagents ratios. Using IR spectroscopy analysis it has been showed that only 4
urea (without by-products) forms from CO and NH 2
3 during the reaction (mp 131-133 ; , sm -1 : 3494 m., 3389 m.,
1691 s., 1610 s., 1030 v.s., 919 s.).
Oxygen addition allows to reactivate Se that was added in deficiency as compared to another reagents
Pressure, at
2
2 2
0
0 2 4 6 8 10 12
Time, h
(Se:NH 3 :CO: 2 =1:7.5:11.7:3) and to run the process by catalytic manner (TON=5.5; eq. 1). Specific catalyst activity increases by the decrease of Se loading
(Se:NH 3 :CO: 2 =1:70:109:41) and also by THF replacing to methanol. Repeated oxygen addition after the reaction completion (see figure below) allowed to
achieve TON up to 110; average specific catalyst activity was 458 (g•h) -1 .
Se
CO + 2NH 3 + 1/2 2 NH 2 CONH 2 + H 2 (1)
So, the reaction of urea obtaining from and NH 3 in the liquid phase catalyzed by Se runs in mild conditions with good rates and noticeable catalyst
activity. The high quality urea without by-products forms during the reaction. This method is convenient for small quantities urea obtaining, but it may be
considered as alternative at the development of new urea manufacturing process from exhaust industrial gas emissions.
References
[1] S. Tsutsumi, N. Sonoda, GB Pat. 1,275,702 (1972).
[2] J.-J. Herman, A. Lecloux, US Pat. 4,801,744 (1989).
[3] H.S. Kim, Y.J. Kim, H. Lee, K.Y. Park, C. Lee, C.S. Chin, Angew. Chem. Int. Ed. 41 (2002) 4300-4303.
185 Decarbonylation reaction in the course of Pd-catalyzed olefin hydrocarboxylation
A.R. Elman a *, .. Batov a , Yu.G. Noskov b , V.M. Nosova c and A.V. Kisin c
a Rostkhim Ltd., 38, Shosse Entuziastov, 111123, Moscow, Russia.
b YRD-Centre, 55/1, build. 1, Leninskii Prospekt, 119333, Moscow, Russia.
c GNIIHTEOS, 38, Shosse Entuziastov, 111123, Moscow, Russia.
*Corresponding author. Tel: +7(495) 916-60-60, e-mail: alexandr@spektr-ttt.ru
Catalytic olefin hydrocarboxylation is one of the most effective green processes for high quality carboxylic acids production based on CO as alternative
raw material [1]. It is known, however [2], that in solutions of Pd and Rh phosphine complexes at high temperature (140 ° and higher) esters, halogen
anhydrides, aldehydes and other carbonyl compounds undergo decarbonylation processes forming corresponding olefins or alkanes. It was interesting to check an
ability of the reverse octanoic acid (OA) decarbonylation reaction under conditions of 1-heptene hydrocarboxylation using PdCl 2 (PPh 3 ) 2 /PPh 3 catalytic system
[3]:
C 5 H 11 –CH=CH 2 + CO + H 2 O C 7 H 15 –COOH
For this purpose 1-heptene hydrocarboxylation was conducted under 13 pressure (5 at, 150 °) in the presence of propionic acid (PA). We supposed that
both 1- 13 C-octanoic acid and unlabeled octanoic acid would be formed due to PA decarbonylation which accompanied with unlabeled CO formation. Maximal
signal in 13 NMR spectrum of isolated product (I) in CDCl 3 relates to labeled 13 = group; other seven signals intensities are not more then 1 %. -Carbon
atom (C-2) signal is superposition of two signals: doublet (34.035 ppm, 1 J C-C =55.08 Hz) of labeled OA fragment - 13 ()- 13 2 - and singlet (34.048 ppm) of
unlabeled acid fragment - 12 ()- 13 2 -. Unlabeled acid part in the product I is about 20 % which is defined by peaks integration. From the other hand
unlabeled OA was not found in isolated product (II) when the reaction was conducted in the absence of propionic acid (in o-xylene as solvent) and under 13
pressure: the ratio of signal intensities of labeled acid and unlabeled one was 98:2. There are weak signals of - groups (39.49 ppm, 1 J C-C =54.30 Hz) in 13
NMR spectrum of the product II due to 2-methyl heptanoic acid small quantities formation.
So, during -olefins hydrocarboxylation process conducted at high temperature obtained carboxylic acid decarbonylation may occur. To exclude this side
reaction and to improve hydrocarboxylation process efficiency, perhaps, carboxylic acids synthesis should be conducted at lower temperature. Now we check this
assumption.
References
[1] O.N. Temkin, In: Encyclopedia of Catalysis. Ed. I.T. Horvath, John Wiley & Sons, 5 (2003) 394.
[2] J. Tsuji, Palladium. Reagents and Catalysts, Chichester: John Wiley & Sons, (1998) 385, 537.
[3] A.R. Elman, A.E. Batov, RU Pat. 2311402 (2007).

209 Oxidation of anisole and 2-methoxyphenol with metal carboxyethylphosphonates
Graça Rocha a* , Teresa Santos a and Claúdia Bispo a
a
Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
*Corresponding author. Tel: +351 234370711, Fax: +351 234370084, e-mail: grrocha@ua.pt
Background
The development of heterogeneous catalytic systems for the oxidation of aromatic compounds is an important topic in chemical research [1,2]. Recently, the use
of metal carboxyethylphosphonates as acid catalysts in various reactions, including oxidation, has received considerable attention. These materials are considered
as solid strong inorganic acids and much of the catalytic activity has been justified by their acidic nature [3, 4]. Having in mind a comparative study with other
types of catalysts previously tested with anisole and 2-methoxyphenol, their oxidation was performed using hydrogen peroxide as oxidant and aluminium(III),
chromium(III) and zirconium(IV) carboxyethylphosphonates as catalysts.
Results
The oxidation reaction of anisole and 2-methoxyphenol gives rise to the formation of 2-methoxyphenol / 4-methoxyphenol and catechol / 2-
methoxybenzoquinone, respectively, depending on the catalyst and reaction conditions. The reactions were performed in acetic acid using hydrogen peroxide as
oxidant in the relation of 1:1 or 1:3 relatively to the subtract. In both reaction conditions 2-methoxyphenol and catechol were synthesised preferentially. Given
the experimental results, we conclude that the layered or pillared structure of our compounds together with the different acidity of the metal centre (Al, Cr and Zr)
and the acidic nature of the carboxylic groups could, effectively play an important role in the selectivity of individual reaction products. The experimental
conditions and the results will be discussed in the presentation.
Justification for acceptance
Metal (IV) phosphates and phosphonates are, easily synthesised at low temperatures in aqueous media, particularly resistant to extremes of temperature and
radiation, simply recovered from the reaction mixtures and reusable. Hydrogen peroxide is an efficient and "clean" oxidant. Theses aspects make these
heterogeneous catalysts and oxidant interesting from the economical and environmental point of view.
References
[1] Rocha, G.; Johnstone, R.; Neves, M. Journal of Molecular Catalysis A: Chemical 187/1 (2002) 95.
[2] Rocha, G.; Rocha, J.; Lin, Z. Catalysis Letters 89/1-2 (2003) 69.
[3] Curini, M., Rosati, O., Costantino, U., Current Organic Chemistry 8 (2004) 591.
[4] Gómez-Alcantara, M. M.; Aranda, M. A. G.; Olivera-Pastor, P.; Beran, P.; Garcia-Muñoz, J. L.; Cabeza, A. Dalton Transactions 4 (2006) 577.
217 Green and eco-friendly heteropolyanion catalysts for the selective oxidation of amine compounds
F. F. Bamoharram a* , M. M. Heravi b , M. Roshani a and F. Abrishami a
a
Department of Chemistry, Islamic Azad University -Mashhad Branch, Mashhad, Iran.
b Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran.
*Corresponding author. Tel: +98 511 8934285, Fax: +98 511 6226605, e-mail: fbamoharram@mshdiau.ac.ir
Background
The products of oxidation of amines are useful as protecting groups, auxiliary agents, oxidants, ligands in metal complexes and catalysts[1]. Also these are of
interest because of their physiological activity, uses in liquid crystal displays and therapeutic medicines [2]. Therefore, a variety of oxidation and catalytic
methods have been investigated [3]. However, most of the used catalysts typically require special conditions to obtain good yields and some of them are toxic,
corrosive and expensive. As a part of research project and in continuation of our researches on heteropolyacids, the present work screens the performance of the
heteropolyacids including Keggin, Dawson, mixed addenda and Preyssler structures in the oxidation of many substituted aromatic amines using H 2 O 2 .
Results
We have found that in these oxidations, these catalysts render effective oxidation in excellent yields. Our data indicate that in pyridine carboxylic acids, the
position of COOH group has important role in the product type and decarboxylation is only taken place at 2-position of nitrogen. Also in every case Preyssler
catalyst produces the highest yield . For substituted anilines the azoxy compounds were major product.The effects of catalyst type, solvent type, temperature,
heteroatom, metal type and time of reaction have been examined and optimum conditions have been obtained. The results showed that the reaction yields were
affected by changing of these parameters. The significance of this study lies in the fact that their use would lead to an alternative technology for the other systems
and aliphatic amines, which are of interest for the pharmaceutical industry, and nanotechnology, with advantages from the point of view of the environmental
care.
Justification for acceptance
The environmental care is one of the world wide increasing worries. This fact encourages scientists to make efforts in finding processes working in this
direction. For this reason, there is still a good scope for research towards finding green and eco-friendly catalysts. The application of heteropolyacid catalysts
cause solving of some problems such as corrosion, and environment problems.
References
[1] Y. Izumi, K. Urabe, M. Onaka, Zeolite, Clay and Heteropoly acid in Organic Reactions, Kodansha/VCH,Tokyo, 1992, p.99.
[2] A. Heidekum, M. A. Harmer, W. F. Hoelderich, J. Catal . 181 (1999) 217.
[3] E. Haslam. Terahedron. 36 (1980) 2409.

218 [NaP 5 W 30 O 110 ] 14- as an efficient and eco-friendly catalyst for synthesis of acylals
F. F. Bamoharram a* , M. M. Heravi b , M. Roshani a and T. Mirghafari a
a
Department of Chemistry, Islamic Azad University -Mashhad Branch, Mashhad, Iran.
b Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran.
*Corresponding author. Tel: +98 511 8934285, Fax: +98 511 6226605, e-mail: fbamoharram@mshdiau.ac.ir
Background
Acylals are suitable protecting groups for aldehydes because of their stability and easy conversion into parent aldehydes [1]. In synthesis of these compounds,
strong protonic acids have been used [2]. However, many of the reported methods involve strongly acidic conditions, high temperature, long reaction times,
expensive catalysts along with high catalyst loadings, excess amounts of reagents, and generation of significant quantities of waste. For these reasons, there is a
demand for a methodology that is mild, efficient, environmentally benign, site selective, with using green and reusable soild acids as catalysts. Heteropolyacids
are useful acid and oxidation catalysts in various reactions because their catalytic features can be varied at a molecular level [3]. In continuation of our program to
develop reactions in eco-friendly conditions, in this work we report an efficient and convenient procedure for the preparation of acylals from a variety of aromatic
aldehydes and their deprotection catalyzed by [NaP 5 W 30 O 110 ] 14- .
Results
The acylals were achieved in good yields at room temperature.The effects of catalyst structure, solvent, catalyst moles and time of reaction were studied. Also
we compared this catalyst with other heteropolyacids. Our data show that H 14 [NaP 5 W 30 O 110 ] with high hydrolytic(pH=0-12) and thermal stability rather than the
other heteropoly anions is a highly efficient catalyst for acylals formation . To show the high selectivity of the method, we studied competitive reactions for
acylation of aldehydes in the presence of ketones . Ketones did not produce any acylal under the same conditions; this suggested that chemoselective protection
of aldehydes in the presence of ketones could be achieved with this process.
Justification for acceptance
Some of the major advantages of this procedure are operational simplicity, high yields, short reaction times, and high selectivity. In addition, as a
nonhygroscopic, noncorrosive, and water-stable compound,the synthesis of H 14 [NaP 5 W 30 O 110 ] is easy, which makes this catalyst suitable for the large-scale
operation.
References
[1] T. W. Greene, P. G. M. Wuts, Protective groups in organic synthesis, 2 nd ed, Jhon Wiley: New York, 1991.
[2] J . G . Frick Jr ., J . Appl . Polym . Sci . 29 ( 1984 ) 1433.
[3] F . F . Bamoharram , M . M . Heravi , M . Roshni , M . Gahangir , A . Gharib , Appl Catal . 302 ( 2006 ) 42 .
219 Heteropoly anions as eco-friendly catalysts for synthesis of lactones
F. F. Bamoharram a* , M.M. Heravi b , M. Roshani a and A. Gharib a
a
Department of Chemistry, Islamic Azad University -Mashhad Branch, Mashhad, Iran.
b Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran.
*Corresponding author. Tel: +98 511 8934285, Fax: +98 511 6226605, e-mail: fbamoharram@mshdiau.ac.ir
Background
Several catalytic synthetic methods for lactones have been developed and reported during these recent years[1,2]. Many of these procedures suffer from lack of
selectivity, unsatisfactory yields, being costly, toxicity of the reagents, or required special conditions. These limitations prompted us towards further investigation
in search for a new catalyst, which will be to carry out the lactonization of diols under simpler experimental set up and eco-friendly conditions. In continuation of
our works on heteropolyacids, herein we wish to report an efficient and green method for the synthesis of lactones from the corresponding diols, in the presence
of hydrogen peroxide as an oxidizing agent and heteropolyacids with different suructures including transition metal substituted Keggins, Keggin, Dawson, and
Preyssler as catalyst.
Results
Lactones are synthesized from related diols, using various heteropolyacids as catalyst and hydrogen peroxide as oxidant. The effect of different reaction
parameters such as temperature, catalyst, concentration of diol and oxidant and solvent were studied on the yield of lactonization and optimum conditions have
been obtained. The results show that The Preyssler catalyst produces the highest yield. The performance of this catalyst was compared with sulfuric acid and the
catalytic activity of sulfuric acid is found to be lower than this catalyst. The green catalysts can be easily recovered and recycled with retention of their initial
structure and activity.
Justification for acceptance
In view of green chemistry, the substitution of harmful liquid acids by solid reusable heteropolyacids as catalyst in organic and inorganic synthesis is the most
promising application of these acids.
Simple experimental procedure as well as high yield and selectivity, makes this method a useful addition to the methodologies that require green super acid solid
catalyst.
References
[1] A. K. Picman, Biochem. Synt. Ecol. 14 (1986) 255.
[2] I. Collins, J. Chem. Soc., Perkin Trans. 1 (1999) 1369.

220 A catalytic route for acetylation of phenols and alcohols in the presence of sodium 30-tungstopentaphosphate
M.M. Heravi a* , F. F. Bamoharram b and F. Behbahani a
a Department of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran.
b
Department of Chemistry, Islamic Azad University -Mashhad Branch, Mashhad, Iran.
*Corresponding author. Tel: +98 9121329147, Fax: +98 21 8047861, e-mail: mmh1331@yahoo.com
Background
Among the various protecting groups used for the hydroxyl function, acetyl is the most common group in view of its easy introduction, being stable to the
acidic reaction conditions, and also easily removable by mild alkaline hydrolysis [1]. Although many methods for the acetylation of alcohols and phenols exist,
there is still a good scope for research towards finding green and eco-friendly catalysts. Development of methods using heteropoly acids(HPAs) as catalysts for
fine organic synthetic processes related to fine chemicals, such as flavore, pharmaceuticals and food industries have been under attention in the last decade[2]. In
continuation with our work using heteropolyacids which are low in toxicity, highly stable towards humidity, being recyclable and air stable, we studied the
catalytic behavior of sodium 30-tungstopentaphosphate heteropolyacid for acetylation of alcohols and phenols with acetic anhydride at room temperature.
Results
We found that a trace of H 14 [NaP 5 W 30 O 110 ] as able to promote quantitative acetylation of alcohols and phenols using acetic anhydride as acetylating agent, at
room temperature, in high yields and short reaction time in solvent free conditions with a simple method and easy workup procedure. In order to extend the scope
of this acetylation reaction, it was carried out on a variety of substrates. The general efficiency of this reaction is evident from the variety of hydroxyl compounds
including primary, secondary, tertiary, benzylic alcohols and phenols, which react in excellent yields within a short reaction time. We also used phenols with
withdrawn, and releasing electron groups, which are converted to the corresponding phenyl acetates in excellent yields and short reaction time.
Justification for acceptance
Heteropolyacids are more active catalysts than conventional inorganic and organic acids for various reactions in solution .They are not corrosive and
environmentally benign, presenting fewer disposal problems.
References
[1] T. W. Greene, P. G. M. Wuts, Protective groups in organic synthesis, third Ed, Jhon Wiley: New York, 1999.
[2]T. Okuhara, N. Mizuno, M. Misono, Adv. Catal. 41 (1996) 221.
224 Production of C 3+ olefins from ethanol by second elements-modified Fe/H-ZSM-5 catalysts
M. Inaba a, *, K. Murata a and I. Takahara a
a National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, 305 8565, Japan
*Corresponding author. Tel: +81 29 861 4776, Fax: +81 29 861 4776, e-mail: mg.inaba@aist.go.jp
Background
Currently, main chemical compounds in industry are synthesized from petroleum. However, the petroleum resources are limited and the combustion of petroleum
produces CO 2 , which causes global warming. Much attention has been paid to biomass as alternative resource to petroleum, since biomass is renewable resources
and its combustion does not lead to increase of CO 2 in atmosphere. Ethanol is one of the main biomass products. We have tried production of C 3+ olefins
(especially propylene), which are useful as not only fuels but also chemicals, from ethanol using Fe/H-ZSM-5 catalysts, since iron is non-toxic and cheap metal.
Results
Catalysts were prepared by impregnation method. H-ZSM-5 zeolite (Si/Al 2 = 29) was used as support. As sources of Fe, Fe(NO 3 ) 3·9H 2 O, FeCl 3·6H 2 O and
Fe 2 (SO 4 ) 3·nH 2 O were used (Fe = 1 wt %). After impregnation, the wet catalysts were dried at 120 C, followed by calcinations in air-flow at 700 C. As catalyst
support, P or Au-modified H-ZSM-5 zeolite were also prepared. (NH 4 ) 3 PO 3·3H 2 O was used as source of P (P = 1 wt %), and HAuCl 4·4H 2 O was used as source of
Au (Au = 2 wt %). Calcination processes of these supports were the same as Fe/H-ZSM-5 catalysts. The catalytic activity was measured in a fixed-bed reactor
(catalyst = 0.2 g), using a vaporized EtOH-N 2 flow (N 2 = 60 cm 3 min -1 ). Reaction temperature was 450 C. As ethanol, neat ethanol and bioethanol were used:
bioethanol was obtained by mixing of neat ethanol and commercial vodka (alcohol = 50 %) in ratio of 1:3. The effluent gas was analyzed by gas chromatography
(GC). The selectivity of C 3+ olefins and propylene was significantly improved in conditions of Fe = 1 wt % and reaction temperature = 450 C, compared with the
case of Fe = 10 wt % and reaction temperature = 400 C (reported in [1]). The maximum selectivity of C 3+ olefins and propylene was ca. 30 and ca. 18 %,
respectively. In the case of Fe/H-ZSM-5 catalysts, the effect of the Fe sources on the selectivity of C 3+ olefins and propylene for neat ethanol was as follows:
FeCl 3 > Fe 2 (SO 4 ) 3 > Fe(NO 3 ) 3 . The selectivity was lower for bioethanol than for the neat ethanol. On the other hand, in the cases of Fe/P or Fe/Au/H-ZSM-5
catalysts, the selectivity for the neat ethanol was lower than those of Fe/H-ZSM-5 catalysts, but, in the bioethanol conversion, the selectivity in P- or Au-modified
catalysts was higher than that in Fe/H-ZSM-5 catalysts. Moreover, the selectivity was higher than the case of neat ethanol, different from the cases of Fe/H-ZSM-
5 catalysts. These results suggest that P- or Au-modified Fe/H-ZSM-5 catalysts are adequate for the conversion of bioethanol containing water. Moreover, P-
loading could improve the catalytic stability.
Justification for acceptance
By these catalysts system, olefins, which are useful as not only fuels but also chemicals, can be obtained in high selectivity from ethanol as biomass resource.
This result can lead to reduction of consumption of petroleum resource and fixation of CO 2 by polymerization of these olefins obtained in this reaction.
References
[1] M. Inaba, K. Murata, M. Saito, I. Takahara, Green Chem., 9 (2007) 638.

241 NMR Determination of the Enrichment Extent in Octanoic Acid during Hydrocarboxylation
of 1-Heptene with labeled 13 CO catalyzed by PdCl 2 (PPh 3 )/PPh 3
V.. Nosova * , .V. Kisin , .R. Elman b
FSUE “GNIIChTEOS”, Shosse Entuziastov, 38, Moscow 111123, Russian Federation.
b Rostkhim Ltd., Shosse Entuziastov, 38, Moscow 111123, Russian Federation.
*Corresponding author. Tel: +7(495) 673-59-70, e-mail: vmno@mail.ru
1- 13 C-octanoic acid obtained in both presence and absence of propionic acid (products I and II respectively) during catalyzed by PdCl 2 (PPh 3 )/PPh 3 process
of hydrocarboxylation of 1-heptene with labeled 13 CO (150 o , 5 bar) was investigated by NMR. In the presence of propionic acid its decarbonylation takes place
and the product of 1-heptene hydrocarboxylation reaction contains 1- 12 C-octanoic acid along with labeled 1- 13 C-octanoic acid. Proton chemical shifts of obtained
product I in CDCl 3 solution actually coincide with those of non-labeled octanoic acid, however, signal multiplicity is more complicated.
The most intensive signal of the eight observed ones in 13 C NMR spectrum is assigned to the labeled 13 = group bonded directly to 12 2 moiety. Other
seven signals are no more than 1 % intensity of maximal one because natural abundance of 13 isotope is 1.1 %. Carbon-13 resonance of the carbonyl group is
accompanied by two satellites with splitting 1 J( 13 C- 13 ) =55.08 Hz; their intensities may be comparable to other signals in the spectrum. The nearest to carbonyl
atom CH 2 group (C-2 in table, IUPAC numbering) shows in 13 C NMR spectrum two signals – doublet (34.035 ppm, 1 J C-C =55.08 Hz) due to fragment
HOO 13 C- 13 CH 2 of labeled acid, and singlet at 34.048 ppm assigned to HOO 12 C- 13 CH 2 of non-labeled one. Signals C-3 and C-4 of the next CH 2 groups look quite
similarly e.g. as superposition of doublet for labeled and singlet for non-labeled octanoic acid respectively. Other resonances in the spectrum are singlets. All
signals were assigned using 2D spectra COSY and HSQC recorded on BRUKER AVANCE 600 spectrometer. Notice that our assignment doesn’t coincide with
that made for octanoic acid in the Data Base SDBS [1]. Ratio of integral intensities doublet to singlet of C-2 carbon in I was found using BRUKER AM-360
spectrometer (delay between pulses 120 s) to be 80 to 20. So contribution of non-labeled acid in the product I is 20 %. 13 C NMR spectrum of product II shows the
degree of enrichment equal to 98 %.
Chemical shift, ppm -1 -2 -3 -4 -5 -6 -7 -8
Labeled octanoic acid 180.636 34.035 24.601 28.967 31.589 28.857 22.520 13.865
n J( 13 C- 13 ), Hz 55.08
n=1
55.08
n=1
1.68
n=2
3.66
n=3
Non-labeled octanoic acid 180.634 34.048 24.603 28.967 31.589 28.857 22.520 13.865
References
[1] Spectral Database for Organic Compounds, SDBS. NMR: T. Saito, K. Hayamizu, M. Yanagisawa and O. Yamamoto,
National Institute of Advanced Industrial Science and Technology (AIST), (www.aist.go.jp; http://riodb01.ibase.aist.go.jp/sdbs/).
282 Acylation of 2-methoxynaphthalene over fly ash supported cerium triflate catalyst.
Chitralekha Khatri a , Deepti Jain a and Ashu Rani a *
a Environmental Chemistry Laboratory, Department of Chemistry, Government P. G. College, Kota-324 001, Rajasthan, India.
* Corresponding author. Tel.: +91 9352619059; e-mail: ashugck@rediffmail.com
Background
Friedel-Craft acylation is an important acid catalyzed reaction to synthesize aromatic ketones which finds a wide range of applications as intermediates of
pharmaceuticals, fine chemicals, dyes, perfumery chemicals, etc. Today, there is a significant demand of product efficient, cost effective and clean processes. The
solid acid catalysts such as modified metal oxides, zeolites, silica immobilized Lewis acids are being tried as alternative of conventional liquid acids to have
green and economic processes. In this series, a new type of solid acid catalyst was synthesized from fly ash, which is a solid waste of coal fired thermal power
plant. Fly ash contains mainly SiO 2 , Al 2 O 3; quartz, mullite and iron in the crystalline phases with unburned carbon [1]. Further chemical and thermal activation
changes the physicochemical properties of the fly ash, to develop an effective solid acid catalyst for acylation reaction.
Results
Fly ash supported cerium triflate heterogeneous acid catalyst was prepared by two-step process. In first step, the fly ash was activated chemically with
concentrated sulfuric acid followed by thermal activation at 450 °C resulting to the activated fly ash. Second step involves the loading of Cerium triflate (5 wt %)
dissolved in methanol on the activated fly ash followed by calcination at 250 °C. The chemical and thermal activation enhances the silica content and BET
surface area of the fly ash, which is evident from the characterization. The catalytic activity of the prepared catalyst was tested by liquid phase solvent free
acylation of 2-methoxynaphthalene with acetic anhydride at 120°C for 6h, which brings excellent conversion 84%, leading to 1-acetyl-2-methoxynaphthalene as
major product. The results showed the presence of significant Lewis acidity in the fly ash catalyst, which was confirmed by ammonia adsorption FTIR. The
catalyst was reused showing equal efficiency in as the fresh catalyst.
Significance
The novelty of the work is the utilization of fly ash, a solid waste, as new solid acid catalyst for single step, solvent free acylation reactions with high conversion,
comparable to other solid acid catalysts. The prepared catalyst is effective to overcome the disadvantages of conventional Lewis acids and can be used for other
acid catalyzed organic transformations.
References
[1] M. Criado, A. Fernandez-Jimenez , A. Palomo, Micropor. Mesopor. Mater. 106 (2007) 180–191.

311
Synthesis of Primary Amides from Aldoximes by Supported Rhodium Hydroxide Catalyst
K. Yamaguchi, H. Fujiwara, Y. Ogasawara, M. Kotani and N. Mizuno*
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo, 113-8656, Japan
*Corresponding author. Tel: +81-3-5841-7272, Fax: +81-3-5841-7220,
e-mail: tmizuno@mail.ecc.u-tokyo.ac.jp
Background
Development of efficient synthetic methods of amides is academically and industrially very important. The interconversion of carbonyl groups and their
derivatives such as aldehydes and oximes is a candidate for the amide synthesis. However, the synthesis of primary amides from aldoximes is very difficult.
Therefore, the development of efficient procedures for the transformation is still in a great challenge. Here, we report that the easily prepared supported rhodium
hydroxide (Rh(OH) x /Al 2 O 3 ) acts as an effective heterogeneous catalyst for the one-pot synthesis of primary amides from various kinds of aldoximes in water
under the conditions of entirely free of organic solvents. 1
Results
The Rh(OH) x /Al 2 O 3 catalyst showed high catalytic activities for the transformation of non-activated, activated, unsaturated, and heteroatom-containing
aldoximes to primary amides. In addition, the Rh(OH) x /Al 2 O 3 catalyst could be applied to the tandem one-pot synthesis of primary amides from the
corresponding aldehydes and hydroxylamine under the similar conditions. The Rh(OH) x /Al 2 O 3 catalyst could easily be separated by filtration and reused
with retention of its catalytic performance for these transformations. The catalysis is truly heterogeneous because the filtrate after removal of the
Rh(OH) x /Al 2 O 3 catalyst is completely inactive and no leaching of the rhodium species was observed. The present transformations likely proceed
through sequential reactions, that is, the dehydration of aldoximes to nitriles followed by the hydration to afford the corresponding primary amides.
Justification for acceptance
The present system has the following significant advantages; (i) applicability to various kinds of substrates, (ii) use of water as a solvent, (iii) simple
workup procedures, namely catalyst/product separation, (iv) reusability of Rh(OH) x /Al 2 O 3 .
References
[1] H. Fujiwara, Y. Ogasawara, K. Yamaguchi, N. Mizuno, Angew. Chem. Int. Ed. 46 (2007) 5202.
318 Development of Dendrimer-Encapsulated Pd Catalysts for Organic Synthesis
T. Mizugaki a , T. Mitsudome a , K. Jitsukawa a , and K. Kaneda b, *
a Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University.
b Research Center for Solar Energy Chemistry, Osaka University,1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
*Corresponding author. Tel & Fax: +81-6-6850-6260, e-mail: kaneda@cheng.es.osaka-u.ac.jp
Background
Dendrimers are highly branched macromolecules with monodispersed molecular weights, precisely determined cascade structures, and capsular shape. One of
the promising applications of metallo-dendrimers lies in catalysis. The organometallic dendrimers have a potential in filling the gap between homogeneous and
heterogeneous catalyses because of their structurally well-defined active sites as well as advantages of facile recovery by filtration or solvent precipitation. The
characteristic structures of dendrimers offer opportunities for nano-platforms of multiple active sites [1] and nanometric templates of metal nanoparticles [2].
However, there are few reports on positive dendritic effects. Here, we described the preparation and selective catalyses of various Pd species such as monomeric
complexes, subnano clusters, and nanoclusters encapsulated within dendrimers.
Results
The dendritic Pd catalysts were prepared by surface functionalization of the third to the fifth generations of poly(propylene imine) (PPI) dendrimers with various
acyl chlorides, followed by treatment with 4-diphenylphosphinobenzoic acid and [PdCl(C 3 H 5 )] 2 to give dendrimer encapsulated monomeric Pd-phosphine
complexes [2]. The encapsulated Pd complexes showed high catalytic activity for Mizoroki-Heck reaction of iodobenzene. Notably, during the catalytic reaction,
coordinatively unsaturated Pd(0) phsphine complex was formed. Positive dendritic effect was observed in the reaction of 1,4-diiodobenzene with styrene, where
the monosubstituted product selectively formed, while the disubstituted one was obtained without the dendrimer.
Furthermore, multimetallic dendrimer-Pd nanocomposites could be prepared by treatment of the functionalized dendrimers with aqueous solution of Na 2 PdCl 4 ,
-
which were reduced by BH 4 to afford dendrimer-encapsulated Pd nanoparticles. The particle sizes were precisely controlled by changing the amount of
preorganized Pd(II) ions within the dendrimers; the Pd particle sizes could be tuned ranging from subnano to nano scale. Interestingly, These Pd nanoclusters
showed specific catalytic activity for hydrogenation of olefinic bonds.
Justification of acceptance
The fine control of the active Pd species using dendrimers have potentials as nanoreactors capable of catalyzing various organic tarnsformations, especially
highly selective reactions for green organic syntheses.
References
[1] K. Kaneda, et al. Chem. Commun. (2002) 52.
[2] a) K. Kaneda, et al. Nano. Lett. 2(2002) 999; b) J. Am. Chem. Soc. 126(2004) 1604; c) Chem. Commun. (2008) 241

349 A non-phosgene synthesis of MDI intermediate derived from CO 2
Xiaoguang Guo a , Jian Li a , Jianpeng Shang a , Xiaoping Zhang b, * and Youquan Deng a, *
a Lanzhou Institute of Chemical Physics, CAS and b Lanzhou University, Lanzhou, 730000, China
*Corresponding author. Fax : +86 931 4968116, e-mail: ydeng@lzb.ac.cn; zxp@lzb.ac.cn
Background
Many non-phosgene strategies for isocyanate syntheses have been exploited for a long time and one of the potentially enable process is carbamate synthesis and
then thermal decomposition to afford corresponding isocyanates. [1] The key process is carbamate synthesis using proper carbonyl reagent such as CO, DMC, etc.
In this work, catalytic syntheses of methyl or ethyl and butyl carbamates (MC, EC and BC) with NH 3 and CO 2 in the presence of lower molecular weight alcohols
and then catalytic synthesis of alkyl N-phenyl carbamates, which is a key intermediate for MDI, via aniline and the MC (or EC and BC) were studied.
O
cat1
CO 2 +NH 3 +ROH H 2 N C OR + H 2 O reaction 1
O
O
NH 2 + NH 2 COR
cat2
NHCOR + NH 3
reaction 2
R= -CH 3 ,-C 2 H 5 ,-C 4 H 9
Results
All reactions were conducted in 90-110 ml autoclaves. For reaction 1, NH 3 0.5 MPa, CO 2 3.5 MPa, N 2 0-8 MPa and methanol (or ethanol and butanol) 0.2-0.6
mol were mixed and reacted over metal oxide (e.g. ZnO) + ionic liquids (e.g. BMIMNTf 2 , EMIMMS) complex catalyst without any dehydrate reagent at 453-473
K for 10-12h. So far, about 3, 9 and 4% of MC, EC and BC yields could be obtained respectively. The main by products were ammonium carbamate and dialkyl
carbonates and the pressure ratio of NH 3 and CO 2 played an important role for the byproducts formation. For reaction 2, a series of ZnCl 2 , NaOCH 3 , PbO,
Bi(NO 3 ) 3 , etc. as catalysts (0.2-0.3 mmol) were tested for the reactions between aniline (5 mmol) and MC or EC and BC (5-40 mmol) to afford corresponding
alkyl N-phenyl carbamates in different solvents (e.g. toluene, butanol, 0-150 mmol) at 453-473 K for 1-8h. At 473 K, butyl N-phenyl carbamate (BPC) could be
efficiently synthesized with 99.5% of aniline conversion and 99.2% of BPC selectivity over Bi(NO 3 ) 3 , but MC and EC gave relatively lower reactivity. A tentative
mechanism for reaction 2, i.e. electrophilic Bi 3+ exert an electrophilic attack on the alkyl carbamate, followed by nucleophilic attack of aniline and a molecular
rearrangement, was proposed. Further investigation is under going.
References
[1] A. M. Tafesh and J. Weiguny, Chem. Rev. 96, (1996), 2035-2052
This work was financially supported by the National Natural Science Foundation of China (No. 20533080).
358 Alkylation of p-cresol with tert-butyl alcohol using novel Bronsted acidic ionic liquids
Sreedevi Upadhyayula*, P. Elavarasan, Kishore Kondamudi
Department of Chemical Engineering, Indian Institute of Technology, New Delhi, 110016, India
*Corresponding author: Tel: +91 11 2658 1083, Fax: +91 11 2658 1120, e-mail: sreedevi@chemical.iitd.ac.in
Background
Butylated hydroxytoluene (BHT), a well known antioxidant and gasoline additive can be produced by t-butylation of p-cresol with t-butyl alcohol (TBA) over
various acidic homogeneous and heterogeneous catalysts. Recently, there has been an increasing interest in developing catalytic reaction processes with minimal
environmental threats and maximal economic benefits. In this context, room temperature ionic liquids (RTILs) are finding growing applications since they
possess negligible vapor pressure, excellent chemical and thermal stability, ease of separation and recyclability. Hence, various acidic RTILs are tried as catalysts
in this reaction and the results are found to be encouraging.
Results
SO 3 H- functionalized Bronsted ionic liquids have been prepared in laboratory following literature procedures [1]. Catalytic activity testing has been carried out
under autogeneous pressure in a 30 ml mini autoclave lined with Teflon over a magnetic stirrer hotplate for 8 hours. The results of the alkylation comparing the
activity of three ILs with solid acid catalyst are shown in Table 1.
Table 1. Activity of the various catalysts for alkylation of p-cresol with t-butyl alcohol
Catalyst
Reactant ratio Temp Conversion Selectivity(%)
TBA :p-cresol
C (%) TBC DTBC
IL1 1 :1 70 72 90 9.5
IL1 3 :2 70 85 66.8 32.3
IL2 1 :1 70 70 82.7 16.9
IL2 2 :1 70 84 72 27
IL3 1 :1 70 80 91 8.9
Al-MCM-41[2] 2 :1 90 96.2 46.3 42.2
References
[1] M.A. Harmer, Q. Sen, Appl. Catal. A. 221 (2001) 45.
[2] M. Selvaraj, S. Kawi, Microporous Mesoporous Mater. 98 (2007) 143.

363 Mesoporous SBA-15 silica-supported nitroxyl radical catalyst for the hypochlorite oxidation of alcohols
A. Machado a , J. E. Castanheiro b , E. Godoy a , I. M. Fonseca a , A. M. Ramos a , J. Vital a*
a REQUIMTE/CQFB, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
b CQE, Departamento de Química, Universidade de Évora, 7000-671 Évora, Portugal
Corresponding author. Tel: +351 212948385, fax: +351 212948385, e-mail: jmv@dq.fct.unl.pt
Background
The oxidation of primary and secondary alcohols into the corresponding carbonyl compounds is a key transformation in modern organic synthesis [1]. Systems involving
nitroxyl radicals such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) have shown great efficiency for the selective oxidation of primary and secondary alcohols to the
corresponding aldehydes and ketones with high yields and selectivitys [2]. In this work TEMPO was successfully immobilized on mesoporous SBA-15 silica and used as
an active and selective catalyst for the oxidation of 1-butanol using sodium hypochlorite as terminal oxidant.
Results
The textural characterization of SBA-15 obtained from physical adsorption–desorption of nitrogen at 77 K, showed a type IV isotherm with H1-hysterisis indicating the
presence of mesopores. The XRD pattern of SBA-15 shows three well defined peaks in the 2 range 1-3º, which can be indexed as (100), (110), and (200) planes which
can contribute to the SBA-15 type mesoporous silica.
During the oxidation procedure with SBA-15-TEMPO, sample aliquots were regularly taken and analysed by GC. The results showed that 93% conversion was achieved
after approximately 1hr, being butanal the main oxidation product.
Justification for acceptance
2,2,6,6-tetramethylpiperidine-1-oxyl has already been immobilized on various organic and inorganic supports. However these radicals have never been immobilized on
mesoporous SBA-15 silica materials, which could be an important goal in the development of new environmentally friendly methods for the selective catalytic oxidation
of alcohol substrates to aldehydes and ketones.
References
[1] P. Ferreira, E. Phillips, D: Rippon, S.C. Tsang, Appl. Catal. A: Env. 61 (2005) 206.
[2] M. Gilhespy, M. Lok, X. Baucherel, Catal. Today 117 (2006) 114.
364 Development of Clay-Palladium(II) Nanocomposite Catalyst for Green Alcohol Oxidation
T. Hara, M. Ishikawa, N. Ichikuni and S. Shimazu*
Department of Applied Chemistry and Biotechnology,
Graduate School of Engineering, Chiba University
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
*Corresponding author. Tel&FAX: +81-43-290-3379, e-mail: shimazu@faculty.chiba-u.jp
Background
The oxidation of alcohols is well known as one of the most fundamental organic transformations. The reaction plays an important role in both laboratory and
industrial chemistry, because the produced carbonyl compounds are useful intermediates in the manufacture of fine chemicals and pharmaceuticals. In the view
point of Green and Sustainable Chemistry, the new catalytic system using molecular oxygen, which produces only water as a by-product, is strongly desired [1].
Results
In this work, an active divalent Pd catalyst supported on the Ni-Zn basic salt (Pd/NiZn) was synthesized by the simple intercalation of Pd(II) hydroxyl complex to
the interlayer of NiZn without organic ligand. The Pd/NiZn acted as an effective heterogeneous catalyst toward alcohol oxidation using an air as oxidant. The
catalytic activity depended on the sort of Pd precursors, the content of intercalated Pd amount, and the type of layer host. It should be noted that the Pd species in
the interlayer of NiZn was maintained the original oxidation state and no formation of Pd metal after catalytic reaction. Pd/NiZn catalyst showed a high turnover
frequency (TOF; mol of product per mol of Pd content per hour) of 148 h 1 . This TOF value of the Pd/NiZn catalyst is the highest ever reported for the divalent
palladium complex-catalyzed aerobic alcohol oxidations so far: Pd(OAc) 2 /pyridine/MS3A (10 h 1 ) [2a], Pd(OAc) 2 /triethylamine/MS3A (33 h 1 ) [2b],
Pd(OAc) 2 /Phen*S/NaOAc (40 h 1 ) [2c], and Pd(IiPr)(OAc)(H 2 O)/NaOAc/MS3A (50 h 1 ) [2d]. Furthermore, the catalyst was able to be reused without any loss
of the catalytic activity and selectivity, where no Pd leaching was observed in the above aerobic oxidation conditions.
Justification for acceptance
Although the highly efficient heterogeneous Pd catalysts are often Pd nanoparticles, active Pd species in our Pd/NiZn catalyst keeps its original divalent structure
even after catalytic reaction due to the strong interaction between anionic Pd(II) species and the layer host. Furthermore, the catalytic activity of Pd/NiZn is the
highest ever reported divalent Pd catalyst.
References
[1] J.H. Clark, Green Chem. 1 (1999) 1–8.
[2] (a) T. Nishimura, T. Onoue, K. Ohe, S. Uemura, J. Org. Chem. 64 (1999) 6750–6755; (b) M.J. Schultz, C.C. Park, M.S. Sigman, Chem. Commun. (2002)
3034–3035; (c) G.-J. ten Brink, I.W.C.E. Arends, R.A. Sheldon, Science 287 (2000) 1636–1639; (d) D.R. Jensen, M.J. Schultz, J.A. Mueller, M.S. Sigman,
Angew. Chem. Int. Ed. 42 (2003) 3810–3813.

371 Immobilization studies and biochemical properties of free and immobilized candida rugosa lipase onto mesocellular silica foams:
A comparative study
Reshmi.R, S. Sugunan *
Department of Applied Chemistry, Cochin University of Science and Technology,
Kochi-682022, Kerala, India. Tel: + 91-484-2575804. Fax: +91-484-2577595
E- mail: ssg@cusat.ac.in, rreshmi@cusat.ac.in
Background
A simple room temperature synthesis of mesocellular silica foams (MCF) was carried out using an emulsion containing surfactant, oil and water.
Immobilization of Candida rugosa lipase in this silica was carried out using three-step process through alkylamine and glutaraldehyde. MCF is a promising
material for immobilizing enzymes, due to its large pore structure and high loading capacity compared to other mesoporous materials, such as MCM-48, SBA-16
and SBA-15[1, 2]. The structural and chemical properties of these prepared materials were characterized by SEM, XRD, FTIR, TG/DTG and nitrogen adsorption.
In aqueous media a comparative study between free and immobilized derivatives was provided in terms of pH, temperature and kinetic constants (V max and K m )
following the hydrolysis of p-nitrophenyl palmitate, in which new optima values were established. The effects of temperature, pH, thermal stability, reusability,
storage stability and the kinetic properties were also investigated.
Results
Immobilization enhanced the enzyme stability against changes of pH and temperature. Better thermal stability was exhibited by the immobilized lipase
and the pH stability was comparable to that of soluble lipase. It was found that lipase immobilized on functionalized MCFs materials is re-useable The lipase was
immobilized by covalently coupling enzyme molecules to the interior surface of functionalized mesostructured cellular foams materials, in which leaching of the
enzyme is prevented. A weak ionic interaction between the enzyme and the surface of the inorganic substrate is thought to be critical in maintaining the activity of
the immobilized enzyme.
Justification for acceptance
A unique porous structure of MCF was found to be a critical factor which renders siliceous mesostructured foam a very promising material for
immobilization of enzymes. We demonstrate the advantage of MCF as an inorganic substrate for immobilization of enzymes.
References
[1] X. Zhang, R.F. Guan, D.Q. Wu, K.Y. Chan, J. Mol. Catal. B 33 2005 43.
[2] K. Szyman´ska, J. Bryjak, J. Mrowiec-Biaon, A.B. Jarzebski, Micropor.Mesopor. Mater 99 2007 167.
383 Allyl transfer reaction of homoallyl alcohols to aldehydes via cleavage of a C-C bond on heterogeneous Ru/CeO 2 catalyst
H. Miura, M. Sai, S. Hosokawa, T. Kondo, K. Wada,* and M. Inoue
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
*K. Wada. Tel: +81-75-383-2511, Fax: +81-75-383-2510, e-mail: wadaken@scl.kyoto-u.ac.jp
Background
Development of heterogeneous catalysts for organic synthetic reaction is highly desired because of their practical application in green chemical processing. On the other
hand, catalytic organic transformation via cleavage and reconstruction of C-C bonds under mild reaction conditions is of great significance. We have already
reported the first homogeneous ruthenium complex-catalyzed deallylation of homoallyl alcohols via -carbon (-allyl) elimination 1 . Afterward, Oshima and
coworkers reported related reactions leading to allyl transfer from homoallyl alcohols to aldehydes and/or aryl halides 2,3 . In the present study, we report the first
allyl transfer reaction of homoallyl alcohols to aldehydes on heterogeneous Ru/CeO 2 catalysts.
Results
CeO 2 was prepared by the treatment of cerium nitrate with aqueous ammonia. Ru/CeO 2 catalysts were prepared by the impregnation of a THF solution of
Ru 3 (CO) 12 on to CeO 2 , followed by the calcination at 400 o C for 30 min. Ru/CeO 2 catalyst was found to be the most effective for the title
OH
reaction. While the reaction of a homoallyl alcohol 1 with pentafluorobenzaldehyde 2a mainly afforded a homoallyl alcohol 4a, the reaction
with aldehydes 2b-2e at 170 o C for 24 h selectively yielded saturated ketones 5b-5e in high yields. These ketones were found to be produced C 6 F 5
via homoallyl alcohols. The control experiments indicated heterogeneous nature of the catalyst.
4a
Ru/CeO
Ph Me
O
2
(0.025 mmol Ru) Ph Me O
HO
1
1.0 mmol
+
R
H
2
0.50 mmol
2b:R=Ph
2c:R=4-MeOC 6 H 4
2d:R=4-FC 6 H 4
2e:R=4-MeC 6 H 4
Mesitylene (2.0 ml)
170 o C, 24 h
Under Ar
References
[1] T. Kondo, K. Kodoi, E. Nishinaga, T. Okada, Y. Morisaki, Y. Watanabe, T. Mitsudo, J. Am. Chem. Soc. 120 (1998) 5587.
[2] S. Hayashi, K. Hirano, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc. 128 (2006) 2210.
[3] Y. Takada, S. Hayashi, K. Hirano, H. Yorimitsu, K. Oshima, Org. Lett. 8 (2006) 2515.
O
+
R
3 5
5b: 62%
5c: 92%
5d: 64%
5e: 78%

388 Ru/CeO 2 -catalyzed addition of aromatic C-H bonds to alkenes
H. Miura, K. Wada, * S. Hosokawa, and M. Inoue
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
*K. Wada. Tel: +81-75-383-2511, Fax: +81-75-383-2510, e-mail: wadaken@scl.kyoto-u.ac.jp
Background
Directive C-C bonds formation via aromatic C-H bond activation reported by Murai and co-workers 1 has attracted much attention. Several transition metal
complexes, mainly Ru complexes, are found to be effective for these reactions. On the other hand, development of heterogeneous catalysts is quite advantageous
from the view point of green chemistry. However, heterogeneous catalysts have not been applied to the title reaction so far. Here, we report the first example of
Ru/CeO 2 -catalyzed selective addition of aromatic C-H bonds to alkenes via C-H bond activation.
Results
Ru/CeO 2 catalysts were prepared by the impregnation method. 1.0 g of CeO 2 prepared by the treatment of cerium nitrate with aqueous ammonia was added to a
solution of 42 mg of Ru 3 (CO) 12 in 10 mL of THF under air at room temperature. After impregnation, light yellow powder was calcined at 400 o C for 30 min. and
the yielded blown powder was used as Ru/CeO 2 catalyst. The reaction of aromatic ketone 1 with alkene 2 selectively proceeded as shown in eq.1. Among the
ruthenium catalysts examined, only ceria-supported ones showed significant activity. Although the reaction required high temperature and the addition of
phosphine ligands, the adduct 3 was selectively obtained in the yield of up to 71%.
O
O
+ Si(OEt) 3
Ru/CeO 2, PPh 3
Mesitylene, 170 o C
~24h
1 2 3
Si(OEt) 3
up to 71% yield
(1)
Justification for acceptance
Transition metal-catalyzed reactions involving the formation of new C-C bonds via aromatic C-H bond activation is a central issue in modern synthetic chemistry.
We believe this paper, which provides the first example of the reactions initiated by Ru/CeO 2 catalysts, has significance to be presented at the 5 th ICEC because of
their potential application to “green” synthetic processes.
References
[1] a) S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, and N. Chatani, Nature 1993, 366, 529-530; b) F. Kakiuchi, S. Sekine, Y. Tanaka, A.
Kamatani, M. Sonoda, N. Chatani, S. Murai, Bull. Chem. Soc. Jpn. 1997, 70, 3117-3128; c) review: F. Kakiuchi, S. Murai, Acc. Chem. Res. 2002, 35, 826-834.
396 Beckmann rearrangement of cyclohexanone oxime to -caprolactam over heteropoly acid supported
on mesoporous silica molecular sieves
N. R. Shiju, M. Bandyopadhyay, D. R. Brown*
Centre for Materials and Catalysis Research, Department of Chemical and Biological Sciences, University of Huddersfield, Queensgate, HD 1 3DH, UK
*Corresponding author. Fax : +44 1484 472182, e-mail: d.r.brown@hud.ac.uk
Background
-Caprolactam, produced by the Beckmann rearrangement of cyclohexanone oxime (Fig. 1), is an important intermediate used in the production of Nylon 6
fibers and resins [1]. Nylon 6, together with nylon 66, accounts for more than 80% of worldwide synthetic fibre production. Since fuming sulfuric acid is used as
a catalyst in the Beckmann rearrangement process, current -caprolactam-manufacturing processes produce large amounts of ammonium sulfate as a by-product.
Environmental regulations and process safety aspects are driving industry and academia towards new processes based on solid acid catalysts.
Results
The objective of this work is to investigate the possibility of using periodic mesoporous silica molecular sieves (SBA-15 and MCM-48) and supported
heteropoly acids (HPAs) as solid acid catalysts for the Beckmann rearrangement of cyclohexanone oxime. Heteropolyacids possess strong Brönsted acidity and
structural flexibility and can stabilize cationic organic intermediates. Periodic mesoporous silicas are promising supports because of their high specific surface
areas, pore volumes, regular pore structures and tuneable pore sizes and immobilised HPAs may interact more strongly with the ordered mesoporous supports
than with amorphous silica, due to the high dispersions achieved [2].
In the reported work, FTIR spectra of the supported phosphotungstic acid (HPW) samples have confirmed the presence of intact heteropoly anions on the
support surfaces. The mesoporous silica and supported HPW samples have shown high activity both in liquid- and vapour- phase Beckmann rearrangements. The
acid properties of the catalysts have been characterised by NH 3 adsorption microcalorimetry and the catalytic activities and selectivities of the catalysts appear to
depend strongly on their acid strengths. The results demonstrate that the investigated catalysts of this type are potential “green” alternatives to the traditional
homogeneous acid catalysts used in Beckmann rearrangement reaction.
References:
[1] G. Dahlhoff, J. P. M. Niederer, W. F. Hoelderich, Catal. Rev. 43 (2001) 381.
[2] Á. Molnár, T. Beregszászi, Á. Fudala, P. Lentz, J. B. Nagy, Z. Kónya, I. Kiricsi, J. Catal. 202 (2001) 379.
[3] G. Bellussi, C. Perego Cattech 4 (2000) 4.

403 The Study of Propanal Condensation and Hydrogenation over Bifunctional Metal/Solid Base Catalysts.
S. David Jackson and Meilin Jia
WestCHEM, Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ, Scotland, UK
Corresponding author. Tel: +44 141 330 4443, Fax: +44 330 6867, e-mail: sdj@chem.gla.ac.uk
Background
The formation of plasticizer alcohols involves hydroformylation, aldol condensation and hydrogenation reactions, with each step involving purification and
changes from low pressure ambient conditions to medium pressure/temperature gas phase. The latter two stages are practiced industrially using homogeneous
aqueous-base catalysts such as sodium hydroxide followed by hydrogenation over supported nickel catalysts. In this paper we report on using combined solid
base/hydrogenation catalysts to convert propanal to 2-methyl-1-pentanol.
Results
The gas phase condensation reaction of propanal was studied over a series of solid base catalysts (5%K/SiO 2 ,
O H
5%Cs/SiO 2 , 5%Mg/SiO 2 and 5%Ca/SiO 2 ) and
-H
O +Base
2 O +H 2
O
O combined solid base/hydrogenation catalysts
O
Propanal
(1%Pd/5%K/SiO 2 , 1%Pd5%Cs/SiO 2 ,
+H 2 2-methyl-pentanal
2-methyl-2-pentenal
1%Pd/5%Mg/SiO 2 and 1%Pd5%Ca/SiO 2 ;
+2H 2
15%Ni5%K/SiO 2 , 15%Ni5%Cs/SiO 2 ,
O H
15%Ni5%Mg/SiO 2 and 15%Ni5%Ca/SiO 2 ). The
Propanol
OH
results demonstrate that 2-methyl pentenal is the only
2-methyl-1-pentanol product over base catalysts even when hydrogen is the
carrier gas. The Pd/base/SiO 2 catalysts show high
selectivity to 2-methyl pentanal, whereas Ni/base/SiO 2 show high selectivity to propanol but also produced 2-methyl-1-pentanol. Achieving a balance between
base and hydrogenation catalysis was further investigated using a two bed system. In those cases there was evidence of deactivation of the hydrogenation system
when complex unsaturated molecules were in the feed.
Justification for Acceptance
This paper highlights the problems associated with developing a combined base/hydrogenation catalyst. It is not sufficient to balance the catalytic rates but
consideration must also be given to potential deactivation and by-product routes that are not present in the isolated systems.
415 The application of alumina-supported palladium catalysts for the hydrogenation of aromatic nitriles in the liquid phase.
Liam McMillan 1 , Justin Baker 1 , David T. Lundie 2 , Colin Brennan 3 , Alan Hall 3 and David Lennon 1 *
1. Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ, U.K.
2. Hiden Analytical Ltd., 420 Europa Boulevard, Warrington, WA5 7UN, U.K.
3. Process Studies Group, Syngenta, PO Box A38, Leeds Road, Huddersfield, Yorkshire, HD2 1FF, U.K.
*davidle@chem.gla.ac.uk, Tel: +44 (0)141 330 4372, Fax: +44 (0)141 300 4888
Background.
The hydrogenation of aromatic nitrile compounds in the liquid phase to form a variety of amines has wide application in the pharmaceutical and
agrichemical industries [1]. Raney nickel is one of the most active catalysts used for the production of primary amines, however, its skeletal
structure and pyrophoric properties make it difficult to handle and, therefore, the development of new catalysts is desirable [1,2]. Moreover, nickel
based catalysts can be unsuitable for fine chemical applications, due to a tendency to compromise selectivity to the nitrile by additionally facilitating
the reduction of other functional groups typically present alongside the nitrile group. Against this background, it was deemed informative to
consider the effectiveness of supported palladium catalysts for this role.
Results.
Benchmark testing of an ambient pressure 3-phase slurry reactor and a pressurised batch reactor for the hydrogenation of benzaldehyde (C 6 H 5 COH) over
Pd/Al 2 O 3 catalysts showed complete conversion to benzyl alcohol (C 6 H 5 CH 2 OH), indicating that the catalyst/reactor configurations were operating satisfactorily.
However, experiments using these catalysts to effect the hydrogenation of a variety of aromatic nitrile compounds proved less straightforward. Whereas
phenylacetonitrile (C 6 H 5 CH 2 CN) could not be hydrogenated to phenylethylamine (C 6 H 5 CHCH 2 NH 2 ), somewhat surprisingly, the catalysts were able to convert
benzonitrile (C 6 H 5 CN) to toluene (C 6 H 5 CH 2 CH 3 ). These preliminary results suggest that, for the supported palladium catalyst studied here, a phenyl group
assists nitrile hydrogenation, whilst a benzyl group appears to hinder the process. In addition, a hydrogenolytic step from benzylamine to form the toluene is also
possible [2]. Furthermore, a significant particle size effect for the benzonitrile reaction was also observed, with larger Pd particles exhibiting enhanced selectivity
for the benzylamine. Collectively, these issues indicate some of the complexities inherent in the selective hydrogenation of aromatic nitriles.
References
[1] C. Debellefon and P. Fouilloux, Catal. Rev.-Sci. Eng., 36 (1994) 459
[2] I. Ortiz-Hernandez and C.T. Williams, Langmuir, 23 (2007) 3172.
[3] L.Hegedus, T.Mathe, Applied Catalysis A: General 296 (2005)

416 The Gas Phase Hydrogenation of 1,3-pentadiene: a FTIR Study.
Neil G. Hamilton 1 , Andrew R. McFarlane 1 , David Siegel 1 , David T. Lundie 2 and David Lennon 1 *.
1. Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ, U.K.
2. Hiden Analytical Ltd., 420 Europa Boulevard, Warrington, WA5 7UN, U.K.
*Corresponding author: Tel: (44)-(0)-141-330-4372. Fax: (44)-(0)-141-330-4888. E-mail: davidle@chem.gla.ac.uk.
Background.
Olefin chemistry on the industrial scale is closely linked with increased refinery capacity and covers a wide range of chemical processes [1]. Diolefins, or dienes,
are also industrially significant, with C 4 and C 5 1,3-dienes featuring strongly. Here, the double bonds are conjugated and the molecules are more reactive than
their monoene counterparts [1]. Of the higher homologues, 1,3-pentadiene presents an interesting case, with recent studies being performed in the gaseous [2]
and liquid [3] phases. Interestingly, the reaction profiles reported in these studies differ significantly [3]. One reason for this discrepancy could be that the gas
phase study used in situ FTIR spectroscopy to determine the reaction profile, rather than the more conventional chromatographic method. In order to check the
reproducibility of the spectroscopic measurements, the hydrogenation reactions of 1,3-pentadiene and a number of pentenes were re-investigated using a new 1%
Pd/Al 2 O 3 catalyst. Vibrational assignments were additionally confirmed by performing a full vibrational analysis of the relevant molecules [4].
Results.
An infrared cell was used as a batch reactor. The catalyst was mounted at the bottom of the cell in such a way that the spectrometer only sampled the gaseous
phase. Thus, the spectrum of the gaseous component that is in direct exchange with the dispersed metal catalyst can be analysed as the reaction proceeds.
Through an appreciation of the active modes of the reactants and products, including stereo-isomers and probable intermediates [4], it is possible to construct a
reaction profile for the hydrogenation process. In agreement with the original work, isomerisation of pentenes is seen to represent an accessible pathway that
operates alongside the consecutive process of the hydrogenation reactions. These studies additionally indicate that the Pd particles are capable of storing
significant proportions of hydrogen.
Justification.
These superficially simple measurements have the advantage of providing reaction profiles under conditions where the gaseous reagents are in
equilibrium with the catalyst surface. As such, they reveal the chemical pathways potentially accessible to the reaction system. This perspective is
helpful in understanding product distributions in more dynamic systems, where kinetic control can play a major role.
References
[1]. K. Weissermel and H.-J. Arpe, in Industrial Organic Chemistry, VCH, Weinheim, 3 rd Ed., 1997.
[2]. E. Opara, D.T. Lundie, T. Lear, I.W. Sutherland, S.F. Parker and D. Lennon, Phys .Chem. Chem. Phys., 2004, 6, 5588.
[3]. S.D. Jackson and A. Monaghan, Catal. Today, 128 (2007) 47.
[4]. David Siegel, Vibrational characteristics of a range of C 5 molecules, Masters Thesis, University of Glasgow, July 2007.
419 Chemical recycling of PET assisted by phase transfer catalysis
R. López-Fonseca*, M.P. González-Marcos, J.R. González-Velasco and J.I. Gutiérrez-Ortiz
Chemical Technologies for Environmental Sustainability Group,
Department of Chemical Engineering, Faculty of Science and Technology,
Universidad del País Vasco/EHU, P.O. Box 644, E-48080, Bilbao, Spain.
*Corresponding author. Phone: +34-94-6015985, Fax: +34-94-6015963, e-mail: ruben.lopez@ehu.es
Background
Chemical or tertiary recycling of waste polymers including PET, poly(ethylene terephthalate), leads to the formation of the raw starting monomers by different
depolymerisation routes [1]. This work was focused on the identification of the catalytic behaviour of a series of quaternary phosphonium and ammonium salts (9
salts with varying alkyl groups, central cation (N or P) and anion (Cl - , Br - , I - , OH - )) as phase transfer catalysts (PTC) for the alkaline hydrolysis of PET, and on
the kinetic modelling of the PTC-assisted-process.
Results
Reaction experiments were carried out in a 300 mL-capacity Parr batch reactor. The selected operating conditions were: stirring rate 400 rpm, particle size 250
m, inert atmosphere 200 kPa N 2 , temperature 60-100 ºC, NaOH concentration 1.67 mol L -1 , PET concentration 0.29 mol L -1 , and PTC concentration 0-0.07 mol
L -1 . Among the catalysts tested tributylhexadecylphosphonium bromide (3Bu6DPB) was found to be the most effective catalyst since it considerably accelerated
the reaction rate. Complete conversion of PET to sodium terephthalate and ethylene glycol with considerably low catalyst concentration and temperature could be
achieved. This quaternary phosphonium salt acted as a shuttling agent by extracting the OH - anion from the aqueous phase into the organic interfacial region (the
surface of solid PET flakes) where the anion could freely react with the organic reactant. The selected phase transfer catalyst fulfilled the requirements of having
enough character in order to be lipophilic, while small enough in order to avoid steric hindrance [2]. The time for complete hydrolysis (>90% conversion) of solid
PET under alkaline conditions with 3Bu6DPB at 80 ºC is 1.5 hours and 10 hours without 3Bu6DPB.
The proposed kinetic model accounted for both uncatalysed and catalysed reactions and predicted a linear correlation for the reaction rate with the concentration
of the quaternary salt. Both non-catalysed and phase transfer catalysed processes presented roughly the same activation energy. The notable increase in the phase
transfer catalysed reaction rate (about 130-190 times greater in the presence of 3Bu3DPB) was mainly related to the greater value of the pre-exponential factor,
which indicated that the number of effective collisions leading to reaction (PET hydrolysis) was remarkably increased. Although the exact mechanism for the
alkaline hydrolysis was not yet clear it could be concluded that it is probably similar to the non-catalytic.
References
[1] B.Z. Wan , C-Y. Kao W-H. Cheng, Ind. Eng. Chem. Res. 40 (2001) 509.
[2] V.A. Kosmidis, D.S. Achilias, G.P. Karayannidis, Macromol. Mater. Eng. 286 (2001) 640.

430 A polyoxometallate-tethered Ru (II) bifunctional catalyst for alcohol carbonylation and solvent-free alkyne oligomerisation
Lee Dingwall, Adam F. Lee, * Karen Wilson, * Jason M. Lynam *
Department of Chemistry, University of York, York, YO10 5DD, UK
*Corresponding authors. : +44 (0)1904 43 2516, afl2@york.ac.uk; kw13@york.ac.uk; jm112@york.ac.uk
Background
Current interest in new solid acid catalysts for bulk and fine chemical synthesis is driven by tightening legislation on waste emissions and the need to replace
current atom-uneconomical practices [1]. Multifunctional heterogeneous catalysts offer ‘one-pot’ processes with reduced time on-stream and increased efficiency.
Alcohol carbonylation and alkyne oligomerisation [2,3] are both conventionally performed using homogeneous catalysts and wherein C-H activation is a key step
in the reaction. We recently synthesised a bifunctional, Ru-doped heteropolyacid catalyst, able to activate both hydrocarbons and CO under mild reaction
conditions.
Results
+
-
We have recently synthesised a novel rutheniumcontaining
polyoxometallate (POM) compound
(Figure 1), which incorporates both POM and
HNEt3
Ru
Ru
Ph 3P
PPh 3
Ph3P
Ph
organometallic Ru functionalities, and is
3P
extremely tolerant towards air, moisture and
diverse solvents.
This strategically designed compound exhibits Figure 1. Proposed RuHPW structure
high activity and good selectivity towards [HNEt 3 ] + [(Ru( 5 -C 5 H 5 )(PPh 3 ) 2 ) 2 (PW 12 O 40 )] - .
carbon-carbon bond formation in phenylacetylene oligomerisation via an atom-efficient, solvent-free protocol. The presence of the POM cage not only confers
great stability upon the Ru-component, but also provides strong acid sites able to readily activate methanol. The formation of a Ru-O=W bond linking the
organometallic fragment and this acidic POM cage, also facilitates the subsequent reaction of resulting alcohol-derived carbocations with CO reversibly
coordinated at the Ru centre. This paves the way for a new generation of heterogeneous alcohol carbonylation catalysts, which obviate the need for corrosive
mineral acids (e.g. HI) and permit ready catalyst separation from the desired acetyl products in a continuous process.
References
[1] I. V. Koshenvnikov Catal. Rev. Sci. Eng. 37 2 (1995) 311.
[2] T. Takahashi Y. Liu A. Iesato S. Chaki K. Nakajim K. Kanno JACS 127 (2005) 11928.
[3] A. D. Burrows M. Green J. C. Jeffery J. L. Lynam M. F. Mahon Angew. Chem. Int. Ed. 38 20 (1999) 3043.
459 Vapor phase Beckmann rearrangement of cyclohexanone oxime on deboronated B-ZSM-5
M. Matsukata*, K. Nakagawa, Y. Sekine, and E. Kikuchi
Department of Applied Chemistry, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan,
*Corresponding Author. Tel & Fax: +81 3 52863850, e-mail: mmatsu@waseda.jp
Background
The vapor phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam is an outstanding achievement of green chemistry. Nest silanols in the
vicinity of the external surface of silicalite-1 has been proposed as active sites. In this study, deborobnation/desilication of B-ZSM-5 was examined to develop a
highly active catalyst for this reaction.
Results
Under the conditions optimized in this study, as shown in Fig. 1, B-ZSM-5 produced was agglomerates of nanocrystals having a large BET surface area,
454 m 2 g -1 . The product was calcined in air and deboronated by the treatment with HCl aq. at 353 K for 3 h. The FT-IR study confirmed the formation of
abundant nest silanols, especially on the sample treated at a low pH of about 1.0. Further, the deboronated sample was successively desilicated with a mixture of
ammonia nitrate and ammonia. The vapor phase Beckmann rearrangement was performed in a plug flow reactor with a fixed bed of catalyst at WHSV = 8 h -1 and
653 K. Fig. 2 gives the pH dependency of the amounts of boron and silica removed and catalytic activity. The catalytic activity was greatly improved by the
deboronation treatment at pH=1 whereas the desilication was not effective for activation of catalyst: The pseudo-first-order reaction constant for the parent B-
ZSM-5 was 1.8x10 -3 s -1 , but that for the deboronated ZSM-5 was 0.13 s -1 .
Justification for acceptance
While the E-factor of the conventional Beckmann rearrangement of
cyclohexanone oxime to -caprolactam with H 2 SO 4 was 2.5, it can be remarkably
decreased to 0.32 by using solid catalysts. This paper shows a new strategy for
preparing a highly active and selective catalyst.
References
[1] For instance, G.P. Heitmann, G. Dahlhoff, W.F. Holderich, J. Catal. 186 (1999) 12. H.
Ichihashi, M. Ishida, A. Shiga, M. Kitamura, T. Suzuki, K. Suenobu, K. Sugita, K., Catal.
Surveys from Asia 7 (2003) 261.
10 m
Deboronation or desilication / atom u.c. -1
Conversion
De-Si
De-B
pH
Conversion / % (TOS=5.5 h)
Fig. 1 Typical SEM views of B-ZSM-5. Particles are agglomerates of ca. 50 nm crystals.
Fig. 2 Dependency of catalytic activity and the amounts of boron and silicon removed.

460 Research of ethanol oxidation over V-Mo-O catalysts
V.L.Baghiyev a *, E.H.Alakbarov b , A.D.Guliyev c
a
Azerbaijan State Oil Academy, Baku, Azerbaijan
b
SRI”Geotechnological Problems of Oil Gas and Chemistry”, Baku, Azerbaijan
c Institute of Petrochemical Processes of ANAS, Baku, Azerbaijan
* Corresponding author. Tel: (+99450) 3280059, Fax: (+99412) 5140349, e-mail: vagif_bagiev@yahoo.com
Background
Last years the increasing attention of scientists concerns to reactions of conversion of ethanol in various monomers such as acetic aldehyde, an acetic acid,
acetone, ethyl acetate, etc. It is caused by that ethanol is considered by scientists as renewable, alternative raw materials which does not negative influence on
environment. In this work results of investigations of oxidizing reaction of ethanol over vanadium-molybdenum oxide catalysts of various compositions are
presented.
Results
Activity of the synthesized catalysts have been studied on flow installation with a quartz reactor in the range of temperatures 150-450 0 . Products of reaction of
vapor-phase oxidation of ethanol on the studied catalysts are acetic aldehyde, ethylene, an acetic acid, a carbon dioxide and at very high temperature carbon
monoxide. The carried out researches have shown, that activity of the investigated catalysts strongly depend on the ratio of elements included into their
composition. Depending on temperature of reaction change of the ratio of vanadium to molybdenum influences in different ways on a yields of reaction products.
So at temperatures above 300 0 with increasing of the amount of vanadium in catalysts acetic aldehyde and ethylene yields decrease, while at lower temperatures
the change of catalyst composition practically does not influence on a their yields. Acetic acid and carbon dioxide yields with growth of the amount of vanadium
increase in all studied interval of temperatures. The maximum yield of an acetic acid (63.6 %) is observed on catalyst V:Mo=8:2 at temperature 250 0 . For an
explanation of such character of dependence of activity of catalyst from its composition we were studied the phase composition of catalysts. X-ray investigation
have shown, that on catalyst V:Mo=1:9 phase of Mo 3 predominates, however in small amounts is formed and a chemical compound V 2 MoO 8 . The increasing of
the vanadium amount in a catalyst composition lead to growth of the phase of chemical compound V 2 MoO 8 and decrease of quantity of phase 3 . The
maximum amount of phase V 2 MoO 8 is observed on catalyst V:Mo=5:5. Since sample V:Mo=3:7 in a composition of the catalyst there is a phase of free V 2 0 5 and
with growth of the amount of vanadium in the catalyst phase of V 2 0 5 increases. Catalyst V:Mo=9:1 practically consists of phase V 2 0 5 though still there is a phase
V 2 MoO 8 in trace quantities.
Justification for acceptance
Thus, it is possible to say, that catalysts rich with molybdenum are active in reaction of dehydration of ethanol to ethylene while catalysts rich with vanadium
display high activity in reaction of formation of an acetic acid. The catalysts V:Mo=8:2 can be used for further investigation in pilot plant.
482 A Catalytic Route for Michael Addition of Indole using Tungstophosphoric Acids as Green Catalysts
M. Mohadeszadeh a, *, M. H. Alizadeh b
a Department of Chemistry, School of Sciences, Azad University of Quchan, Quchan, Iran
b Department of Chemistry, School of Sciences, Ferdowsi University, Mashhad 91779-1436, Iran
*Corresponding author. Tel: +98 511 8797022, Fax: +98 511 8797022, e-mail: mohadeszadeh@yahoo.com
Background: Indole derivatives as the important intermediates in organic synthesis have received much attention, because of various physicological properties,
biological and pharmacological activities. Several methods have been reported for the 3-substituted indole with various aldhydes or ketones using protic acids, Lewis
acids and heterogeneous catalysts [1]. Along this time, heteropolyacides as solid catalysts are considered green because of producing low waste, low in toxicity and
easily recycling. Following our previous studies on the catalytic activities of heteropoly anions [2], we report using inorganic solid tungstophosphoric acids (Keggin
H 3 [PW 12 O 40 ], Wells-Dawson H 6 [P 2 W 18 O 40 ], and Preyssler H 14 [NaP 5 W 30 O 110 ]) as catalysts in the synthesis of bis(indolyl)methanes (BIMs).
Results: BIMs were formed in the reaction of indole with aliphatic and aromatic aldehydes or ketones in the presence of the tungstophosphoric acids as green lewis
acids. The influence of parameters: catalyst, substituent in the aromatic ring of the aldehyde, solvent, and the molar ratio of the catalyst on the yield of BIMs were
studied. Effect of catalyst: The reaction of indole with benzaldehyde (2:1 molar ratios) over tungstophosphoric acids as catalysts in CH 3 CN at room temperature
indicates that the yield of bis(indolyl)phenylmethane follows the sequence: H 3 PW 12 O 40

485 Side-chain alkylation of toluene with propene over a basic catalyst. A DFT study.
Sawomir Ostrowski 1 and Jan Cz. Dobrowolski 1,2
1 Industrial Chemistry Research Institute, 8 Rydygiera Street, 01-793 Warsaw, Poland
2
National Medicines Institute, 30/34 Chemska Street, 00-725 Warsaw, Poland
E-mail: janek@il.waw.pl
The toluene methyl group alkylation by propene over a basic catalyst, approximated by the Na 2 molecule, was modeled by the B3LYP/6-311++G** method. The
process starts by formation of the PhCH 2 Na molecule in complex with the NaH molecule. Then, the two reaction paths are considered: Path A at which PhCH 2 Na...NaH
complex is dissociated, and Path B at which the whole PhCH 2 Na...NaH complex enters in the next reaction step. Next, at the two paths both insertion of the propene
double bond into the C-Na bond and the Na/H exchange, leading to one of the isomers of butylbenzene, are examined. At Path A, the PhCH 2 Na molecule plays role of
catalyst: it is re-formed in the last stage and can return to the propene insertion step. At Path B, the Na 2 molecule is a catalyst: it is re-constructed in the last stage and can
return to the beginning step of formation of the PhCH 2 Na molecule. The energy levels at Path A are always above those of Path B, whereas the barriers at the essential
steps of Path A are always significantly lower than the appropriate ones at Path B. Path A seems to be preferred kinetically while Path B thermodynamically. At the two
paths isobutylbenzene is favored over n-butylbenzene by both thermodynamic and kinetic factor. This is in good agreement with experimental findings. We interpret Path
A as describing the reaction in the bulk gas phase whereas Path B as describing the reaction at the metal surface. Because, the number of molecules is usually greater in
the bulk than in the surface Path A, which is practically the same as that described by Pines et al. more than fifty years ago, is the main mechanism describing the toluene
side chain alkylation by propene over a basic catalyst.

POSTER
ABSTRACTS
Clean Energy

111 Mechanism of remarkable hydrogen occlusion and catalytic reaction over Ir metal clusters confined in the hollow SiO 2 nanospheres
S. Naito*, H. Yamada, and T. Miyao
Department of Material and Life Chemistry, Faculty of engineering, Kanagawa University,
3-27-1, Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan.
*Corresponding author. Tel.+81-45-481-5661, Fax.+81-45-413-89770, e-mail:naitos01@kanagawa-u.ac.jp
Background
Recently, we have reported the synthesis of tailor-made hollow silica nanospheres containing ultrafine particles of precious metals such as Ir, Rh, Ru and Pt
in their cavities by using a crystal template method in a reversed micelle system [1-3]. In the case of Ir-SiO 2 nano-hollow samples, more than three times larger
amounts of hydrogen than total Ir metal atoms (bulk and surface) was adsorbed at room temperature(RT), indicating that such metal containing nano-cavities
formed in silica spheres possess an anomalous affinity with hydrogen molecules. In the present report, we have investigated the mechanism of hydrogen
occlusion and its catalytic behavior over Ir-SiO 2 (nh) by using in-situ FT-IR and EXAFS techniques.
Results
Silica nanospheres containing Ir ultrafine particles in their hollow (denoted as Ir-SiO 2 (nh)) were prepared by a reversed micelle technique, employing
Ir(NH 3 ) 6 Cl 3 as precursors and cyclohexane solution of NP-6 surfactants (hexaoxyethylene nonyl phenyl ether), followed by TEOS hydrolysis. The TEM
images of Ir-SiO 2 (nh) clearly showed that the SiO 2 spheres(30nm) contained hollows(7nm) in their center and ultrafine Ir clusters(1nm) inside the hollow as
well as in the framework of SiO 2 sphere(sub nm). In-situ XPS of the reduced sample exhibited that these Ir clusters were positively charged. Three times more
hydrogen than bulk Ir was adsorbed over Ir-SiO 2 (nh) at RT, which desorbed reversibly at 473K.
When H 2 was introduced onto the reduced Ir-SiO 2 (nh) at RT, two distinct infrared absorption bands were observed at 2118 and 3390 cm -1 , which could be
assigned to the vibrational modes of Ir-H and Si-OH, respectively. When the sample was evacuated at 473K, both bands disappeared completely which
reappeared again by the introduction of H 2 at RT. By replacing H 2 with D 2 , these bands disappeared immediately and two new bands emerged at 1511 cm -1 and
2515 cm -1 , which could be assigned to the vibrational modes of Ir-D and OD groups ( D 0.7 H ). These results suggest that hydrogen is adsorbed
dissociatively on the Ir clusters in the silica nanohollows forming Ir + H - and H + species, which may be spilled over from Ir clusters to the SiO 2 forming SiO - H +
group. This spillover process could be responsible for the excess amount of hydrogen occlusion.
In-situ EXAFS spectra of the reduced Ir-SiO 2 (nh) showed the existence of Ir-O bond at R=1.75A, whose intensity decreased significantly by the exposure
of the sample with H 2 at RT. At the same time a new peak emerged at R=2.6A assignable to Ir-Ir bond, whose intensity decreased again by the evacuation at
473K accompanied with the re-appearance of Ir-O peak. From these results we propose a novel Ir cluster aggregation-dispersion mechanism as follows; in the
case of hydrogen adsorption, reduced Ir species may aggregate together forming bigger clusters, which re-dispersed again forming Ir-O bonds by the
desorption of hydrogen at higher temperatures. The H 2 -D 2 isotopic exchange and C 2 H 4 -H 2 reaction were investigated over these catalysts at lower temperatures
and the role of occluded hydrogen for these catalytic reactions was discussed in depth.
References
[1] S.Naito et al., J.Mater.Chem. 15(2005)2268 ; [2] S.Naito et al. ,Topics in Catalysis, 39 (2006) 131-137; [3] S. Naito et al., Sci.Bas.Prep. Hetero. Catal.,
162 (2006) 63-70.
118 Catalytic Purification Process for the Upgrading of Landfill Gas to Fuel Cell Quality
W. Urban*, J. I. Salazar Gómez, H. Lohmann
Fraunhofer Institute for Environmental, Safety and Energy Technology (UMSICHT), Oberhausen, Germany
*Corresponding author. Tel: +49 208 8598-1124, Fax: +49 208 8598 1423, e-mail: wolfgang.urban@umsicht.fraunhofer.de
Background
The efficient utilisation of biogases like landfill gas as an alternative energy source (e.g. feed stock for fuel cells) imposes some challenges, since the purity
requirements for a fuel cell are higher than those for conventional engines [1]. Since the major components of landfill gas (LFG) are methane (40-60%) and
carbon dioxide (35-50%) [2], its utilisation in molten carbonate fuel cells (MCFC) is a cost-effective and environmentally friendly process, which has the
advantage of using two main contributors to the greenhouse effect as an energy source, reducing the dependency to fossil fuels. Besides the major constituents,
LFG contains a wide family of pollutants (minor components MC) [3] generally, at the trace level but harmful enough to destroy any fuel cell in a short time.
Therefore, their elimination is compulsory.
Results
A catalyst screening showed that two commercial materials, a vanadium-based catalyst and an activated alumina, exhibited the highest activity and selectivity
for the total oxidation of volatile organic compounds (VOCs) and the removal of siloxanes, respectively. For the most stable compounds (hardest to remove),
such as chlorocarbons (CC) and chlorofluorocarbons (CFC), the conversions observed are in the range 78-97%. For other compound types (aromatics, sulphurcontaining
compounds, etc.) the conversions are roughly 100%. After a lab-scale testing period, the catalysts are being tested under real conditions in a fieldtest
facility, where the on-going experiments have shown equally encouraging results. One of the advantages of the catalytic system is that due to the low
temperature (300°C) the methane contained in the LFG is not oxidised. Moreover, the oxygen and water contained inherently in LFG serve as in situ reagents
for the degradation process. The catalytic process reduces the complex spectrum of MC to a single compound class “acid gases” (HCl, HF, SO 2 ), which can be
easily removed by state-of-the-art technologies, such as adsorption. Despite of this, trace levels of by-products such as COCl 2 , COF 2 and Cl 2 have been
observed too. Current experiments focus on the adjustment of process parameters to hinder the formation of these compounds.
References
[1] R. Bove, P. Lunghi, Energy Conversion and Management 47 (2006) 1391.
[2] S. Rasi, A. Veijanen, J. Rintala, Energy 32 (2007) 1375.
[3] H.-C. Shin, J.-W. Park, K. Park, H.-C. Song, Environmental Pollution 119 (2002) 227.

120 Finely dispersed Au-Cu and Au-Ag alloy particles for CO removal from H 2 fuel
Aiqin Wang, Xiaoyan Liu , Wanjun Li, Tao Zhang *
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, CAS, Dalian 116023, China
*Corresponding author. Tel: +86 411 84379015, Fax: +86 411 84691570, e-mail: taozhang@dicp.ac.cn
Background
Finely dispersed gold particles on a variety of reducible supports are effective for preferential oxidation (PROX) of CO in a H 2 -rich stream. However,
controlling gold particle size on a non-reducible support (e.g., silica) is often difficult. In the present work, we for the first time reported that by alloying gold
with silver or copper, the gold particle size could be successfully controlled within 2~3 nm even on an inert silica support, and thus the catalytic performances
for PROX are enhanced significantly.
Results
The preparation of Au-Ag and Au-Cu alloy particles on silica support involved the adsorption of gold precursor on the functionalized support [1] , followed by
reduction with NaBH 4 , and then adsorption of the second metal (Ag or Cu) precursor. The recovered solid was finally calcined at 500 o C in static air and
reduced at 500 o C in H 2 . Both XRD and TEM characterizations show that the Au-Ag and Au-Cu alloy particles are highly dispersed on the silica support. The
average particle size varied with the gold molar fraction. Despite an average particle size of 5.67 nm was obtained on the Au/SiO 2 , it was only 2.46 nm with
Au/Ag = 3/1 and 3.13 nm with Au/Ag = 1/1. The similar trend was also observed on Au-Cu/SiO 2 samples. UV-Vis spectra clearly demonstrated the formation
of Au-Ag alloy and Au-Cu alloy, and in situ XRD examinations on the Au-Cu/SiO 2 confirmed that calcination induced the phase segregation of Au-Cu alloy,
but the subsequent reduction in H 2 led to the homogeneous alloying of gold with copper. PROX tests showed that both the Au-Ag and Au-Cu were significantly
active and selective for CO oxidation than either of their pure-metal counterparts. The decreased particle size and the modified electronic properties by alloying
with Ag or Cu are believed to be responsible for the improved catalytic performances.
Justification for acceptance
The production of clean hydrogen is important for the application of PEMFC. Preferential oxidation of CO in H 2 -rich stream is regarded as one of the most
promising methods for purification of H 2 . Our present work develops new catalysts for this reaction and provides additional understanding for the reaction
mechanism.
References
[1] C. H. Tu, A. Q. Wang, M. Y. Zheng, X. D. Wang, T. Zhang, Appl. Catal. A 297 (2006), 40
123 Evaluation of a flexible fuel autothermal reformer using Rh catalyst
X. Karatzas a* , M. Nilsson a , B. Lindström b , L.J. Pettersson a
a KTH – Royal Institute of Technology, Department of Chemical Engineering and Technology,
Teknikringen 42, SE-100 44 Stockholm (Sweden)
b PowerCell, Sven Hultins gata 9D, SE-412 88 Göteborg (Sweden)
*Corresponding author. Tel: +46 87909150, Fax: +46 8108579, e-mail: xanthias@ket.kth.se
Background
A reformer was developed for a fuel processing/fuel cell system running on various transportation fuels and designed for an electrical output of 1-5 kWe. The
target application was a mobile auxiliary power unit (APU). APU offers an energy efficient and clean technology for the future transport sector. APU is most
likely to be integrated in heavy-duty trucks. In the present study, alumina-supported Rh catalysts were examined in autothermal reforming (ATR) of various
transportation fuels; both using logistic fuels (diesel, gasoline and E85) and alternative fuel candidates (methanol, ethanol and DME). The aim of the study was
to evaluate the practical feasibility of the ATR reactor, using the same reformer and catalyst composition for the different fuels.
Results
The experiments were performed in a reactor designed to generate hydrogen by ATR for a 1-5 kWe polymer electrolyte fuel cell. Rh catalysts were prepared by
incipient-wetness impregnation of -Al 2 O 3 powder and deposited on 400 cpsi cordierite monoliths. ATR operating parameters O 2 :C and H 2 O:C were altered to
match the varying properties of the different fuels. The key criteria for evaluating practical feasibility were based on fuel conversion, H 2 and CO 2 selectivity.
Results from the study indicate that the Rh-CeO 2 -La 2 O 3 , supported on -Al 2 O 3 , catalyst is highly selective for autothermal reforming; particularly in the case of
diesel, gasoline and E85. Fuel conversion >90 % were established for diesel, gasoline, ethanol and E85. H 2 selectivity > 45% were achieved for all fuels.
Finally, the temperature profiles, prior to and after the catalyst section in the reformer, differ between the various fuels.
Reference
[1] The European Commission, Euro VI proposal. http://ec.europa.eu/enterprise/automotive/
mveg_meetings/meeting98/euro_vi_proposal.pdf, last visited 2008-01-10.
[2] California Air Resources Board, Assembly Bill (AB) 32 Fact Sheet – California Global Warming Solutions Act of 2006, Sacramento, California.

124 New heteropolyacid based catalyst for the removal of mercaptans from kerosene
A. de Angelis*, C. Flego, F. Cavani 1) , A. Frattini 1) , C. Rizzo, P. Pollesel, and W.O. Parker,Jr.
Eni Refining & Marketing Division, via Maritano 26, I-20097 San Donato Milanese, Italy
1) Dept. of Chimica Industrially e dei Materiali, University of Bologna, viale Risorgimento 4, 40136 Bologna, Italy
phone number: +390252046202, fax number: 0252056757 e-mail: alberto.de.angelis@eni.it,
Background
Mercaptans are toxic, foul smelling and can be a poison for several classes of catalysts, thus, their elimination from fuels is highly desirable. To remove them
from kerosene, they are oxidised in alkaline medium to obtain the corresponding disulfides. As a consequence, relevant quantities of strongly alkaline solutions
contaminated by sulphur compounds are obtained as by-products in the industrial processes.
Results A new catalyst was produced through hydrolysis with an aqueous solution of a Keggin heteropolyacid (H 4 PVMo 11 O 40 ) of different molar ratios of
tetraethoxysilane (TEOS) and dimethyldimethoxysilane (DDOS). Three samples were prepared from pure TEOS (B), 90%TEOS+ 10% DDOS (C), 70%
TEOS+ 30 %DDOS (D); the heteropolyacid content in the three samples was always equals to 30%wt. Samples were dried under vacuum at mild temperature
(100°C) and characterized by 29 Si, 51 V NMR and FT-IR spectroscopies. Analyses revealed that vanadium exited the Keggin structure, which still maintained its
general features within the dried gel. Incorporation within the siliceous matrix reduced the Brönsted acid strength, but not the redox properties of the catalyst.
In fact these new catalysts were tested in the oxidation of 1-octanethiol with air, in isooctane, at mild temperature (80°C) and all proved to be active oxidising
mercaptans to the corresponding disulfides. Catalytic activity increased as the acidity increased (D < C < B) and the number of silanol groups (i.e.
hydrophilicity) increased, probably due to an enhanced attractive interaction between the polar part (-SH) of the mercaptan molecule and organo-silica surface.
B
C
D
Conv.%
20
18
16
14
12
10
8
6
4
2
0
0 20 40 60 80 100 120 140 160 180 200
Figure 1. Yield of disulfide product, obtained by oxidation of 1-octanethiol, using the HPA inside silica (B) and organo-silica (C, D) matrices, as a function of time on
stream (t.o.s.).
The catalysts were recycled and re-use without any significant loss of catalytic activity. No heteropolyacid leaching in octane was detected.
t.o.s. ( min.)
125 Effect of chlorine on the catalytic behavior of Ir/CeO 2 for preferential CO oxidation
Yanqiang Huang, Aiqin Wang, Lin Li, Xiaodong Wang, Tao Zhang*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China
*Corresponding author. Tel: 86-411-84379159, Fax: 86-411-84691570, E-mail: taozhang@dicp.ac.cn
Background
Ir/CeO2 catalyst has been found to be efficient for removal of traces of CO from hydrogen through the so-called preferential CO
oxidation (PROX) process [1-2]. However, the presence of chlorine diminishes its activity towards the CO oxidation reaction. In the
present work, the surface chemistry occurring on the Cl-free and Cl-containing surfaces is derived from HRTEM, XPS, and DRIFTS
results which reveal the effect of chlorine on Ir/CeO2 catalyst behavior for the PROX reaction.
Results
For the PROX reaction, the catalytic performance of the Cl-free Ir/CeO2 catalyst was considerably superior to that of the Cl-containing
sample. From HRTEM observation, it was found that Ir particles were highly dispersed on both samples. The higher metal dispersion of
the Cl-containing catalyst may imply that the presence of chlorine favors the dispersion of Ir metal particles on the ceria support. The
replacement of the lattice oxygen by chloride ions would produce CeOCl species, which was also confirmed by the HRTEM
characterization. The XPS results indicated that the CeOCl species hindered the formation of surface hydroxyl groups on the Ir/CeO2
catalyst. It has been reported that the OH groups were highly active and played an important role in CO oxidation. The DRIFTS
characterization showed that the presence of Cl species greatly retards the kinetic rate of CO chemisorption on iridium.
Moreover, chlorine hindered the formation of carbonates during CO exposure, which was found to be the intermediates for CO
oxidation. The possible mechanism for CO oxidation in PROX mixture is proposed based on these experimental findings.
Justification for acceptance
The PROX process has been recognized as the most straightforward method for purification of H2 fuel. Our previous activity test has
shown that Ir/CeO2 was reasonably active and selective for this reaction. Therefore, detailed characterization on this catalyst to clarify
the detrimental role of chlorine is helpful to gain further insight into the reaction mechanism.
References
1. F. Mariño, C. Descorme, D. Duprez, Appl. Catal. B 54 (2004) 59.
2. Y. Q. Huang, A. Q. Wang, X. D. Wang, T. Zhang, Inter. J. Hydro. Energy. 32 (2007) 3880.

135 Mg-promoted Cu/ZnO/Al 2 O 3 catalysts for water-gas shift reaction
K. Takehira a, *, K. Nishida a , D. Li a , T. Shishido b , Y. Oumi a and T. Sano a
a Department of Chemistry and Chemical Engineering, Graduate School of Engineering, Hiroshima University, Kagamiyama 1-4-1, Higashi-Hiroshima, 739-8527,Japan.
b Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Katsura 1, Nishigyo-ku, Kyoto, 615-8510, Japan
*Corresponding author. Tel: +81-824246488, Fax : +81-824246488, e-mail: takehira@hiroshima-u.ac.jp
Background Polymer electrolyte fuel cells (PEFCs) have been extensively studied due to their attractive properties, such as high power density, low
emissions of pollutants, low temperature operation and compactness. In this system, hydrogen is used as a fuel; it is obtained by steam reforming of
hydrocarbons. However the reformed gas contains CO at the level of 1-10 % which adsorbs irreversibly on the Pt electrode of the PEFCs at the operating
temperature and hinders the electrochemical reaction. Sustainable water-gas shift (WGS) catalyst is indispensable for removal of CO since the WGS reaction is
moderately exothermic reaction and the reaction temperature is easy to control.
Results Trace amount of Mg was doped on Cu/Zn/Al catalysts by adopting “memory effect” of hydrotalcite. The Mg-doped Cu/Zn/Al catalysts showed high
and sustainable activity in the WGS reaction. Ternary Cu/ZnO/Al 2 O 3 catalysts were prepared from metal nitrates by co-precipitation (cp) at various pH with
NaOH or Na 2 CO 3 as a pH controller; the Cu/Zn ratio was fixed at 1/1, and Al content was varied between 0-25 mol%. A combination of pH = 9 and NaOH was
the most effective for the selective precipitation of aurichalcite, (Cu,Zn) 5 (CO 3 ) 2 (OH) 6 , together with hydrotalcite, (Cu,Zn) 6 Al 2 (OH) 16 CO 3·4H 2 O. The Cu/Zn/Al
precursor thus prepared was applied for the Mg-doping as follows: the precursor was calcined at 300 ºC and dipped in an aqueous solution of Mg nitrate,
hydrotalcite was reconstituted by the “memory (m) effect,” resulting in a Mg incorporation in the surface layer of the catalyst particles. The m-Mg-Cu/Zn/Al
(45/45/10) was active and sustainable, whereas the m-Mg-Cu/Zn/Al (37.5/37.5/25) was less active and unstable for the WGS reaction, suggesting that
aurichalcite was indispensable for producing active Cu/ZnO sites. Contrarily small amount of hydrotalcite was effective for improving the sustainability of the
catalyst by the surface modification. As a comparison, cp-Mg/Cu/Zn/Al (-/45/45/10) catalyst was prepared by co-precipitation of the nitrates of Mg, Cu, Zn and
Al showed high activity, but the sustainability was far lower than the m-catalysts, Mg species distribute in whole particle in the cp-preparation, while Mg
species is enriched in the surface layer of the catalyst particles in the m-preparation, suggesting that the surface Mg species is important in the catalytic
behaviour. We reported that Cu works as the WGS catalyst by the reduction-oxidation between Cu 0 and Cu + : the reduction of Cu + to Cu 0 is coupled by the
oxidation of CO to CO 2 , while the oxidation of Cu 0 to Cu + is coupled by the reduction of H 2 O to H 2 [1]. By Mg incorporation, TOFs of Cu increased on the m-
Mg-Cu/Zn/Al catalysts, whereas such increase was not observed on the cp-Mg-Cu/Zn/Al catalysts. It is concluded that Mg works as an electron donor to active
Cu metal species resulting in an enhancement of the activity and the stability of active Cu species against sintering caused by the oxidation into Cu 2+ .
References
[1] T. Shishido, M. Yamamoto, D. Li, Y. Tian, H. Morioka, M. Honda, T. Sano, K. Takehira, Appl. Catal. A 303 (2006) 62.
136 Development extraction of oil from clay by friendly phase transfer catalyst
A.K El morsi a* and A.M.A.Omar b
a,b
Egyptian Petroleum Research Institute, P.O.box 11272, Nasr city, Cairo, Egypt
*
Corresponding author.Tel: 002—0101501148, e-mail: drakilakamel158@yahoo.co.uk
Background
The waste oil separation from clay was studied using benzyl triethanol ammonium chloride as phase transfer catalyst. The study showed that the surface tension has an
effect on oil recovery. Induced air floatation process was also used and polymeric decyl phenol formaldehyde ethoxylate used as collector. The effects of various
parameters include concentration of catalyst, collector, time of flotation; contact angle and zeta potential were studied.
Results
The results show that the maximum oil recovery obtained was 87%. Furthermore kinetic study proved that the process is first order and depend on
catalyst concentration. It is seen that the oil recovery increases with time of flotation and approaches an asymptote. From all figures it can generally
be noted that the oil recovery is marginal if the flotation time is extended beyond 12 minutes. For example, oil recovery increases by only 4% for 25
g oil and 20 g surfactant in the feed when flotation time increases from 12 to 15 minutes. Also it increases with surfactant dose. Further more, the
oil recovery was enhanced by controlling the interfacial tension at oil /water and water/air interfaces. The mechanism of oil separation was
discussed according to micelle composition and calculated by Gibbs adsorption equation. The molecular interaction parameter at the aqueous
solution/ air interface was also calculated. The results proved that, extraction of oil from solid phase can be developed by adding phase transfer
catalyst. Moreover the paper suggest a model of oil separation from soil according to the type of oil and analyzed chromatography
Justification for acceptance
Oily sludge is generated from petroleum refineries during storage operation. This sludge contains reasonable amount of oil (hydrocarbons) during
cleaning operation. All this wastes are removed , therefore, recovery of oil from this sludge is very important to prevent water and soil pollution. In
this study a new technique using catalysis and serfactant will be applied to reach maximum recovery of oil.
References
1- A.M.A.Omar, Separation of emulsifiable oil from a flotation solution by surface tension control, ADSORPTION SCIENCE and TECHNOLOGY , v.19,no. 1, 2001

150 Understanding and controlling the catalytic hydrolysis of sodium borohydride for the production of high-purity hydrogen
S. Bennici a, *, A. Garron a , D. wierczyski a , A. Auroux a
a Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), UMR 5256 CNRS/Université Lyon1, 2 avenue Albert Einstein, 69626 Villeurbanne Cedex,
France.
*Corresponding author. Tel: +33 472445379, Fax : +33 472445399, e-mail: simona.bennici@ircelyon.univ-lyon1.fr
Background
H 2 is recognized as the environmentally desirable clean fuel of the future and a primary technical challenge is to be able to safely generate, deliver and store
adequate amounts of H 2 . That is the case of borohydride solutions which essentially act as both the H 2 carrier and the storage medium. Aqueous alkaline
sodium borohydride solutions in contact with selected catalysts hydrolyzes to H 2 gas and sodium metaborate NaBO 2 . However the key feature of using a
catalyzed reaction to produce H 2 is that H 2 generation in strongly alkaline solutions occurs only when these solutions contact selected heterogeneous catalysts.
Results
In this work the reaction mechanism, (including kinetics and thermodynamics), of hydrogen release from the hydrolysis of a stabilized sodium borohydride
solution in the presence of cobalt based catalysts has been successfully resolved by using liquid phase reaction calorimetry. The experiments were carried out in
a differential reaction calorimeter from Setaram, linked to a volumetric flow-meter in order to measure both the heat and the hydrogen evolved during the
hydrolysis reaction as a function of time. The catalyst, composed of nanoparticles of Co 2 B, was generated in situ by reaction of the stabilized NaBH 4 solution
with a cobalt chloride solution. This finding was demonstrated by combining magnetic and wet-STEM studies. An accurate and detailed study of the
calorimetric reaction was necessary to elucidate the complicated nature of the system in which many reactions take place in parallel.
Several factors affecting the hydrogen generation yield and rate such as the NaBH 4 , NaOH and CoCl 2 concentrations, the reaction temperature, the presence of
stirring were studied. The tests performed at high concentrations of NaBH 4 have made it possible to show that the reaction mechanism over this type of catalyst
consists of three elementary steps, namely:
1) Exothermic reduction of the surface layer of cobalt borate to cobalt boride.
2) The catalytic reaction proper, in which the evolved energy depends on the hydration state of the metaborates generated as reaction products, between -217
kJ·mol NaBH4
-1
at high hydration and -249 kJ·mol NaBH4 -1 at low hydration.
3) Endothermic regeneration of the protective borate layer.
It was also shown that the cobalt boride nanoparticles formed in situ were not stable in alkaline solution and were coated by a borate surface layer characterized
by DRX and XPS.
151 Supported hydrotalcites for enhanced and stable CO 2 capture
N.N.A.H. Meis a ,*, J.H. Bitter a , K.P. de Jong a
a Inorganic Chemistry and Catalysis, Department of chemistry, University Utrecht, P.O. Box 80083, 3508 TB Utrecht, The Netherlands
*Corresponding author: Tel: +31(0)302536760, Fax: + 31(0)302511027, e-mail: n.n.a.h.meis@uu.nl
Background
In order to reduce the substantial emissions of CO 2 into the atmosphere, CO 2 capture and sequestration are proposed. For CO 2 capture, the current available
materials do not meet the required storage properties with respect to sorption capacities and rates as well as mechanically strength.
Due to the acidic character of CO 2 , basic oxides are expected to be suitable sorbents. Earlier work from our group [1] showed a high potential of
hydrotalcites (HTs) for the sorption of CO 2 . Therefore we investigate these materials in detail for CO 2 capture. In particular, we paid attention to the influence
of the HT platelet size. Two different types of samples were prepared i.e., unsupported HTs and HT supported on carbon nanofibers (CNF).
Results
Unsupported hydrotalcites with lateral size range from 40 nm to 2 m were prepared. In
addition, very small HT platelets (~20 nm) were prepared by deposition onto carbon nanofibers [1].
The CO 2 absorption characteristics of unsupported HT at 250 °C showed a low and invariant
absorption capacity (0.1 mmol•g -1 ) of all samples regardless of the platelet size. However, small
supported hydrotalcites showed a considerable higher uptake (1.3 mmol•g -1 ) of CO 2 . Currently we
tentatively relate this higher uptake to a higher density of defects in the Mg(Al)O x phase that binds
CO 2 . Moreover, supported hydrotalcites gave improved cycle stability. We speculate that by anchoring
individual HT platelets on CNF their mobility is limited, resulting in less agglomeration and annealing
of defects on the Mg(Al)O x phase, thus less deactivation upon cycling. These results indicate the
advantage of supported hydrotalcites for the uptake of CO 2 capture.
Justification for acceptance
We improved not only the specific capacity by a factor 13 for the CO 2 capture material
hydrotalcite, we also improved mechanical strength and cycle stability for these CO 2 capture materials.
Reference
[1] F. Winter , A.J. van Dillen, and K.P. de Jong, Chem. Commun., 31 (2005) 3977.
CO 2 uptake mmol*g -1 HT
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
HT-CNF
1 st cycle 2 nd cycle
0.0
0 50 100 150 200 250 300 1800 2000
Size (nm)

157 Methanolysis of frying oil catalyzed by papaya lipase for biodiesel fuel synthesis
P. Porntippa a, * , P. Jakkrite b
a Department of Chemistry, Faculty of Science and Technology, Uttaradit Rajabhat University, Thailand
b Department of Public Health, Faculty of Science and Technology, Uttaradit Rajabhat University, Thailand
* Corresponding author. Tel: +66 55 411096 ext 1308, Fax : +66 55 411096 ext 1312, e-mail: pimung@hotmail.com
Background : Biodiesel comprises long-chain fatty acid methyl ester. The property of biodiesel is better than petroleum fuel [1]. Biodiesel can be synthesized
by methanolysis of triglycerides which are catalyzed by chemical catalysis or biocatalyst. Acid- or alkali-catalyzed methanolysis has some disadvantages.
Lipase-catalyzed methanolysis have become more attractive because enzymatic catalysis has overcome the drawbacks of chemical catalysis. In the present, the
cost of plant oil is high so the production of biodiesel from frying oil is worthier than vegetable oil. This research indicated that papaya lipase would be a useful
in inexpensieve biocatalyst for biodiesel production from frying oil.
Results : The fatty acid composition of frying oil were determined by acid-catalyzed methanolysis. Papaya lipase obtained by incision of unripe fruit from
several sources of papaya trees was used as a biocatalyst. Improvement activity of lipase was investigated by immersion lipase in isopropanol at various time.
Methanolysis reaction was studied using substrate mixture composed of frying oil 1 mmol and dried methanol 3 mmol. The reaction was started by adding 1 g
of lipase and performed at 37 o C with shaking at 200 rpm for 24 hours. The products formed from the reaction were analyzed by GC-MS.
Frying oil composed of 0.60% lauric acid, 1.23% myristic acid, 47.22% palmitic acid, 0.38% palmitoleic acid, 5.84% stearic acid, 43.00% oleic acid,
1.24% linoleic acid and 0.49% eicosanoic acid. The precipitate of papaya latex showed hydrolysis activity of frying oil at 30.2 4.4 unit/gram of fresh latex.
The activity of enzyme was improved through immersing enzyme with isopropanol for 3 hours, 6 hours and 24 hours. Lipase immersed with isopropanol
catalyzed hydrolysis of frying oil better than those from native of 31 folds, 24 folds and 18 folds for immersion 3 hours, 6 hours and 24 hours, respectively.
Papaya latex lipase immersed with isopropanol for 3 hours could catalyzed methanolysis of frying oil which produced methyl ester 70%. This can be explained
that immersed papaya lipase was surrounded by isopropanol which can act as an intermediate solvent for better solubility of frying oil and methanol. An
addition of 1% (w/w) of water to the enzyme slightly increased the yield of methyl ester after 24 hours of reaction time since this added water make the
enzyme had optimum water activity (0.208). When the reaction was carried out at various mmol ratio of frying oil and dried methanol, the highest content of
methyl ester (80%) was obtained from the methanolysis using a 1 : 2 mmol ratio of frying oil : dried methanol. This may be explained that increasing of
methanol led to lesser dissolution of triglyceride in frying oil and then the entering of triglyceride into active site of enzyme would decrease.
References : [1] S.J. Clark, L. Wangner, M.D. Schrock, P.G. Piennaar, J. Am. Oil Chem. Soc. 51 (1984) 1632.
159 Comparative Study on the Transesterification of Triolein into Fatty Acid Methyl Ester (FAME) Using Homogeneous and
Heterogeneous Quaternary Ammonium Functional Group (QN + OH - )
H. W. Yussof and A.P. Harvey*
Process Intensification Group, School of Chemical Engineering and Advanced Materials,
Merz Court, Newcastle University, Newcastle upon Tyne, NE1 7RU, United Kingdom.
Corresponding author: Tel: +44 191 222 7268, Fax: +44 191 222 5293, Email: a.p.harvey@ncl.ac.uk
Biodiesel is produced by transesterification of vegetable oils or animal fats with an alcohol usually lower alcohols such as methanol and ethanol, in the presence
of a catalyst. Most commercial biodiesel processes use homogenous base catalysts, as they result in a rapid reaction and over 95 % conversion. However,
homogenous base catalysts cannot be economically recovered, and necessitate a glycerol neutralisation step and place a greater load on a number of downstream
separation steps. Replacing liquid homogeneous catalysts with solid heterogeneous catalysts is expected to yield a cleaner product and result in lower production
costs, as the catalyst will not have to be continually replaced. Separation of heterogeneous catalysts can be easily achieved using filtration. The aim of this
research is to produce an active, stable and reusable heterogeneous basic catalyst that operates at low temperature. FAME conversion should be the same as that
for homogeneous catalysts (although the rate may be reduced) in the same conditions, but the greatest issue has been found to be the chemical stability of the
catalyst. In this work, the catalytic performances of homogeneous and heterogeneous base catalysts in the transesterification of triolein are compared. The
quaternary ammonium functional group in liquid form is compared to a solid polymeric ion exchange resin acting as a substrate for the same group. This
functional group is expected to be stable to leaching and the FAME conversion between the liquid and solid quaternary ammonium functional group is identical.
References:
[1] Liu, Y., Edgar, L., Goodwin Jr., J.G., Lu, C. Journal of Catalysis, 2007. 246(2): p. 428-433.
[2] Shibasaki-Kitakawa, N., Honda, H., Kuribayashi, H., Toda, T., Fukumura, T., Yonemoto, T. Bioresource Technology, 2007. 98(2): p. 416-421.

170 Catalytic pyrolysis of biomass for the production of alternative fuels and chemicals: Effects of catalyst’s acidity
E.F. Iliopoulou a , * , K. Papazisi a , A.A. Lappas a and K.S. Triantafyllidis b
a Chemical Process Engineering Research Institute, CERTH, 570 01 Thessaloniki, Greece
b
Department of Chemistry, Aristotle University of Thessaloniki, 541 24 Thessaloniki, Greece
*Corresponding author. Tel: +30 2310498312, Fax: +30 2310498380, e-mail: eh@cperi.certh.gr
Background
Biomass is a renewable energy source expected to play a substantial role in the future global energy balance. It is capable of providing a wide range of liquid, solid and
gaseous raw materials utilized for the production of thermal and electrical energy, transportation fuels and chemicals. Among the various thermochemical conversion
processes of biomass, pyrolysis is considered to be an emerging technology for liquid oil (bio-oil) production, potentially used as a fuel or as a source of high value
chemicals. In order to minimize the undesirable properties of bio-oil (high viscosity, corrosivity, instability), its composition has to be fine-tuned. One of the most
promising processes to achieve this is the in-situ catalytic upgrading of biomass pyrolysis products 1,2 .
Results
In the present study several microporous (zeolites USY, H-ZSM-5 and Beta) and mesoporous (Al-MCM-41 and amorphous silica-alumina-ASA) aluminosilicate
materials have been tested as catalysts for biomass pyrolysis in order to identify the effect of acidic and porosity characteristics of the catalysts on the product yields
and selectivity. Almost all catalysts decreased the total liquid yield and increased the gaseous products and coke yield, in comparison to the non-catalytic pyrolysis,
mainly through hydrocarbon conversion reactions, such as cracking, dehydrogenation and cyclization/ aromatization. Concerning bio-oil composition, the use of USY
and Al-MCM-41 materials increased phenols production, while most of the catalytic materials reduced the fractions of undesirable oxygenates (alcohols, carbonyls
and acids) resulting in the production of a bio-oil with improved quality, in terms of stability, corrosivity and potential use as fuel or as a “green” feedstock to
conventional refinery processes. Variations in acidity (number, type and strength of acid sites) were determined by FTIR-adsorption of pyridine studies and TPD-NH 3
experiments. The acidity results in combination with the porosity characteristics of the catalysts were the basis for understanding the effects of various catalysts on the
product yields in bio-oil.
References
[1] E.F. Iliopoulou, E.V. Antonakou, S.A. Karakoulia, A.A. Lappas, I.A. Vasalos, K.S. Triantafyllidis, Chem. Eng. J. 134 (2007) 51.
[2] K.S. Triantafyllidis, E.F. Iliopoulou, E.V. Antonakou, A.A. Lappas, T.J. Pinnavaia Micropor. Mesopor. Mat. 99 (2007) 132.
179 Granulated Lithium Zirconate for CO 2 Sorption
H. Stephenson a , * , A. Lapkin b and A. Holt c
a
MEL Chemicals, PO Box 6, Lumns Lane, Swinton, Manchester M27 8LS, England.
b
University of Bath, Bath, BA2 7AY, England. c Catal International Ltd, Box 507, Sheffield, S10 3YT, England.
*Tel: +44 161 911 1179, Fax: +44 161 911 1052, e-mail: hazel.stephenson@melchemicals.com
Background
MEL is currently developing a range of products based on lithium zirconate using a novel patented process for use in a range of applications from adsorption
enhanced steam reforming to CO 2 capture from gas streams. [1] The products have been shown to be regenerable and have near stoichiometric CO 2 uptake at
400-550 C, with certain variants showing up to 10 wt% CO 2 uptake below 200 C. This work looks more closely at factors influencing the low temperature
uptake, and the effects of binder addition and granulation on the formulation of the final sorbent products.
Results
To prepare the granules ~500 g of melsorb 1597/03 powder was mulled with a liquid binder to produce a dough suitable for extrusion/granulation. The dough
was then granulated in a rotating mixer and dried at 80 C for 4 hours in a fan oven. The material was then crushed and sieved to produce 0.8-1.8 mm granules.
TGA analysis was then carried out using a Setaram instrument with air as purge gas and standard grade CO 2 (BOC) to measure CO 2 capacity and kinetics at
various temperatures. Activation was carried out at 750 ºC for minimum 6 hours in air.
Reference Binder Max
Sorption
Capacity
(wt%)
Temperature
of max rate of
sorption (°C)
Onset of
desorption
in the flow
of CO2 (°C)
1597/03 - 20.0 492 681
HS1716 AZC 25.5 155 / 456 733
HS1717 ZrO2 nano sol 23.7 317 / 453 733
HS1730 Diluted AZC 25.0 317 / 453 711
HS1731 Zirmel 1000 22.5 338 / 433 750
CO 2 wt% / -
35
30
25
20
15
10
5
0
0 5 10 15 20 25
In addition, reproducibility and optimisation of the chosen binder system will be reported, along with CO 2 breakthrough experiments and further
characterisation data including surface area, porosity, XRD and SEM.
References
[1] H. Stephenson, WO07023294 , Synthesis of lithium zirconate
HS1716
HS1717
HS1730
HS1731
800
700
600
500
400
300
200
100
0
Temperature / ºC

183 Bio-oil upgrading using platinum catalysts
C.A. Fisk a , T. Morgan a , M. Crocker a, *, C. Crofcheck b and S.A. Lewis c
a University of Kentucky Center for Applied Energy Research, Lexington, Kentucky 40511, USA; b Biosystems and Agricultural Engineering, University of Kentucky, Lexington,
KY 40546, USA; c Fuels, Engines and Emissions Research Center, Oak Ridge National Laboratory, Knoxville, TN 37932, USA
*Corresponding author. Tel: +1 859 257 0295, Fax: +1 859 257 0302, e-mail: crocker@caer.uky.edu
Background
Biomass can be converted into fuels and chemicals indirectly (by gasification to syngas followed by catalytic conversion to liquid fuels) or
directly to a liquid product. Direct thermochemical conversion processes include pyrolysis, high-pressure liquefaction, and solvolysis. The
crude bio-oils afforded by these processes are chemically complex and are typified by a high oxygen content. As a consequence, crude biooils
exhibit instability with respect to condensation reactions which lead to the formation of heavier compounds during prolonged storage.
In this context, we are studying new approaches for catalyst-assisted stabilization of crude biomass-derived pyrolysis oils, for the
ultimate production of fuels and high value chemicals.
Results
The complexity of bio-oils, together with the fact that they do not possess a single, standard composition, greatly hampers the study of
catalytic upgrading processes. With this in mind, a model bio-oil was employed in this study, designed to mimic the composition of a
typical softwood pyrolysis oil. Specific oil components comprised methanol, acetaldehyde, acetic acid, glyoxal, acetol, glucose, furfural,
guaiacol, vanillin and water. Upgrading experiments were performed under inert atmosphere at 350 °C in a slurry reactor, employing
either Pt or Rh catalysts. A variety of support materials were tested (metal oxides and activated carbon), with the metal loading being
fixed at 1 wt%. In general, Pt catalysts showed the most promising results, affording light oils with significantly reduced oxygen content.
Of the catalysts tested, Pt/Al2O3 was found to be the most active for deoxygenation, the oxygen content of the synthetic oil decreasing from
an initial value of 41.4 wt% to 2.8 wt% after upgrading. GC-MS analysis of the oil showed it to be highly aromatic, the major components
corresponding to alkyl-substituted benzenes and cyclohexanes. Gaseous products were also formed, consisting of CO2 as the major
product, together with lower yields of H2 and C1-C6 hydrocarbons. Based on the product spectrum, a reaction scheme is proposed in which
light oxygenates predominantly undergo reforming to CO2 and H2, with C-O bond breaking/hydrogenation (to afford alkanes) as a minor
pathway. In a parallel process, aromatics undergo C-O cleavage/hydrogenation, affording the observed benzenes and cyclohexanes. These
results suggest that liquid phase reforming may represent a viable technology for upgrading crude bio-oils.
186 Ni 5 P 4 , a Highly HDS Active Phase of Bulk and Silica-Supported Nickel Phosphide Catalysts
G. Berhault a,* , H. Loboué a , T. Cseri b , A.Lafond c , C. Geantet a
a Institut de Recherches sur la Catalyse et l’Environnement de Lyon, IRCELYON, UMR 5256 CNRS – Université de Lyon, Villeurbanne, 69100, France.
b IFP-Lyon, IFP, Direction Catalyse et Séparation, Vernaison, 69390, France
c Institut des Matériaux Jean Rouxel, IMN, UMR 6502 CNRS – Université de Nantes, Nantes, 44322, France
*Corresponding author. Tel: +33 472445320, Fax : +33 472445399, e-mail:.berhault@ircelyon.univ-lyon1.fr
Background
The declining quality of petroleum feedstock and the drastic regulations about the sulfur content of vehicle transportation fuels have triggered research about
more efficient hydrotreating (HDT) processes. In this respect, silica-supported nickel phosphides were found recently to be excellent HDT catalysts with
superior activities compared to the well-known (Ni)CoMo/Al 2 O 3 [1]. The activation of nickel thiophosphate precursors into nickel phosphides was used herein
as a fingerprint to determine the real nature of the active phase of both bulk and silica-supported nickel phosphide. Catalysts were characterized by TEM-EDS,
in situ XRD, magnetic susceptibility and EXAFS. Results reveal the presence of a Ni 5 P 4 phase more active than the commonly found Ni 2 P phase.
Results
The Ni-P phase diagram is quite complex with many Ni/P compositions going from Ni 3 P to NiP 3 . However, only three of them were reported to be stable under
hydrotreating conditions : Ni 2 P, Ni 12 P 5 and Ni 5 P 4 . While Ni 12 P 5 was recognized to be much less active than Ni 2 P, Ni 5 P 4 was rarely studied and its possible
contribution to the HDT activity was hardly examined. The activation of nickel thiophosphate precursor, NiPS 3 allows the possibility to synthesize different
nickel phosphide phases depending on the crystallinity of the thiophosphate compound. Using this approach, bulk Ni 5 P 4 was found to be six times as active as
bulk Ni 2 P for the HDS of thiophene (Ni 5 P 4 : 250 x 10 -8 mol/g Ni .s vs Ni 2 P: 40 x 10 -8 mol/g Ni .s). In a second step, studies were extended to silica-supported nickel
phosphide catalytic systems. By correlating EXAFS and TEM-EDS analyses to HDS activity results, it was found that optimized procedures of preparation led
to a highly dispersed active phase mainly composed of Ni 5 P 4 particles. Such an optimized catalyst was 50 % more active for the HDS of thiophene than
NiMo/Al 2 O 3 .
References
[1] S.T. Oyama, X. Wang, Y.K. Lee, W.J. Chun, J. Catal. 221 (2004) 263.

190 Experimental Study of Sulphur Impact on Biogas Catalytic Steam Reforming:
Deactivation and Regeneration of Nickel-based Catalysts
M. Ashrafi,*, C. Pfeifer, T. Pröll, H. Hofbauer
Institute of Chemical Engineering, Vienna University of Technology, Getreidemarkt 9/166, 1060 Vienna, Austria
Corresponding Author: Tel: +43 1 58801 15974, Fax: +43 1 58801 15999, e-mail: mashrafi@mail.zserv.tuwien.ac.at
Background:
Through biogas steam reforming H 2 -rich synthesis gas will be produced from which gas engines benefits in terms of higher efficiency and NO x emissions
reduction of more than 90% compared to direct combustion of raw biogas. Furthermore, pure hydrogen can be produced out of a renewable energy source.
The effect of H 2 S on the effectiveness and deactivation behaviour of Ni-based catalysts in terms of biogas steam reforming is experimentally studied in this
work. Various partial pressures of H 2 S, in the range of 15-145ppm, are introduced to the model biogas using a constant molar ratio of CH 4 /CO 2 =1.5. The feed
gas is led over a laboratory scale fixed bed reformer at atmospheric pressure in a temperature range of 700-900°C. The catalyst activity is characterized in
terms of methane conversion. Furthermore, a comparison of two different catalysts is carried out. In order to study the regenerate-ability of the catalyst the
effects of sudden sulphur removal from the feed gas, temperature enhancement and oxidative treatment are studied.
Results:
The results show that the catalyst resistance against H 2 S depends strongly on operating temperature. Initially the catalyst shows methane conversion rates of
more than 95%. The sulphur-poisoned Ni-based catalyst keeps an appreciable residual activity at 900°C being rather tolerant event towards higher
concentrations of H 2 S. At 700°C the catalyst poisoning is independent of H 2 S concentration (in the investigated range) and looses its activity totally even for
15ppm of H 2 S. The poisoning shows a strong dependency on poison concentration at 800°C. Based on these results, the activity of the catalyst will be regained
rather quickly when H 2 S is removed from the feed gas at 900°C. It is also found that H 2 S poisoned catalysts can effectively be recovered by increasing the
temperature. The extent of catalyst regeneration by H 2 S removal increases with increasing temperature. For practical operation with Ni-based catalysts and
biogas at small scale, temperatures of 900°C seem necessary for the catalytic reforming process.
193 Catalyst developments for ultra-deep hydrodesulfurization of gas oil
Koichi Segawa*, Qiang Gao, Christopher T. Williams
Department of Chemical Engineering, Swearingen Engineering Center
University of South Carolina, Columbia, SC 29208, USA
*Corresponding author, Tel: +1 803 777 4693, Fax: +1 803 777 0971, e-mail: kohichi@engr.sc.edu
Background
The exhaust gases from motor vehicles contribute to a large extent to air pollution through their contents of NO X and SO X , CO, hydrocarbons, and particulate
matters (PM). In addition, sulfur in fuels is a well-known poison for catalysts for clean-up exhaust gas devises. Those situations lead the governments of
numerous countries to adopt new regulations which aim at a drastic reduction of sulfur content in fuels (50 ppm or less by 2005; 10 ppm or less by 2009).
Results A one example, we have prepared TiO 2 -Al 2 O 3 composites by chemical vapor deposition technique using TiCl 4 as a precursor, and high dispersion of
TiO 2 over -Al 2 O 3 has been elucidated. NiMo/TiO 2 -Al 2 O 3 catalysts exhibit a much higher hydrodesulfurization (HDS) activity for 4,6-dimethylbenzothiophen
(4,6-DMDBT) compared to those supported on alumina or titania under mild operating conditions (573K, 3MPa). The product ratio results showed that TiO 2 -
Al 2 O 3 composites as a support for NiMo sulfide catalysts promotes the HDS pathway. The XPS investigations of the NiMo catalysts before and after
sulfidation suggested that the interaction between Mo and Al 2 O 3 is stronger than that between Mo and TiO 2 -Al 2 O 3 composite. XPS investigations also indicated
that molybdenum phases supported on TiO 2 -Al 2 O 3 composites present higher reducibility/sulfidability properties compared to those supported on alumina.
We have also studied the effect of chelating reagent on the sulfidation of NiMo catalysts supported on Al 2 O 3 . The reaction rate of NiMo catalyst with citric acid
shows much higher HDS activity than that of the catalyst without citric acid. In addition, the maximum HDS activity of both catalysts was obtained at around
0.3 of Ni atomic ratio. It should be noted that addition of Ni results in a significant increase in the HDS activity, and that the product selectivity at 50 %
conversion level shows the similar values (MCTH; 60 %, DMBP; 40 %) for all the catalysts investigated here. The results suggest that the active phases for
HDS of 4,6-DMDBT have a uniform structure (NiMoS phase) regardless of Ni/Mo ratio and the preparation method.
References
[1] Saih, Y., Nagata, M., Funamoto, T., Masuyama, Y., Segawa, K., Applied Catalysis A: General, 295, 11 (2005).
[2] Saih, Y., Segawa, K., Catalysis Surveys from Asia, 7, 235 (2003).
[3] Saih, Y., Segawa, K., Catalysis Today, 86, 61 (2003).
[4] Takahashi, K., Saih, Y., Segawa, K., Studies in Surface Science and Catalysis, 145, 311 (2003).
[5] Segawa, K., Takahashi, K., Satoh, S., Catalysis Today, 63, 123 (2000).

196 Activity and selectivity of PdZn-based catalysts in dimethyl ether autothermal reforming
M. Nilsson a* , P. Jozsa b , and L.J. Pettersson a
a Department of Chemical Engineering and Technology, KTH–Royal Institute of Technology, 100 44 Stockholm, Sweden
b Volvo Technology Corporation, SE-412 88 Göteborg, Sweden
* Corresponding author. E-mail: marita@ket.kth.se
Background
Dimethyl ether (DME), derived from biomass, has been proposed as an energy source for the future transport sector. DME is an interesting fuel candidate, both
as a diesel engine fuel and as a hydrogen carrier for fuel cells. The reforming temperature of DME (300-450 C) is lower than for conventional fuels such as
diesel and gasoline, which means that the concentration of CO in the reformate will be lower and, therefore, the fuel processor less complex. In the present
study, Pd-supported ZnO/ZnAl 2 O 4 /Al 2 O 3 mixtures have been evaluated for hydrogen generation by autothermal reforming (ATR) of DME. The objective of
the study was to correlate the catalytic properties of the materials to the activity and selectivity during DME ATR. The catalysts were characterized by CO
chemisorption, liquid nitrogen adsorption, temperature-programmed desorption of ammonia, temperature-programmed reduction, transmission electron
microscopy and X-ray diffraction. The catalysts were deposited on cordierite monolith substrates and the performances of the catalysts were evaluated in a
small-scale reactor. The results were compared to those obtained using a PdZn/-Al 2 O 3 catalyst.
Results
The results showed that Pd-based catalysts can be optimized for DME ATR with high selectivity to H 2 and CO 2 . It was found that impregnation of Pd onto
mixtures of ZnO, ZnAl 2 O 4 , and Al 2 O 3 , followed by reduction treatment, results in catalyst materials with high activity for the reactions involved. Higher
activity for the steam reforming reaction results in higher H 2 selectivity and can be attained by having a sufficient amount of acid sites available on the surface.
The less acidic oxide mixtures required higher temperatures for conversion. By physically mixing the catalysts with alumina, a higher activity was obtained,
but migration of metallic Pd to the added alumina contributed to a lowering of the CO 2 selectivity during reaction. High CO 2 selectivity was attributed to the
presence of a 1:1 PdZn phase. The CO generated during DME ATR is suggested to originate primarily from decomposition of methanol or dimethyl ether.
202 The Water Gas Shift activity of Pt, Pd, and Re on Pr-doped ceria
S. Srikhwanjai a , P. Nachai a , W. Wongphathanakul, and S. Hengrasmee a*
aDepartment of Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen, Thailand 40002
*Corresponding author. Tel: +66-0897134145, E-mail: sunhen@kku.ac.th.
Background
In WGS reaction, ceria is usually used as catalyst support due to its oxygen storage capacity. Sintering at high temperature
reduced this property and lowered the catalytic activity of the catalyst. Addition of zirconia to ceria was reported to improve ceria thermal
stability and oxygen storage characteristic [1]. Recently many material researches reported that addition of other lanthanide ions to ceria
lattice also caused defect and increased oxygen mobility of ceria [2-3]. They also pointed out that lanthanide ions-doped ceria should be a
better catalyst support than ceria. In this experiment we studied the effect of addition of Pr to ceria for WGS reaction. Different transition
metals (Pt, Pd and Re) were selected as catalysts for comparison.
Results
It was found that Pd and Re on Pr-doped ceria exhibited higher WGS activities than those of the same metals on pure ceria. Pt catalysts
on modified ceria did not show activity enhancement. Maximum activities for Pd and Re catalysts were found when ceria was doped with
5 wt% of Pr. XRD results indicated that Pr incorporated into ceria lattice to form solid solutions that maintained the fluorite structure of
CeO2 with increases in lattice constants. The single allowed Raman F2g mode of ceria was observed at 462 cm -1 . Addition of Pr to ceria led
to shifting of the Raman allowed mode to lower frequency and an apparent of small broad peak at 570 cm -1 . The additional peak confirmed
the existent of oxygen vacancies which were introduced into the lattice when Ce 4+ was replaced by Pr 3+ . The H2-TPR indicated that
addition of Pr to ceria led to lowering of reduction temperature of surface ceria for Re/Ce-Pr-O and Pd/Ce-Pr-O which in turn increased
the catalytic activity. For H2-TPR of Pt/CeO2 and Pt/Ce-Pr-O, Pt catalyzed the surface reduction of ceria and was more effective than Pr in
lowering the reduction temperature of surface ceria.
References:
[1] G.Vlaic, P. Fornasiero, S. Geremia, J. Kaspar, M. Graziani, J. Catalysis 168 (1997) 386.
[2] M.Y.Sinev, G.W.Graham, L.P.Haak, M.Shelef, J.Mater.Res. 11(1996)1960.
[3] Z. Song, W. Liu, H. Nishiguchi, A. Takami, K. Nagaoka, Y. Takita, Appl. Catal. A: General, 329 (2007) 86.

203 Deep Hydrodesulfurization of Diesel over Co/Mo Catalysts Supported on Oxides Containing Vanadium
C.M. Wang a , Ikai Wang a *
a Department of Chemical Engineering, National Tsing-Hua University, Hsinchu, Taiwan
* Corresponding author. Tel: +886 3 5713763, Fax: +886 3 5724725, e-mail: ikwang@che.nthu.edu.tw
Background
Generally, hydrodesulfurization (HDS) can lower the sulfur contents of various fuels in the petroleum refinery. However, the most refractory sulfur
compounds, typically dibenzothiophene(DBT) and alkylated DBT, still exist after desulfurization with most HDS catalysts. To remove sulfur from those
refractory molecules, reactions should be processed through the hydrogenation (HYD) pathways [1]. In this research, the supports of the HDS catalysts with
more HYD pathways are prepared by impregnating V 2 O 5 on -Al 2 O 3 or TiO 2 -ZrO 2 .
Results
Both -Al 2 O 3 and TiO 2 -ZrO 2 supports were modified by impregnating with a vanadium salt. The HDS of DBT tests indicated that the selectivity of HYD
pathway could be greatly improved by the modification. The ratio of pathway selection of HYD to DDS (directly desulfurization) over Co-Mo/(V 2 O 5 /TiO 2 -
ZrO 2 ) and Co-Mo/(V 2 O 5 /-Al 2 O 3 ) were 2.87 and 0.85, respectively, while the ratio of Co-Mo/-Al 2 O 3 was 0.18. The results of TPR suggested that CoO-MoO 3
was well-dispersed on the V 2 O 5 /TiO 2 -ZrO 2 support. Furthermore, the results of XPS indicated that the impregnated V 2 O 5 could affect the interaction between
MoS 2 and the supports. It could also make MoS 2 form active sulfur-coordinated sites for the HYD pathways. These active sites were the so-called brim sites in
the literature [2].
Justification for acceptance
We improve the HDS catalysts by pre-impregnating V 2 O 5 on the conventional supports, such as -Al 2 O 3 and TiO 2 -ZrO 2 . With these catalysts, we can
effectively remove sulfur from the refractory DBT through the HYD pathway. In addition, the catalysts with higher HYD activity can also raise the cetane
number of the diesel fuel.
References
[1] D.D. Whitehurst, T. Isoda, I. Mochida, Adv. Cata. 42 (1998) 345.
[2] H. Topsøe, Catal. Today, 107-108 (2005) 12.
215 Development of catalysts for hydrogen production from dimethyl ether
Kaoru TAKEISHI
Department of Materials Science and Chemical Engineering, Shizuoka University, Hamamatsu, 432-8561, Japan.
Corresponding author. Tel: +81-53-478-1159, Fax: +81-53-478-1159, e-mail: tcktake@ipc.shizuoka.ac.jp
Background
Dimethyl ether (DME) contains no poisonous substances, and burns without particulate matter (PM), meaning it is highly anticipated as a clean fuel of the 21st
century. DME can replace light oil and liquefied petroleum gas (LPG), and its physical properties resemble the latter. There is also the possibility that DME
infrastructures will be settled more rapidly than those of hydrogen and methanol, because existing LPG infrastructures can also be used for DME. With this in
mind, I have been studying the steam reforming of DME for hydrogen production.
Results
I have developed new catalysts for hydrogen production by steam reforming of DME. Cu-Zn/Al 2 O 3 catalysts prepared by a sol-gel method produce large
quantities of H 2 and CO 2 by DME steam reforming under lower reaction temperature. H 2 production by steam reforming of DME consists of two reaction
steps. The first reaction is hydrolysis of DME into methanol. The second reaction is steam reforming of methanol that produces H 2 and CO 2 . For this reason,
the mixed catalysts of DME hydrolysis catalysts and methanol steam reforming catalysts are used for hydrogen production by DME steam reforming.
However, the copper alumina catalysts prepared by the sol-gel method in single use are more excellent for H 2 production by DME steam reforming than the
mixed catalysts. The reason is that -Al 2 O 3 sites for DME hydrolysis and Cu sites for methanol steam reforming are co-existing closely on the catalyst
surface. The consecutive reactions smoothly occur, and hydrogen is produced more effectively over the sol-gel Cu/Al 2 O 3 in single use than over the mixed
catalysts. Addition of Zn, Mn, or Fe into Cu/Al 2 O 3 activates steam reforming of DME. The Cu-Zn(29-1wt.%)/Al 2 O 3 catalyst showed the excellent activity of
DME steam reforming; the DME conversion was 95%, H 2 yield was 95%, and CO concentration was 0.8 mol.%. I have developed new catalysts for H 2
production from DME, and the catalysts give us a great potential for H 2 supply from DME.
Justification for acceptance
DME is one of clean fuels of the 21 century, and hydrogen will be the cleanest fuel for environment. Therefore, hydrogen production from DME is very
important for reducing the global warming. Also, DME steam reforming will be performed at lower temperature than that of methane steam reforming.

230 Gold catalysts based on ceria doped with lanthanides for pure hydrogen production
D. Andreeva * , I. Ivanov, R. Nedyalkova, L. Ilieva
Institute of Catalysis, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria
*Corresponding author: Tel.:+359 2 979 2568: Fax: +359 2 971 2967,
E-mail: andreev@ic.bas.bg
Background
During the last years, it was found that gold catalysts are very promising in the low temperature WGS, which explain the dramatic growth of interest of the
researchers to this reaction, related mainly to its application in fuel cell power systems and the key role of this reaction in automobile exhaust processes since
the hydrogen produced is a very effective reductant for DeNOx. Recently, we have found evidences that gold/ceria catalysts are very active in WGS reaction at
low temperatures [1-3]. The nature of the support plays a decisive role on the activity and stability of this type of catalysts.
Results
The present study is focused on the modification of ceria by the addition of Me 2 O 3 , where Me= La, Sm, Gd and Yb on the structure and catalytic properties in
WGS. The mixed oxide supports were prepared by mechano-chemical activation. The amount of Me 2 O 3 was 10 wt %. The gold (2 wt %) was loaded by
deposition-precipitation method. The catalysts were characterized by XRD, TPR and Raman spectroscopy. After re-oxidation with air of the spent samples, the
catalytic activity was fully recovered and even it increases. The higher activity exhibit gold catalysts based on CeO 2 /Yb 2 O 3 and CeO 2 /Sm 2 O 3 comparing to that
of the catalysts on CeO 2 /Gd 2 O 3 and CeO 2 /La 2 O 3 support. By XRD the phase composition and the particle size of ceria were evaluated. The oxygen vacancies
formed in the defective CeO y structure were estimated by the FWHM (full width at half maximum) parameter of the dominant ceria line in the Raman spectra.
From the TPR spectra the H 2 consumption of the catalysts during the reduction process was calculated. The role of the defective ceria, including oxygen
vacancies in ceria is discussed.
References
[1] D. Andreeva et al., Catal. Today, 72 (2002) 51.
[2] D. Andreeva et al., Appl. Catal. A, 302 (2006) 127.
[3] D. Andreeva et al., Topics in Catal. 44 (2007) 173.
233 New active and selective Rh-REOx-Al 2O 3 catalysts for ethanol steam reforming
F. CAN, A. LE VALANT * , N. BION, F. EPRON and D. DUPREZ
Laboratoire de Catalyse en Chimie Organique (LACCO), Poitiers, France
* Corresponding author. Tel: +33549453908, e-mail :levalanta@yahoo.fr
Background
Ethanol steam reforming (ESR) is a very promising way [1] to produce hydrogen which is generally requires as the ideal environmental fuel to supply fuel
cells, and to answer the present challenge aiming to reduce the greenhouse gas emission. In the literature [2], it has been shown that the addition of an element
of rare earths group to steam reforming materials enhanced the performances of catalysts. The aim of this work is to determine for the first time the promoting
effect of a wide range of rare earth oxides (Sc, Y, La, Er and Gd) for ESR over Rh/Al 2 O 3 -based catalysts.
Results
BET, ICP, DRX, TPR, H 2 chemisorption measurements have been used to characterize the Rh-REOx-Al 2 O 3 catalysts (RE= Sc, Y, La, Er or Gd). It was shown
that the support rare earth addition amends shortly BET surface of the alumina and rhodium metallic accessibility.
Since it is known that the acido-basic properties of the support plays a critical role in steam reforming reactions, the acidity and basicity of the various supports
have been probed by pyridine and CO 2 chemisorption monitored by IR, respectively and discussed taking into account the catalytic results. The ESR tests were
performed at 675°C and 2 bars. The molar ratio R between water and ethanol was chosen equal to 4.
In this study, a direct correlation between basicity of the catalysts, characterized by carbonates infrared after CO 2 adsorption, and hydrogen yield has been
established. The most basic materials lead to higher yields. The characterization of the Lewis acidity by pyridine thermodesorption followed by infrared has
shown that the rare earth addition decreases the amount of strong acid sites. The amount of medium or low acid sites depends heavily on the rare earth addition.
These variations not only alter the amount of coke deposited after 8 hours of reaction but also its nature. Thus, the characterization of the catalysts after
reaction by temperature programmed oxidation (TPO) has shown that the unmodified alumina, coke was mostly in the very stable graphitic form, while on rare
earth modified catalysts, much was deposited on the metallic phase, and hence could be more easily eliminated. The amount of coke deposited on the metallic
phase is directly proportional to the basicity of the medium.
References
[1]: S. Cavallaro, V. Chiodo, S. Freni, N. Mondello, F. Frusteri, Appl. Catal. A 249 (2003) 119-128.
[2]: A.N. Fatsikostas and X.E. Verykios, J. Catal., 225 (2004) 439-452.

244 Strong effect of CO 2 and H 2 on the rate of water-gas shift reaction
T. Ishikawa a , K. Shimada b , O. Okada b , S. Tsuruya a , Y. Ichihashi a and S. Nishiyama a *
a Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University,
Rokkodai, Nada, Kobe 657-8501, Japan.
b Renaissance Energy Research Corporation, Kitahama, Chuo, Osaka 541-0041, Japan.
*Corresponding author. Tel: +81-78-803-6173, Fax : +81-78-803-6173, e-mail: nishieng@kobe-u.ac.jp
Background
The water-gas shift reaction is an important process for hydrogen production industry, because the rate of reaction for water-gas shift reaction is a most slowest
process among hydrogen production. To design highly active catalysts at lower reaction temperature than 473 K is very important for obtaining minimum space
and cost for hydrogen stations. Our preliminary experiments indicated the products of the water-gas shift reaction, CO 2 and H 2 , strongly affect the performance
of the reaction. It is markedly important to investigate inhibition effect of CO 2 and H 2 for design of the on-site type of hydrogen station.
Results
The reaction rate for water-gas shift reaction over Cu-Zn-Al mixed oxide catalysts was evaluated under various composition of mixture of CO, CO 2 , H 2 and H 2 O
at 233-273 K. It is indicating that the main products of water-gas shift reaction, CO 2 and H 2 , markedly suppressed the rate of the reaction. The reverse WGSR
did not significantly proceed on the Cu-Zn-Al catalysts at 233-273 K. The suppression of activity was due not to equilibrium limitation but to poisoning effect of
CO 2 and H 2 . The rate of the reaction can be expressed by a Langmuir-Hinshelwood type rate equation. The order of reaction for CO 2 and H 2 was negative. The
rate was proportional to squire of partial pressures of H 2 O and CO on the catalysts. The higher partial pressure of CO 2 is considered to form a cupper carbonate
species on the catalyst surface bringing about the poisoning. It should be noted that the design of a highly resistant catalysts against CO 2 is very important for
high performance WGSR. Effect of 4th component addition to Cu-Zn-Al catalysts will be discussed to synthesize CO 2 resistant catalysts at the conference.
Justification for acceptance
The commercial water-gas shift reaction is usually carried out under a low space velocity, SV< 2,000 h -1 . This would be ascribable to poisoning of the products
of WGSR. So it is obviously important to elucidate the reaction kinetic of WGSR and discuss poisoning behavior of CO 2 and H 2 .
249 High temperature steam reforming of methanol catalyzed over Cu/ZnO/ZrO 2
Yasuyuki Matsumura a, * and Hideomi Ishibe b
a National Institute of Advanced Industrial Science and Technology (AIST)
Kansai Center, Midorigaoka, Ikeda, Osaka 563-8577, Japan.
b Nippon Seisen Co., Ltd., Hirakata Plant, Ikenomiya, Hirakata, Osaka 573-8522, Japan.
*Corresponding author. Tel: +81-72-751-7821, Fax : +81-72-751-9623, e-mail: yasu-matsumura@aist.go.jp
Background
Methanol is a capable feedstock of hydrogen processors for fuel cells. Selective methanol steam reforming is usually carried out below 300°C over copper
catalysts such as Cu/ZnO/Al 2 O 3 to produce hydrogen, because the catalysts are easily deactivated and less selective (by-production of unfavorable carbon
monoxide) at the higher temperature. However, the operation temperature should be high in the processor due to the thermal efficiency and the compactness of
the endothermic reactor. Hence, a new active catalyst durable at a high temperature is required for the hydrogen production whose reactor can be heated
directly by combustion of the off-gas.
Results
Catalysts (Cu/ZnO, Cu/ZrO 2 and Cu/ZnO/ZrO 2 ) were prepared by a coprecipitation method. The catalytic activity of a commercial Cu/ZnO/Al 2 O 3 to the
methanol steam reforming was first tested at 400°C for 8 h. The initial methanol conversion was 82% and the conversion decreased with the time period of the
reaction to 51%, while the CO selectivity increased from 5.8% to 7.7%. No products except H 2 , CO 2 , and CO were detected. The reactants with the molar
ratio of CH 3 OH/H 2 O/Ar being equal to 1.0/1.2/0.5 were fed at the F/W of 95 dm 3 h 1 g 1 . At 250°C the initial conversion was 27%. The activity of
50%Cu/ZnO at 400°C was similar to that of Cu/ZnO/Al 2 O 3 , and the conversion decreased to 29% by repetition of the 8-h reaction. Addition of ZrO 2 to
Cu/ZnO improved the catalytic activity significantly. The initial activity of 40%Cu/40%ZnO/ZrO 2 was as high as 99% and that at 8 h was 95% (CO
selectivity, 6.1%). The activity gradually decreased with repetition of the 8-h reaction. The final conversion was 79% after the 4th run and the CO selectivity
decreased to 3.6%. The mean crystallite size of Cu particles was 20 nm at the initial stage and increased to 24 nm after the 4th run. The size of ZnO also
increased from 14 nm to 28 nm while the size of ZrO 2 was always 910 nm during the reaction. The BET surface area was 28 m 2 g 1 after the run. The area of
50%Cu/ZnO after the 2nd run was 15 m 2 g 1 , while the mean particle sizes of Cu and ZnO were 24 nm and 28 nm, respectively. The surface atomic
concentration of Cu in 40%Cu/40%ZnO/ZrO 2 after the 4th run was 17% and similar to that for 50%Cu/ZnO (21%). Hence, the high BET surface area shows
that the surface quantity of Cu is increased by the addition of ZrO 2 , and it probably causes the improvement in the activity. Since the activity of 30%Cu/ZrO 2
was steeply decreased from 67% to 22% in the 8-h reaction, ZnO is indispensable for the active catalyst. Presence of the fine ZrO 2 particles is considered to
stabilize the activity of Cu/ZnO in the high temperature reforming.
Justification for acceptance
Production of hydrogen from methanol is a clean process, but needs progress in the portability especially for fuel-cell applications such as electric vehicles.
Although the durability must be improved in the actual use, the Cu/ZnO/ZrO 2 catalyst shows possibility of the high temperature reforming, which realizes the
compact hydrogen processor.

256 Effect of structural and acidity/basicity changes of CuO-CeO 2 catalysts on their activity for water-gas shift reaction
P. Djinovi, J. Batista, J. Levec and A. Pintar*
National Institute of Chemistry, Hajdrihova 19, P.O. Box 660, SI-1001 Ljubljana, Slovenia
*Corresponding author. Tel: +386 1 4760283, Fax: +386 1 4760300, e-mail: albin.pintar@ki.si
Background CuO-CeO 2 catalysts are gaining popularity as very active materials for various reactions, including PROX, WGS reaction, ethanol and lower
hydrocarbon transformation into synthesis gas.
Results In this study, CuO-CeO 2 catalysts with a 10, 15 and 20 mol % Cu content were synthesized with a method of coprecipitation and calcined at
temperatures in the range of 400 to 750° C. Catalysts were characterized with BET, XRD, TPR/TPD analyses and subjected to pulse WGS activity tests in the
temperature range of 180-400° C. Catalyst stability under operating conditions, as well as pretreatment atmosphere effect on H 2 production were also
evaluated. Effect of catalyst acidity on WGS activity was also determined by means of NH 3 chemisorption/TPD. XRD results confirm average CeO 2 crystallite
growth with increasing calcination temperature and the presence of a solid solution [1]. H 2 -TPR/TPD curve deconvolution indicates that Cu reduction for
samples with the lowest Cu content proceeds stepwise (Cu 2+ Cu 1+ Cu 0 ), as opposed to direct Cu 2+ to Cu 0 reduction for those with a higher load. Final extent
of CuO and CeO 2 reduction is achieved at temperatures, lower than those applied during the WGS reaction, indicating constant catalyst composition during the
reaction. The extent of finely dispersed nanosized Cu species varied little with increasing Cu content, but CeO 2 reduction increased drastically [2], because of
more CuO-CeO 2 contact points, which are believed to initiate CeO 2 reduction. Samples with a 20 mol % Cu, calcined in the temperature range of 400-500° C
exhibited the highest WGS activity, while those with a 10 mol % Cu showed the lowest. Strong surface structure-activity dependence in WGS reaction was
observed for all catalyst samples. A trend in WGS activity among numerous and variously synthesized catalysts was successfully predicted with a product of
H 2 amount, consumed for partial CeO 2 reduction and average CeO 2 crystallite size 1/(d CeO2 ) 2 . An unexpected rise of activity of catalyst samples with 10 mol %
Cu calcined at 550 and 600° C, was observed and successfully correlated with an increase of surface acidity, which also coincides with increased Cu
dispersion at these calcination temperatures. CO 2 was found to strongly adsorb on the catalyst surface in the form of carbonates that caused a noticeable
decrease of catalyst activity [3], which could be only partly renewed by degassing. Hindrance due to carbon formation was not noticed.
References
[1] M.F. Luo, J.M. Ma, J.Q. Lu, Y.P. Song, Y.J. Wang, J. Catal. 246 (2007) 52; [2] A. Pintar, J. Batista, S. Hoevar, J. Colloid Interface Sci. 307 (2007) 145; [3] F. Marino, C. Descorme, D.
Duprez, Appl. Catal. B 58 (2005) 175.
269 Low temperature two-step process for hydrogen production
N. Ballarini, F. Cavani*, S. Passeri and L. Pesaresi
Dip. di Chimica Industriale e dei Materiali, ALMA MATER STUDIORUM – Università di Bologna
Viale del Risorgimento 4, 40136 Bologna, Italy
*Corresponding author: tel. & fax: +39 051 2093680, e-mail: fabrizio.cavani@unibo.it
Background
Hydrogen is a clean alternative fuel for energy production. In the recent years many processes for the production of hydrogen have been proposed, comprising
thermal, electrolytic and photolytic processes [1]. The thermal/catalytic processes are the most studied also because the necessary quantity of energy can be
obtained from renewable resources. Actually the steam reforming of natural gas at high temperature is the technology most used industrially for the production
of hydrogen [2]. In this work we report about a two-steps approach for the catalytic production of hydrogen from methanol and water.
Results
The two-steps catalytic tests were performed in a down-flow tubular reactor. The first step of the process is the reduction of the catalyst with methanol at
420°C. During this step methanol was converted with high yield to CO, CO 2 , CH 4 and H 2 . Also the accumulation of C on the solid was observed, the amount of
which was a function of the reduction degree of the catalyst. In the second step water is fed over the reduced catalyst, at 420°C. In this step hydrogen formed.
The catalyst used for the two-steps process was a spinel-type mixed oxide, CoFe 2 O 4 , synthesized with the co-precipitation method. The control of the
calcination temperature allowed the formation of samples having crystal size ranging from 17 to 50 nm. Thermal-Programmed-Reduction analysis with
hydrogen evidenced that the crystal size of the samples affected the reducibility of the ferrite. The reduction of the spinel led to the formation of a Co/Fe alloy
that however was fully reoxidized with water back to the ferrite. During three cycles of reduction and oxidation, the amount of hydrogen produced did not
change significantly.
References
[1] A. Haryanto, S. Fernando, N. Murali, S. Adhikari, Energy & Fuels, 19 (2005) 2098
[2] J. N. Armor, Applied Catalysis A: General, 176 (1999) 159

278 Stability of bimetallic monolithic catalysts in autothermal reforming of isooctane
N. Guilhaume a, *, L. Villegas b , F. Masset b
a Institut de recherches sur la catalyse et l'environnement de Lyon IRCELYON, UMR 5256 CNRS Université Lyon 1,
2 Avenue Albert Einstein, F-69626 Villeurbanne Cedex, France.
b PSA Peugeot Citroën, 2 Route de Gisy, F-78943 Velizy Villacoublay Cedex, France.
*Corresponding author. Tel: +33 472 445 389, Fax : +33 472 445 399, e-mail: Nolven.Guilhaume@ircelyon.univ-lyon1.fr
Background On-board hydrogen production by reforming of gasoline for fuel-cell powered vehicles enables a significantly more efficient energy utilization
than internal combustion engines. As monoliths are particularly suitable in automotive applications, the preparation, characterization and testing of monolithic
catalysts in autothermal reforming of isooctane (model compound of gasoline) has been investigated. Special attention was paid to the stability of catalysts
during long-term activity tests (up to 140 h), under temperature cycles and steep variations in the feed composition.
Results Rh/Al 2 O 3 , Ni/Al 2 O 3 and Ni-Rh/Al 2 O 3 catalysts were washcoated on cordierite monoliths (400 cpsi) according to a previously described
procedure [1]. SEM-EDS analyses of the bimetallic monolith showed a homogeneous distribution of Ni and Rh within the monolith axial direction, with
Rh/Ni= 7 at.%. XPS analyses revealed a strong Rh enrichment of the alumina washcoat surface in the radial direction, the Rh/Ni reaching 22-39 at.% in the
analyzed surface layer (5 nm). Tests in autothermal reforming of isooctane were performed at O/C=1 and H 2 O/C=2, which corresponds to the optimal reaction
conditions determined previously [2]. The Ni/Al 2 O 3 and Rh/Al 2 O 3 catalysts showed a similar activity, whereas the bimetallic Ni-Rh/Al 2 O 3 bimetallic catalyst
was clearly more active at low temperature, the reformate composition reaching the equilibrium composition in the whole 420-750°C temperature range. The
isooctane convention was always total and the products selectivity unchanged when the gas hourly space velocity was varied between 2340 and 23400 h -1
(referred to monolith volume). Measurement of the catalyst temperature when the O/C ratio was varied showed that thermoneutral conditions were obtained at
O/C=0.66, in agreement with thermodynamic calculations. In addition, the bimetallic catalyst showed a remarkable stability, the reformate composition
remaining perfectly stable after 140 h time-on-stream at 700°C. In order to simulate an accidental break off in the fuel supply, and consequently metals
oxidation due to catalyst exposition to oxidizing conditions, the isooctane feed was cut off for 30 min (leaving the oxygen, steam and inert flows unchanged at
700°C), then admitted again. The catalyst activity was unchanged, meaning that the metals are easily reduced in-situ without a specific activation procedure.
References
[1] L. Villegas, F. Masset, N. Guilhaume, Appl. Catal. A-Gen., 320 (2007) 43.
[2] L. Villegas, N. Guilhaume, H. Provendier, C. Daniel, F. Masset, C. Mirodatos, Appl. Catal. A-Gen., 281 (2005) 75.
280 Single stage bimetallic water gas shift conversion catalysts for fuel cell applications
K. Seshan * , K.G. Azzam, I. B. Babich, and L. Lefferts
Catalytic Processes and Materials, Faculty of Science & Technology, IMPACT, University of Twente, PO Box 217, 7500 AE, Enschede, The Netherlands
*Corresponding author. Tel: +31 53 4893254, Fax : +31 53 489 4683, e-mail: k.seshan@utwente.nl
Background
Supported noble metal catalysts are promising “single stage” water-gas-shift (WGS), CO + H 2 O = CO 2 + H 2 , to generate hydrogen for fuel cells because they
are robust, stable during start-up – shutdown cycles [1]. Among noble metals, Pt may be an appropriate choice due to availability and cost.
Due to the inability of Pt to interact with water [2], its combination with a hydrophilic oxide support is essential [2-4], where Pt activates CO and support
activates H 2 O. Two pathways for water activation on the support are proposed [3,4]. Water can either help re-oxidise the support in a red-ox cycle or form
hydroxyl groups which interact with adsorbed CO forming intermediate surface species, decomposition of which complete the WGS reaction. In this
communication, we report on the influence of oxide support on the WGS reaction with an aim to develop active and stable catalysts for single stage
commercial application in fuel cells.
Results
The mean Pt particle size was comparable in all catalysts (1.8 ± 0.2 nm). All the catalysts were selective to hydrogen; no CH 4 formation. The most active
catalyst was obtained with TiO 2 as support. Thus, support has an influence on the intrinsic activity of the catalyst.
Table 1 Pt Dispersions, Intrinsic WGS Activities for
Catalysts; Metal Loadings in All Cases were 0.5 wt%,
300 C, P = 2 bar, pCO 60 mbar, pH2O 1200 mbar,
pN2 1820 mbar, GHSV = 410,000 h -1
Catalyst H/Pt (%) TOF (s -1 )
Pt/ZrO2 60 2
Pt/CeO2 65 5
Pt/TiO2 60 7
Pt-Re/TiO2 65 11
Even though, Pt/TiO 2 catalyst is very promising, it lost about 30 -35 % of initial activity after 20
hours on stream. Detailed kinetic, in situ spectroscopic and catalyst characterization studies indicate
that sintering of Pt is the main reason for deactivation. Further, sintering of Pt is assisted by the g
catalytic composition containing Pt and Re on TiO 2 support (bi-metallic catalyst) has been developed.
This catalyst possesses higher activity than Pt/TiO 2 and is very stable for at least 20 h.
Kinetic and in situ spectroscopic studies indicate that the reducibility of the support, as well as stability
of intermediate formate and carbonate species contribute to the various WGS reaction pathways. Our
studies show that, for Pt/TiO 2 , both the associative formate route with a red-ox regeneration as well as the
classical red-ox ropresence of oxygenates such as formaldehyde. In order to improve the stability of
the catalyst, a new promisinute are possible WGS reaction pathways. Our results [5] indicate that Re anchored the Pt particles prevents sintering and provides
extra sites for H 2 O activation (rate determining step). In the Pt-Re/TiO 2 catalyst under WGS reaction conditions, rhenium is present at least partly as ReO x ,
providing an additional red-ox route for WGS reaction in which ReO x is reduced by CO generating CO 2 and re-oxidized by H 2 O forming H 2 . The Pt-Re
catalyst has high enough activity to meet the requirements (8 . 10 -5 mol H2 g -1 cat s -1 ) of 50kW fuel cell using 1kg catalyst.
References
[1] Olympiou, G.G.; Kalamaras, Ch.M.; Zeinalipour-Yazdi, C. D.; Efstathiou, A.M. Catal. Today, 2007, 127, 304-314; [2] Azzam, K.G.; Babich, I.V.;
Seshan K.; Lefferts, L. J. Catal., 2007, 251, 153-162 ; [3] Jacobs, G.; Graham, U.M.; Chenu, E.; Patterson, P.M.; Dozier, A.; Davis, B.H. J. Catal., 2005 229,
499-504; [4] Gorte, R.J.; Zhao, S. Catal. Today 2005, 104, 18-24; [5] Azzam, K.G.; Babich, I.V.; Seshan K..; Lefferts, L., J. Catal., 2007, 251, 163-174

288 Low temperature shift reaction catalyst : preparation, spectroscopic study and activity test
Karim H Hassan
Department of Chemistry, College of Science, University of Diyala, Baquba Iraq.
Corresponding author, Head of Chemistry Department , College of Science , University of Diyala, Baquba , Iraq, mobile 07901749122 ,
e-mail drkarim53@yahoo.com
Background
The CuOZnOAl 2 O 3 catalysts are very important, some of these catalysts are used in urea fertilizer industry for the low temperature, 180-260 C conversion
of CO to CO 2 in the presence of steam, the reaction known in industry as Low Temperature Water Gas Shift Reaction (LTS) reaction. Other types are used in
methanol production units from CO/H 2 mixture at low pressure of 70 bar and a temperature of 220-240 C and this will be very important when methanol will
replace oil fuel in the near future. As far as environmental catalysts are concerned these catalysts will play an important role to be use in removing the toxic CO
gas and converting it to CO 2 , also It can be used to purify exhaust gases delivered from vehicles during combustion. It composed of a mixture of the three
oxides with different proportions ratio which depends upon the operating conditions and the process used.The oxide composition used are quiet different,
coming from Cu : Zn : Al = 30 : 50 : 20 (atomic) for LTS reaction to 50 : 30 : 20 (atomic) for CH 3 OH synthesis. Any way the function of the catalyst depends
upon its composition ratio and the operating conditions of the process used. Several methods were experimented in the preparation of these catalysts such as
precipitation , kneading, impregnation and mechanical alloying etc… and the one used depends on the relative composition of the three oxides , the properties
of the catalysts, in addition to process needs required.
Results and justification
The catalyst with the chemical composition weight of 40 : 50 : 10 for the CuO : ZnO : Al 2 O 3 respectively was prepared from copper nitrate, zinc nitrate and
aluminum oxide using sodium bicarbonate as precipitating agents, followed by filtration , drying and calcinations steps. X-ray diffraction spectroscopic studies
of the prepared and commercial catalysts in addition to the catalysts performance confirm the structure of the catalyst. The results show the presence of CuO
and ZnO as separate oxide in addition of being fused mixed oxide. Formulation of the catalysts was achieved by mixing the calcined catalyst with graphite and
poly vinyl alcohol suspension. The mixture is then dried in oven at two step the first one at 110 C and the second one at 225 C . It is then converted to
5X5mm tablets using a high pressure press or tablet machine. Performance of the catalyst was done in a pilot plant unit using stainless steel reactor and using
CO/H 2 gas mixture as a feed. Gas chromatography analysis of the products showed a very good results in conversion and activity in addition to selectivity of
CO to carbon dioxide at relatively low temperatures by comparing it with other industrial catalysts used in such process.
References
[1] R.G.Herman, K.Klier, W.Simmons, B.P.Finn, J.B.Bulko, T.P.Kobylinski
J.Catalysis 56 (1979) 407
[2] S.Gusi, F.Trifiro, A.Vaccari, G.Del. Piero, J.Catalysis 94 (1985) 120
[3] R.H.Hoppener, E.B.M..Desburg J.J.F.Scholten, Applied Catalysis 25 (1986)109
[4] H.Fukui, M.Kobayashi, T.Yamaguchi, H.Kusam, K.Sayama, K.Okabe, H.Arakawa, Studies in Surface Science and Catalysis 114 (1997) 529
321 Extractive Regeneration of Lipophilic Amine CO 2 Absorbent
Y.H. Tan*, R. Misch, D.W. Agar
Lab. of Technical Chemistry B, Dortmund University of Technology, Emil-Figge-Str. 66, 44227 Dortmund Germany
* Corresponding author. Tel: +49 231 7552334, Fax: +49 231 755 2698, e.mail: yudy-halim.tan@bci.uni-dortmund.de
Background
A new class of amine absorbent for CO 2 removal has been investigated. This class of amine is initially present as a biphasic liquid solutions turning into a
homogeneous liquid phase with increasing CO 2 loading. During regeneration the regenerated amine forms an upper organic layer as a result of thermally
induced phase separation and extracts the remaining amine out of the residual loaded aqueous solution. Extensive regeneration can thus be achieved even at
temperatures well below 100°C. A novel regeneration method discussed here is investigated further to reduce the regeneration temperature to temperatures
below 80°.
Results
Reactions between CO 2 and amine result in formation of ionic species [1], which are more stable in a
polar environment. Due to the unique properties of lipophilic amine, the free lipophilic amine in the
loaded solution can be extracted into additional hydrophobic solvent, destabilising the equilibrium in
the loaded solution and resulting in release of CO 2 without a change in temperature. The loaded 3M
1:3 N,N-Dipropylamine to N,N-Dimethylcyclohexylamine, a thermomorphic secondary/tertiary amine
mixture previously studied was selected as the test system. The experimental results with various
hydrophobic solvents depicted in Fig. 1 demonstrate the feasibility of the concept. The regeneration
was carried out at 40°C under atmospheric condition in a single stage equilibrium step. A high degree
of regeneration approaching 65% with partitioning of amine approaching 70% in favour of the organic
phase was obtained for n-pentane. By utilising counter current arrangements, the degrees of
regeneration and amine recovery may be enhanced still further.
Reference: [1] W.J. Choi, K.C. Cho, S.S. Lee, Green Chemistry 9 (6) (2007) 594-598.
Methy-tert-Buthylether
2-Methyl-Butane
2-Methyl-2-Butene
Cyclopentene
n-Pentane
Cyclopentane
3-Methyl-Pentane
n-Hexane
0 10 20 30 40 50 60 70
Values
Amine Extracted [%]
CO 2 Released [%]
Fig. 1: CO 2 regeneration performance with various
solvents at single stage equilibrium

329 Hydrogen from biomass derived oxygenates – steam reforming of acetic acid over supported Nickel-catalysts
B. Matas Güell*, K. Seshan and L. Lefferts
Catalytic Processes and Materials, University of Twente, PO Box 217, 7500 AE Enschede, The Netherlands
*Corresponding author. Tel: +31534893536, Fax : +31534894683, e-mail: b.matasguell@tnw.utwente.nl
Background Environmental friendly energy is a major goal in our society. Over the past few years, hydrogen has aroused tremendous interest as an energy
carrier especially if it is produced from renewable feedstock. Currently, one of the limitations of hydrogen generation is that it is based on fossil fuels, leading
to a net production of greenhouse gases. Thus, the use of biomass as alternative source of hydrogen, with its CO 2 -neutral impact, will play an important role in
the coming future. Steam reforming of liquefied biomass (bio-oil) is a promising route for hydrogen generation. However, the development of active and stable
catalyst for this process is severally hindered by oligomers accumulation on the catalyst, leading to catalyst deactivation. The strategy to overcome this
problem is to simultaneously prevent oligomers accumulation and keep the catalyst surface clean during reaction.
H2 Yield (%)
100
80
60
40
20
0
0 6 12 18 24
reaction time (h)
Results The aim of this study is to develop active and stable catalysts by minimizing coke
accumulation. The strategy is to enhance steam reforming activity, the limiting step for which
is activation of water, and facilitate coke/oligomer precursor reforming.
Supported nickel catalysts have been studied because (i) unlike Pt, Ni can interact with water
at steam reforming conditions providing an additional route to steam activation and (ii) the
support, ZrO 2 , was promoted by potassium and lanthanum. The alkali was added to improve
coke gasification by enhancing water activation and lanthanum doping to form oxygen
containing species during reaction, which could enhance coke combustion.
Catalysts promoted with La and K show excellent activity and good stability (see Figure 1) and
show promise for the generation of hydrogen from biomass. Kinetic and mechanistic aspects of
Figure 1. Hydrogen yields vs. time of 3.5%Ni/ZrO2, () 3.5%N
the catalysed reaction will be discussed.
La-ZrO2 () 3.5%Ni/ K-ZrO2, ()3.5%Ni/K-La-ZrO2 a
334 Nano-particle metal sulfides for ultra-deep HDS of diesel fuels
Zongxuan Jiang, Lu Wang, Can Li*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
*Corresponding author. Tel: 86-411-4379070, Fax: 86-411-4694447, e-mail: canli@dicp.ac.cn
Background
Developing the hydrodesulfurization (HDS) catalysts with the super high activity has been a challenging project for achieving the ultra-deep desulfurization of
diesel fuels [1]. Here, we report a surfactant-assisted co-precipitation method for the preparation of unsupported Ni-Mo-W sulfide catalysts. The catalysts exhibit
super high HDS activity for the real diesel up to 7.5 times excelling the conventional commercial catalysts. The sulfur level of the diesel fuels can be decreased to
less than 1 ppm from 1400 ppm under the conventional operating conditions.
Results
A series of Ni-Mo-W sulfide catalysts were prepared with the different solvents and surfactants to investigate the effect of the catalyst properties on the
HDS activity of Ni-Mo-W sulfide catalysts. The HDS catalytic activities of the sulfide catalysts were evaluated in a flow fixed-bed micro reactor. The sulfur
content of the desulfurized diesel is reduced to less than 1 ppm from 1400 ppm.
A model fuel containing 4,6-DMDBT in decalin was used to test the HDS activity and to calculate the 4,6-DMDBT HDS reaction kinetic parameters for
the catalysts. The catalysts also exhibited a higher intrinsic HDS activity. It is found that the overall rate constants for HDS reaction of the catalysts showed
about 3.0 times higher than that of the commercial catalyst.
The catalysts were characterized by XRD, TEM, TPR, and XPS. The catalysts exhibit a uniform distribution of nanoparticles with the size of about 20 nm and
possibly forms some composite sulfide active phases with the average slab length of 2-5 nm and the average stack layer number of 4-8.
Justification for acceptance
The nano composite sulfide catalysts were synthesized through using a special method. These catalysts demonstrated an excellent HDS activity for the
real diesel fuels, which is about 7 times higher than the conventional commercial catalysts, and the ultra-low sulfur diesel (< 1 ppm sulfur) can be obtained.
References
[1] D. Genuit, P. Afanasiev, M. Vrinat, Journal of Catalysis, 235 (2005) 302.

335 Ultra-deep desulfurization of fuels by emulsion catalysis
Can Li*, Zongxuan Jiang, Jinbo Gao, Hongying Lu, Yongna Zhang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
*Corresponding author. Tel: 86-411-4379070, Fax: 86-411-4694447, e-mail: canli@dicp.ac.cn
Background
Although the conventional hydodesulfurization (HDS) can remove the majority of sulfur-containing molecules in fuels, 4,6-dimethyldibenzothiophene and
their derivatives are very difficult to be removed via the conventional HDS [1]. Oxidative desulfurization is one of the most promising ultra-deep desulfurization
methods. Here, we report the application of emulsion catalysts in ultra-deep oxidative desulfurization of fuels. The catalysts demonstrate high performance
(96% efficiency of H 2 O 2 , and ~100% selectivity to sulfones).
Results
We have developed a series of emulsion catalysts, which are composed of the quaternary ammonium salt cations and heteropolymetalate anions. The
catalysts are assembled at the interface of two immiscible liquids and form emulsion droplets. These emulsion droplets act as a homogeneous catalyst to
efficiently oxidize the sulfur-containing molecules to sulfones in diesel.
As an example, the catalyst, [C 18 H 37 N(CH 3 ) 3 ] 4 [H 2 NaPW 10 O 36 ], in the W/O emulsion system exhibits very high catalytic activity such that all sulfurcontaining
compounds in either model or real diesel can be selectively oxidized into their corresponding sulfones using hydrogen peroxide as an oxidant. The
sulfur level of a prehydrotreated diesel can be lowered from 500 to 0.1 ppm after oxidation and then extraction, whereas the sulfur level of a straight-run diesel
can be decreased from 6000 to 30 ppm after oxidation and extraction.
Justification for acceptance
The amphiphilic catalysts assembled at the interface of emulsion droplets, which can be separated easily from reaction systems, shows high selectivity and
activity in the oxidation of sulfur-containing molecules to sulfone. The sulfur level in diesel is reduced to only a few ppm from several hundred ppm using the
oxidation/extraction approach.
References
[1] C. Li, Z.X. Jiang, J.B. Gao, Y.X. Yang, S.G. Wang, F.P. Tian, F.X. Sun, X.P. Sun, P.L. Ying and C.R. Han, Chem. Eur. J., 10(2004) 2277.
338 Water gas shift reaction over tungsten carbides for CO removal
Tsutomu Kakinuma and Masatoshi Nagai*
Graduate School of Bio-applications and Systems Engineering,Tokyo University of Agriculture and Technology,2-24 Nakamachi, Koganei, Tokyo 184-
8588, Japan
*Corresponding author. Tel/Fax: +81 42 388 7060, e-mail: mnagai@cc.tuat.ac.jp
Background
The Polymer Electrolyte Fuel Cell (PEFC) is being developed for both transport and stationary applications at low temperatures. Hydrogen in the reforming
gas is supplied to the PEFC, but contains 1020 percent CO. The water-gas shift reaction (WGSR) is effective in reducing CO from a few percent in the
reforming gas to below a ppm level. In a previous paper [1], tungsten carbide has been used a WGSR catalyst: the 1123 K-carburized catalyst was more active
than the 1073 K- and 1173 K-carburized catalysts. In this study, tungsten carbide was selected from the various transition metal carbides due to its strength at
high temperature, high melting points, and wear resistance make it an obvious candidate for many commercial applications.
Results
The MoW carbide catalysts (Mo:W=0, 0.1-0.9) were prepared in a stream of 5-20%CH 4 /H 2 . The tungsten carbide catalysts were prepared and characterized
using TPC, TPR, and TPO, and tested for WGSR at low temperature (453 K) with respect to the CO conversion. The tungsten carbide catalyst carburized in a
stream of 20%CH 4 /H 2 exhibited no activity, and the TPR analysis showed that the sample was covered by Graphitic Carbon. But the catalyst carburized in a
stream of less than 5%CH 4 /H 2 has activity (CO conversion; 21%). The XRD analysis showed that the catalysis structure was composed of WC and -W 2 C, and
dominant structure was WC. The TPO analysis revealed that -W 2 C on the WC was active species. The addition of 50, 70, and 90%Mo to tungsten carbide
increased activity. The activity of the W-Mo carbide catalysts was correlated with the BET surface area, except for the addition 90%Mo to tungsten carbide.
From the XRD and TPC analysis, the addition of 50, 70%Mo to tungsten oxide had the W-Mo bimetallic oxide (W 0.71 Mo 0.29 O 3 ).
Reference
[1] M. Nagai, T. Kakinuma, K. Matsuda, J. New Materials Electrochem. Systems 10 (2007) 217.

342 Experimental and Numerical Investigation of Catalytic Partial Oxidation of Higher Hydrocarbons over Rhodium coated Catalysts
M. Hartmann*, L. Maier, H. D. Minh and O. Deutschmann
Institute for Chemical Technology and Polymer Chemistry, Universität Karlsruhe (TH), Kaiserstraße 12, 76128 Karlsruhe, Germany
*Corresponding author: Tel: +49 7271 608 6646, Fax: +49 7271 608 4805, e-mail: Hartmann@ict.uni-karlsruhe.de
Background
Hydrogen and synthesis gas, produced on-board by Catalytic Partial Oxidation (CPOX) of hydrocarbons such as gasoline and diesel fuels, can not only be used
as fuel for fuel cells (PEM and SOFC, resp.) with a better energy utilization than by conventional combustion [1, 2]. It can also serve as additive to the internal
combustion engine during the cold start-up periods, which drastically reduce the formation of nitrogen oxides, and for exhaust-gas after-treatment through
selective catalytic reduction (SCR) of NO x . Optimization and reliable application of on-board CPOX reactors calls for an understanding of the complex
chemistry in those reforming processes based on well-defined experiments and detailed modeling and simulation.
Results
This paper presents both new experimental results for CPOX of gasoline surrogates in a monolithic honeycomb structure coated with rhodium and newly
developed models for the description of the reactive flow and the heterogeneous reactions on the catalyst. Transient and stationary investigations of CPOX with
various higher hydrocarbons and fuel surrogates have been performed on rhodium coated monoliths. Since fragmentation and condensation impede mass
spectrometry, a combined method of simultaneously applied analysis tools (FT-IR, MS, GC/MS, Magnos) have been used. By this combined method, the
instantaneous exploration of the reactive flow with closed carbon, hydrogen, and oxygen balances is possible and allows time resolved monitoring of more than
10 major species at closed balances. Moreover, a kinetic model is presented for CPOX of higher hydrocarbons for reformate / hydrogen production considering
detailed mechanisms for the reactions in the gas phase and on the surface at transient and steady-state reaction conditions. The gas phase chemistry model for
higher hydrocarbons consists of over three thousand reactions among approximately four hundred species. The heterogeneous chemistry is modeled by a set of
elementary reactions representing the molecular behavior for the smaller hydrocarbons (C 1 -C 3 ) and lumped steps for adsorption of larger hydrocarbons
assuming that their adsorption quickly leads to the smaller molecules that are explicitly described by the mechanism. The interplay between heterogeneous and
homogeneous reactions and the interaction between gas phase and surface chemistry were studied.
References
1. J.R. Salge, B. J. Dreyer, P.J. Dauenhauer, L.D. Schmidt, Science, 315, 801-804 (2006).
2. G.J. Panuccio, B. J. Dreyer and L.D. Schmidt, AICHE Journal, 53, 187-197 (2007).
3. H. D. Minh, H. G. Bock, S. Tischer, O. Deutschmann, AIChE J., submitted.
4. O. Deutschmann, S. Tischer, S. Kleditzsch, V.M. Janardhanan, C. Correa, D. Chatterjee, N. Mladenov, and H. D. Minh, DETCHEM Software Package, 2.1 ed,
www.detchem.com, Karlsruhe (2007).
366 Study of Rh-doping on Ni-based supported catalysts for CPO of CH 4
V. De Grandi a * , V. Dal Santo b , P. Benito c , A. Vaccari c and R. Psaro b
a Dip. CIMA, Università degli Studi di Milano, Milan, Italy
b ISTM-CNR, Milan, Italy
c Dip. Chimica Industriale e dei Materiali, Università degli Studi di Bologna, Italy
*Corresponding author. Tel: +39 02 50314384, Fax: +39 02 50314405, e-mail: valentina.degrandi@unimi.it
Background
Catalytic partial oxidation of methane (CH 4 -CPO) is considered a promising solution for the development of delocalized small-scale hydrogen production
plants. Nickel based catalysts are active, and cheaper than noble metals based ones, but suffer deactivation by coke deposition. One way to overcome such
disadvantage is represented by doping with very small amounts of noble metals able to prevent coke formation.
Results
Ni-based hydrotalcite-type catalysts were doped with low amounts of rhodium by CVD of Rh(acac)(CO) 2 (Ni=2 and 8% wt; Rh=0.18% wt.). They were tested
in CH 4 -CPO reaction and compared with similar catalysts prepared by co-precipitation, showing good performances both in activity and selectivity. The effect
of Rh doping was investigated on fresh and aged samples by different techniques (XRD;CO-DRIFTS-QMS; TPR).
The addition of Rh results in an increase in Ni dispersion ascribable to the formation of a RhNi alloy [1], in which superficial segregation of Rh inhibits Ni
particles growth and promotes reduction due to electronic effect. However the effect of Ni loading is determining for formation and growth of particles since
dispersing effect of Rh results less evident in high-loaded samples. Both fresh and aged CVD catalysts prepared at the same loading result quite similar. In fact
CO-DRIFT spectra show how aging processes do not deeply modify the structure. An increase of particle sizes at higher Ni loading is confirmed and also in
this case the possible dispersing and reducing effects from Rh addiction were quite overturned in 8% Ni-Rh samples. Particles size determination is currently
under investigation by XRD.
References
[1] M. Nurunnabi, Y. Mukainakano, S. Kado, B. Li, K. Kunimori, K. Suzuki, K. Fujimoto, K. Tomishige, Applied Catalysis A: General 299 (2006) 145.

374 Catalytic activity in WGS reaction of gold catalysts supported on mixed ceria-titania oxides:
role of the calcining temperature of the support
F. Vindigni a* , M. Manzoli a , A. Chiorino a , T. Tabakova b , V. Idakiev b , F. Boccuzzi a
a Department of Inorganic, Physical and Materials Chemistry and NIS Centre of Excellence, University of Torino, via P. Giuria 7, 10125 Torino, Italy
b Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria,
* Corresponding author:Tel: +39 011 6707540, Fax: +39 011 6707855, e-mail: floriana.vindigni@unito.it
Background
Ceria containing gold catalysts are very active for the WGS reaction [1]. However, deactivation by the blockage of the active sites by carbonates and/or
formates formed during the reaction occurs [2]. In order to optimize the performances of these catalysts and to understand if the conditioning of the CeO 2
surface by the addition of other constituents could be a solution to the deactivation, Au/CeO 2 -TiO 2 (1:1) catalysts were prepared, tested in the WGS reaction
and carefully compared with the pure ceria catalyst by HRTEM and FTIR techniques.
Results
The catalysts were prepared by deposition-precipitation of Au on mixed ceria-titania
calcined at 400°C, 500°C, 600°C and 700°C, to investigate the effect of the calcination
temperature. Recent work [3] has shown that the Au dispersion is different on Au/CeO2 and
on gold catalysts on the mixed oxide. TheAu/CeO2-TiO2 samples with the supports calcined
at 400°C and 500° C showed a catalytic activity similar to the pure ceria catalyst (Fig. 1).
On the contrary, the activity of Au supported on CeO2-TiO2 calcined at 700°C decreases
above 200°C. Interestingly, Au on the mixed oxide calcined at 600°C exhibits the highest CO
conversion between 100°C and 250°C. A HRTEM and FTIR characterisation will be
presented to study the nature of the promising low temperature activity of the catalyst with
the support calcined at 600 °C. FTIR measurements before and after the reaction, using CO
as probe molecule at 120 K have been undertaken
CO conversion, %
WGS equilibrium
100
80
60
Au/CeO 2 -TiO 2 (400°)
Au/CeO 2 -TiO 2 (500°)
40
Au/CeO 2 -TiO 2 (600°)
Au/CeO 2 -TiO 2 (700°)
Au/CeO 2
20
100 150 200 250 300 350
Temperature, o C
References:
[1] T. Tabakova, F.Boccuzzi, M. Manzol, i J. W. Sobczak, V. Idakiev, D. Andreeva, Appl. Catal., B, 49 (2004) 73.
[2] C. H. Kim, L. T. Thompson, J. Catal., 230 (2005) 66 and references therein.
[3] F.Vindigni, M. Manzoli, A. Chiorino, T. Tabakova, F. Boccuzzi, J. Phys. Chem B, 110 (2006) 23329.
387 Industrial Development of FCC Catalyst for Increasing Diesel Yield and Reducing Olefins in Gasoline
Qin SongYin Jiudong*
Catalyst Plant, Lanzhou Petrochemical Company, PetroChina, No.10, Yumen St. Xigu, Lanzhou, Gansu, 730060 P.R.China.
*Corresponding author. Tel: +86 9317934704, Fax : +86 931 7932804, e-mail: yinjiudong@petrochina.com.cn
Background About 80% of gasoline in China is coming from FCC units in refineries. The average of olefins contents in it is being measured between 40%-
60% due to the heavy feeding of the units. At the same time, over 40% of the total diesel demand in china is fulfilled by FCC units also. Along with the
booming of fuel consumption in China, the environmental problems resulted from vehicle discharge is getting more and more concern. Olefins content is
restricted by clean fuel standard in china at no more than 35%.
Results A new FCC catalystID-RO catalystto both reduce olefins content in gasoline and increase the diesel yield of the FCC unit at the same time has
been developed successfully by PetroChina and was put in to commercial scale production and application in order to meet the increasingly constricted
national requirements of gasoline standard and optimize the economic effect of customer oil refineries. Heavy oil conversion can be increased and excessive
cracking of middle distillate can also be restrained effectively at the same time by this catalyst which is composed of new type of active component (with
effective activity for hydrogen transfer and high diesel selectivity [1] ), optimized macro-pore matrix and shape selective zeolite. It was showed by medium-sized
experiment results that diesel yield had increased by 2% and the olefins in gasoline had decreased by 8%-12% after the use of ID-RO catalyst when compared
with olefins reducing catalysts by the others. A significant industrial application result showed that over 10% of olefins in gasoline had been reduced when both
the yield of diesel and the RON of gasoline were being kept in a high stable level and an ideal product distribution had been achieved in this industrial
application in a refinery located in the northeastern of China. The comprehensive reaction performances of the olefins reduction catalyst had been improved
with good social and economic effects obtained.
Justification for acceptance By the help of creaking level control and other technology innovations, this catalyst not only provide a right solution of both the
demand of diesel yield and olefins contents in gasoline, but also the methodology to develop more environmental friendly catalysts.
References
[1] J. Miller, P. Hopkins, B. Meyers, Appl. Catal. A: General, 1996, 136(1):29-48

400 Vanadium-molybdenum based catalysts for residue hydrodemetallation
Background
D. Soogund a , A. Daudin a,* , B. Guichard a , M. Digne a , D. Guillaume a , C. Lamonier b and E.Payen b
a IFP-Lyon, BP n°3, 69390 Vernaison, France, b Unité de Catalyse et de Chimie du Solide, Bât. C3, 59650 Villeneuve d'Ascq, France
*
Corresponding author : Tel : +33478022989, Fax : +33478022066, e-mail : antoine.daudin@ifp.fr
With the increasing production of low quality crude oil and heavy petroleum streams (high sulfur and Ni+V contents), and in front of more stringent
environmental specifications [1], more active and more stable hydrotreatment catalysts are required. As shown in the literature [2], ex-porphyrin vanadium
deposit during hydrodemetallation (HDM) reactions can generate an interesting catalytic activity. Nevertheless results and conclusions remain contradictory for
the activity levels, as well as for the exact role of vanadium. HDM catalysts are usually Mo based catalysts supported on macroporous alumina. In order to
(3+x)-
understand the role of vanadium and its interaction with Mo atoms, mixed heteropolyanion (HPA) precursors PMo (12-x) V x O 40 have been prepared [3] and
deposited by impregnation Activity measurements on model and on real feedstock have been performed after standard sulfidation step.
Results
Solutions containing Keggin phosphomolybdenum heteropolyanions (HPA), in which molybdenum is partially substituted by vanadium (PMo (12-x) V x O (3+x)- 40 ),
have been prepared for the synthesis of HDM catalysts according to three different degrees of substitution of vanadium desired (x=1, 3 and 6). The intense
band at 990 cm -1 with a shoulder at 970 cm -1 corresponding to the Keggin-like structure was identified by Raman spectroscopy for the three solutions. 31 P and
51 V NMR allowed us to identify a single species, PMo 11 VO 4- 40 , for the monosubstituted solution, whereas several species in equilibrium with different degrees
of substitution were identified for the other solutions (x=3 and 6). Solutions were then impregnated on an alumina support and the different preparation steps
were followed by Raman spectroscopy. On dried precursor, a part of the Keggin HPA is preserved and lacunar Keggin structures (PX 11 O 34 and PX 9 O 39 where X
= Mo, V) are also observed. After calcination, the Keggin structure is partially decomposed. After sulfidation, the catalysts showed mild performances during
toluene hydrogenation tests at low concentrations of vanadium and the catalytic activity increased with the loading in vanadium. During tests on real feedstock
interesting HDM activity were observed compared to reference promoted and non-promoted catalysts (Mo and NiMo/Al 2 O 3 ). We can conclude that vanadium
does not have a promoter role for HYD reactions but it may promote HDM. In particular, HDNi activity scale is the following : MoV = NiMo > Mo.
References
[1] Rapport EIA : International Energy Outlook 2007, Chapter 3: Petroleum and Other Liquid Fuels, Energy Information Administration,
www.eia.doe.gov/oiaf/ieo/pdf/0484(2007).pdf
[2] Hubaut R., Applied Catalysis A : Gen., 322 (2007) 121.
[3] Odyakov V.F., Zhizhina E.G., Maksimovskaya R.I., Matveev K.I., Kinetics Katalysis., 36 (1995) 795.
402 Promoting and Support effect in HDO of Guaïacol on CoMoS catalysts
Bui Van-Ngoc, Laurenti Dorothée*, Geantet Christophe
IRCELYON, UMR5256 CNRS-Univ. Lyon1, 2 av. Albert Einstein, 69626 Villeurbanne, France
*corresponding author: tel: +33 472445327-fax: +33 472445399- dorothee.laurenti@ircelyon.univ-lyon1.fr
Background: The limited resources of crude oil, the expanded demand for fuel during these last years and the new environmental standards on the greenhouse
gas emissions arouse a strong interest to develop the use of biomass [1]. New biofuels obtained from pyrolysis or high pressure liquefaction of wood contain
high oxygen proportion which confers on these bio-oils some deleterious properties. Their practical use thus asks for a treatment of hydrodeoxygenation
(HDO) which consists in breaking the C-O bond of an organic molecule by hydrogen.
Results: The object of this study is to describe the use of conventional CoMoS catalysts in the HDO of Guaiacol chosen as model molecule since phenolic
compound was considered as one of the most refractory compound for HDO [2]. Experiments were performed at 573 K and 4 MPa of H 2 in a continuous fixed
bed reactor in the presence of H 2 S (100 ppm). The reactive partial pressure was controlled by a condenser-saturator system to attain to 2,7 KPa in the reactor.
Products distribution was analyzed on line by FID-GC chromatography. Contact time was varied in order to get a wide domain of conversion. A strong support
effect has been observed considering supported catalysts on -alumina, titania and zirconia. Supported and unsupported catalysts (promoted or unpromoted)
have been evaluated in HDO of Guaiacol and it appeared that the promoting effect is considerably enhanced on zirconia-supported catalysts. Guaiacol is
transformed into catechol which is then converted to phenol and hydrocarbons, but in the case of CoMoS/ZrO 2 , an unusual direct demethoxylation is observed
giving directly phenol and then benzene (route R2, scheme 1). A reaction scheme has been drawn for each catalyst.
OH
OCH 3 R1
OH
OH
OH
Benzene Cyclohexene Cyclohexane
Scheme 1
Guaiacol
Catechol
R2
Phenol
O
OH
Cyclohexanol
Justification for acceptance: This work describes a process representative of the catalysis for the production of clean fuels and for the first time a support
effect coupled with a promoting effect was observed in HDO reaction.
References:
[1] Directive 2003/30/EC of the European Parliament and of the Council (2003).
[2] E. Furimsky, Applied Catalysis A: General 199 (2000) 147.

408 Hydrogen production by glycerol steam reforming
V. Dal Santo a , * , V. De Grandi b , A. Gallo b , L. Sordelli a and R. Psaro a
a ISTM-CNR, Milan, Italy. b Dip. CIMA, Università degli Studi di Milano, Milan, Italy.
*Corresponding author. Tel: +39 02 50314428, Fax: +39 02 50314405, e-mail: v.dalsanto@istm.cnr.it
Background
Hydrogen production from renewables is one of the key points for the development of hydrogen economy. Glycerol is a good candidate since it is a by-product
of biodiesel industry, that is expected to increase in the next years, thus resulting in large availability of such raw material [1]. From a fundamental point of
view glycerol is a good model molecule for more complex polyols, since it is quite volatile. Glycerol steam reforming studies were mainly focused on the
development of catalysts and/or processes applicable. Here we will address more on the understanding of catalysts nanostructure / performance relationship.
Results
Glycerol steam reforming experiments were carried out in a fixed bed atmospheric pressure quartz reactor, typical conditions are T=873K; H 2 O/Glycerol ratio
= 10:1 wt. 0,5 mLmin -1 ; He carrier flow = 50 mLmin -1 ; Catalyst amount (as metal) 0.5 mg; reaction products were analyzed by double column GC-TCD and
unreacted glycerol by titration. Catalysts were prepared by CVD of appropriate metal precursors on alumina supports.
A series of low loaded Rh/Al 2 O 3 catalysts was tested (Rh = 0.5 – 1 – 1.5% wt) and the effect of metal loading investigated. All the catalysts showed similar
performances reaching high glycerol conversion and selectivity towards H 2 and CO 2 , typical values at 873K are the followings: Conv= 80-90%; Sel(H 2 )= 90%;
Sel(CO 2 )= 89%. Noteworthy even 0.5% Rh catalyst shows good performances, but deactivation occurs. Significant amounts of coke were found on exhausted
catalysts (10% weight loss from TGA analysis, compare to 2% of -Al 2 O 3 extrudates vaporizing bed) and can account for the observed deactivation.
Role of Rh nanostructures in reaction and deactivation mechanisms are currently under investigation by multi-technique characterization approach.
Justification for acceptance
The development of nanostructured catalysts for H 2 production from waste/renewables and the study of catalysts nanostructure/performance relationships, in
our opinion, makes this work suitable for an oral presentation in the “Catalysis for the production of clean fuels, including from renewables” ICEC section
topic.
References:
[1] S. Adhikari, S. D. Fernando, A. Haryanto, Renewable Energy 33 (2008) 1097.
414 Probing hydrocarbonaceous overlayers on doped Ni/Al 2 O 3 autothermal methane-reforming catalysts
Ian Silverwood 1 , Neil G. Hamilton 1 , R. Mark Ormerod 2 , Hayley Parker 2 , John Staniforth 2 , David T. Lundie 3 , Stewart F. Parker 4 and David Lennon 1* .
1. Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow, G12 8QQ, UK
2. School of Physical & Geographical Sciences, Keele University, Staffs, ST5 5BG, U.K.
3. Hiden Analytical Ltd., 420 Europa Boulevard, Warrington, WA5 7UN, U.K.
4. ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, UK
*Corresponding author. Email: davidle@chem.gla.ac.uk; Tel: +44 141 3304372 Fax: +44 141 3304888.
Background:
With oil reserves dwindling and becoming increasingly difficult to access, methane from natural gas or biomass offer an alternative both as a fuel and chemical
feedstock. Catalytic reforming of methane to produce carbon monoxide and hydrogen (synthesis gas) fulfils both these roles. Although steam reforming can
produce hydrogen more cheaply than the autothermal reaction with CO 2 , the lower ratio of H 2 :CO is better suited to the production of synthetic fuels for this
case [1]. Consumption of CO 2 and optimisation of the process with a coupled Fischer-Tropsch reactor, potentially allows the production of greener liquid fuels
and oils. This communication applies a variety of spectroscopic techniques to characterise the nature of the hydrocarbonaceous overlayer that readily forms on
the catalyst under reaction conditions.
Results:
A series of Ni/Al 2 O 3 catalysts were tested for the reforming of CH 4 with CO 2 to form syngas. Two temperature regimes were examined – 550 and 750 ºC –
which were selected to feature different kinetic regimes [1]. In order to characterise the carbonaceous overlayer, the catalysts were examined by inelastic
neutron scattering (INS) using a combination of crystal analyser (TOSCA) and chopper based (MAPS) spectrometers available at the ISIS Facility of the
Rutherford Appleton Laboratory [2]. These studies necessitated the construction of a medium-scale reactor and associated gas handling facilities, which
enabled catalyst sample charges of ca. 20 g to be analysed. Reaction profiles were comparable to those observed using the more conventional micro-reactor
arrangement. Preliminary INS results backed up by Raman scattering measurements have established the general nature of the overlayer, which gives some
insight as to how the substrate remains active despite the laydown of substantial quantities of carbonaceous material about the metal particles.
References
[1] Y.Chui, H. Zhang, H. Xu and W. Li, Appl. Cat. A 318 (2007) 79
[2] S.F. Parker et al, Vibrational Spectroscopy with Neutrons, World Scientific, Singapore, 2005.

422 Hydrogen production via methanol steam reforming over Ga-promoted copper based catalysts: in situ DRIFT-MS study
Jamil Toyir a, *, Pilar Ramirez de la Piscina b , Narcis Homs b
a
Laboratoire de l’énergie, des ressources naturelles et de la modélisation, FP- Taza, Fez University, Morocco
b Departament de Química Inorgànica, Facultat de Química, Universitat de Barcelona, Barcelona, 08028, Spain
*Corresponding author: Fax number: (+212) 37675730, E-mail address: toyir@yahoo.com
Background
Recently we reported high performances of gallium-promoted copper-based catalysts supported on ZnO or hydrophobic silica in methanol synthesis from CO 2
and H 1, 2 2 . In the present paper, new application of the systems is reported for the reaction of methanol steam reforming. In situ DRIFT-Mass spectroscopy
study is performed in attempt to suggest a relationship between elementary pathways involved in the methanol steam process and reverse reaction of methanol
synthesis.
Results
Preparation and characterization of catalysts used were previously reported in related works 1, 2 . Catalytic tests were performed in a U-shaped quartz reactor
using 0.1g of the catalyst. Over Cu-Ga/ZnO catalyst, methanol was almost 100% converted at 593 K exclusively to carbon dioxide and hydrogen leading to a
product distribution compatible with the reaction of methanol steam reforming. It is important to note that CO formation did not occur (limit of detection of CO
is 17 ppm). Cu-Zn-Ga/SiO 2 (HD) shows a maximum methanol conversion of 35 % at 593 K into formaldehyde and hydrogen. In all of temperature range
examined there was no formation of CO 2 or CO. Temperature programmed oxidation of post-reaction catalyst did not show any CO 2 indicating that there was
no deposit of carbon over the catalyst during the catalytic test. Reactive formate species over copper were observed by in situ DRIFT-MS experiments for Cu-
Ga/ZnO whereas for Cu-Zn-Ga/SiO 2 formate species produced on ZnO leading to a desorption of formaldehyde at early stage of reaction.
Justification for acceptance
The paper reveals new application of the gallium promoted copper-based catalysts as alternative steam reformers of methanol leading to CO free hydrogen
production. These materials should be developed for a potential use in the field of clean renewable fuels and CO 2 mitigation.
References
[1] J. Toyir, P. Ramirez de la Piscina, J. L. G. Fierro and N. Homs, Appl. Catal. B : Environ., 2001, 34, 255.
[2] J. Toyir, P. Ramirez de la Piscina, J. Llorca, J. L. G. Fierro and N. Homs, Phys. Chem. Chem. Phys., 2001, 3, 4837.
429 Effective utilization of electrical field/discharges for hydrogen production
Y.Sekine*, M.Matsukata, E.Kikuchi
Waseda University, Okubo, Shinjuku, Tokyo 169-8555 Japan
*Corresponding author, Tel. & Fax +81-3-5286-3114, email ysekine@waseda.jp
Background
For high catalytic activity at lower reaction temperature, hybrid reaction of non-equilibrium plasma and catalyst, or catalytic reaction in an electric field was
investigated in this research. We examined several kinds of reactions; steam reforming of hydrocarbons/ethanol, degradation of hydrocarbons/ethanol and so
on. As for the degradation of ethanol, a synergic effect of plasma and catalyst was confirmed and the ethanol conversion greatly increased over 523K and the
selectivity to products also changed drastically.
Results
The effect of discharge on the catalytic reaction was investigated by the decomposition of ethanol. Four kinds of reactions like as a conventional catalytic
reaction (Mode I), a non-equilibrium electrical discharge reaction (Mode II), a hybrid reaction of non-equilibrium discharge and catalyst
C 2 H 5 OH
100
(Mode III) and a catalytic reaction in an electric field (Mode IV) were performed in this research. As a result,
synergic effect of non-equilibrium discharge and catalyst was confirmed and the production rate of hydrogen
greatly increased over 523K. Energy efficiency (LHV based) of reaction using electrical discharge was very
high and almost 100 %. So, reactions using non-equilibrium discharge and catalyst were very efficient process
for hydrogen production at low temperature. Some informations about reaction mechanism of the hybrid
reaction was acquired from the emission spectra, and the investigation revealed the difference between an
electrical discharge and an electirc field.
hybrid
products
conversion / %
80
60
hybrid
40
(A) + (B)
plasma (A)
20
catalyst (B)
0
400 450 500 550 600 650
temperature / K
Figure: Effect of temperature on the hybrid reaction for ethanol degradation.
References
[1] Y.Sekine, et al., Chem.Eng.Sci. (2008) in press.
[2] Y.Sekine et al., Energy&Fuels (2008) 693.

431 Investigation of two-stage hydrodearomatization of gas oils
G. Nagy* 1 , J. Hancsók 1 , Gy. Pölczmann 1 , Z. Varga 2 , D. Kalló 3
1 University of Pannonia, Dep. Hydrocarbon & Coal Proc., H-8201 Veszprém, P.O Box: 158, Hungary, Phone: +36 88/624413, Fax: +36 88/624520, E-mail:
nagyg@almos.uni-pannon.hu
2 MOL Hungarian Oil and Gas Plc., Százhalombatta, P.O. Box 1, H-2443, Hungary
3 Chem. Res. Cent., Inst. of Chem., Hungarian Academy of Sciences, Budapest, P.O. Box 17, H-1525, Hungary
Background
In 2009 in the European Union sulphur content of diesel fuels will be limited to 10 mgS/kg, around 2010 the limit of polycyclic aromatics will be 2-4%
and limitation (

441 Kinetics of CH 4 partial oxidation over Rh/Al 2 O 3 and Rh/ZrO 2 : role of CO 2 reforming
A. Donazzi, A. Beretta*, G. Groppi, P. Forzatti
a Dipartimento di Energia, Politecnico di Milano, piazza Leonardo da Vinci 32, 20133 Milano, Italy
*Corresponding author: Tel +39-02 23993284 FAX – 3318, alessandra.beretta@polimi.it
Background
The debate on the role of CO 2 reforming in the kinetics of CH 4 partial oxidation over noble-metal catalysts is open. Wei and Iglesia 1 proposed a unifying
mechanism of CH 4 activation, according to which steam reforming (SR) and CO 2 -reforming (CO 2 -R) share the same rate determining step (the breaking of the
first C-H bond) and the same kinetics (proportional to methane concentration and independent on the nature and amount of the co-reactant). Other authors 2,3
however have shown that CO 2 reforming has a negligible role in the performance of autothermal CH 4 -CPO reformers. In this work, pieces of evidence were
searched on the kinetic role of CO 2 and in particular on the relationship between steam- and CO 2 -reforming. The kinetic insight was pursued by comparative
tests of steam reforming, CO 2 -reforming, reverse-WGS and their theoretical analysis.
Results
A kinetic study on the reforming of CH 4 with CO 2 over 4 wt% Rh/ -Al 2 O 3 catalysts was performed in a short contact time annular reactor. CO 2 -reforming
experiments were carried out under nearly isothermal conditions , at high GHSV (2 . 10 6 Nl/Kg cat /h) between 300°C and 800°C, at varying CO 2 /CH 4 ratio and
co-feed of O 2 ; the results indicated that H 2 O had a limiting role on the conversion of CH 4 . A quantitative analysis of data was performed by means of a 1D
heterogeneus model of the reactor, by assuming that SR and R-WGS were uniquely active and proceeded according to kinetics that were estimated on the basis
of independent data. Though neglecting the rate of CO 2 reforming, all the observed trends could be well described as a cycle of H 2 O reforming and RWGS
(initiated by a trace amount of H 2 O in the feed) wherein the rate determining step (either SR or R-WGS) depends on the gas-phase composition 3 .
Analogous results were obtained over a wt% Rh/ZrO 2 .
References
[1] J. Wei, E. Iglesia, J. Catal. 225 (2004) 116
[2] A. Schneider, J. Mantzaras, P. Janshon, Chem. Eng. Science 61 (2006) 463
[3] R. Horn, K.A. Williams, N.J. Degenstein, A. Bitch-Larsen, D. Dalle Nogare, S.A. Tupy, L.D. Schmidt, J. Catal. 249 (2007) 378.
[4] A. Donazzi, A. Beretta, G. Groppi, P. Forzatti, J. Catal. in press
469 Light Hydrocarbon Reforming over Doped Ceria-Zirconia Catalysts for SOFC Applications
U. Wetwatana, D. Chadwick *
Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ
*Corresponding author. Tel: +44 20 7594 5579, e-mail: d.chadwick@imperial.ac.uk.
Background
An integrated internal reforming solid-oxide fuel cell (IIR-SOFC), in which the reformer is in good thermal contact with the SOFC is in principle an energy
efficient mode of operation. However, the relatively rapid and highly endothermic catalytic steam reforming causes undesirable local cooling at one point or
another within the SOFC system. The potential ways to achieve stable near-authothermal operation have been investigated by simulation of fuel cell
performance and experimental study of catalytic steam reforming over a range of catalysts [1,2]. It is well established that ceria based materials are useful in
applications involving oxidation or partial oxidation of hydrocarbons and as anodes for SOFC. The high oxidation capacity (OSC) is advantageous in the
oxidation process and imparts resistant to deactivation by carbon deposition. The present paper is concerned with the utility of oxide catalysts for fuel
processing for SOFCs and presents results for reforming of light hydrocarbons, the RWSR, and relevant probe reactions over Nb and Gd doped CeO 2 -ZrO 2 .
Results
The doped CeO 2 -ZrO 2 catalysts have been prepared using non-chloride precursors in contrast to previous work [1], and extend the doping range to lower
levels. XRD was used to establish single phase materials; bulk and surface compositions were determined by XRF and XPS. Generally, BET area was found to
decrease with calcination temperature above 400ºC as expected. A maximum occurs in the range 0.8-1.6 % as cation of metal loaded. RWGS was investigated
over all catalysts at temperature in a range of 400-1000 ºC. Doping either Nb or Gd into ceria gives higher conversion. On the other hand, doping into CeO 2 -
ZrO 2 gives slightly lower conversion. PrOH decomposition has been used to probe surface segregation of Nb and Gd by both steady-state and temperature
programmed methods. Selectivity to acetone is found to increase with doping Nb or Gd in CeO 2 or CeO 2 -ZrO 2 . Results are also presented for methane and
propane steam reforming.
Justification for Acceptance
The aim of this work is to assess the suitability of oxide catalysts for fuel processing in solid oxide fuel cells (SOFCs); which is an alternative of clean energy
to reduce world’s pollution and also global warming problem.
References
[1] E. Ramírez-Cabrera, A. Atkinson, D. Chadwick, Applied Catalysis B: Environmental, 36 (2002) 193
[2] Lay Tiong Lim, David Chadwick, Lester Kershenbaum, Ind. Eng. Chem. Res., 46 (2007) 8518.

470 Non-parametric determination of distribution of active species on sulfided Mo/Al 2 O 3 catalyst
H. Tominaga, A. Irisawa, M. Kiyoshi, M. Nagai*
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, 2-24 Nakamachi, Koganei, Tokyo 184-8588, Japan
*Corresponding author. Tel/Fax: +81 42 388 7060, e-mail: mnagai@cc.tuat.ac.jp
Background
The nonparametric determination of the activity distribution of the active sites is applied to the kinetics of the rate of dibenzothiophene HDS on the sulfided
Mo/Al 2 O 3 catalyst. In order to extract this information, a model contains the simplification of assumption that the individual species reacts in a first-order
manner and the adsorbed reactive species have rate constants depending on the activity of the catalytic sites. Integral formulation applies to the activity
distribution of active sites of the sulfide catalysts was studied during the HDS reaction.
Results
The HDS of dibenzothiophene on the 12.5% Mo/Al 2 O 3 catalysts sulfided at 573, 623, and 673 K in a stream of 10%H 2 S/H 2 was carried out at 573 K and a
total pressure of 10.1 MPa using a fixed-bed microreactor. The liquid feed, consisting of 13.6 mmol L -1 dibenzothiophene in xylene, was introduced into the
reactor at 5.56 L s -1 with a hydrogen flow of 74.4 mol s -1 . The equation was calculated in programmed in C using a PC station. The numerical method
applied to first kind Fredholm integral equations of the first kind is as follows, r(t) = h(t,k)f(k)dk where r(t) is normalized data of the HDS rate, (f(k)) is a
distribution of site activity (rate constant), and (h(t,k)) is a nondegenerate kernel, in our case, the change in the concentration of strength of active species on
the catalyst surface.
In order to distinguish the active sites with the different catalytic reactivity is measured by the rate, r(t), dibenzothiophene HDS over the sulfided 12.5%
Mo/Al 2 O 3 catalyst. In the case of h(t,k) = exp(-kt), for the 623 K-sulfided catalyst, two peaks are deconvoluted: At k=1.56 h -1 (rate constant), the activity
distribution of the surface sites is 1.08 and below k = 0.23, the distribution is 0.409. Also, the 573 and 673 K-sulfided catalysts contained two distributions of
active sites with different rate constants. Thus, the two distinct distributions support that two active sites with different activities are present on the sulfided
12.5% Mo/Al 2 O 3 catalysts for the dibenzothiophene HDS.
Reference
[1] H. Tominaga, M. Kiyoshi, M. Nagai, Chem. Eng. Sci. 62 (2007) 5368.
473 The relevance of support on the performances of Pt and Pt-Ni catalysts for the low temperature ethanol steam reforming
P. Ciambelli*, V. Palma, A. Ruggiero
Department of Chemical and Food Engineering, University of Salerno, 84084 Fisciano (SA), Italy.
*Corresponding author: Tel. +39 089 964151 – FAX +39 089 964057 e-mail: p.ciambelli@unisa.it
Background
Electric power generation by H 2 fed fuel cells is the most promising technology for the reduction of fossil fuels dependence, greenhouse gas emissions and
atmospheric pollution. Among different H 2 sources ethanol is very attractive when obtained from biomass minimizing CO 2 emissions. At low temperature ethanol
steam reforming to H 2 or pre-reforming to CH 4 can increase the overall system efficiency, but the byproducts formation leads to reduced selectivity and catalyst
durability because of coke formation. Metal catalyst coking is also influenced by the support properties. In this work the performance of Pt and Pt-Ni based
catalysts supported on Al 2 O 3 and CeO 2 were studied.
Results
The catalysts were prepared by wet impregnation of Al 2 O 3 (160 m 2 /g) or CeO 2 (80 m 2 /g) with a PtCl 4 aqueous solution, drying at 120°C and calcination at
600°C for 3h. Pt-Ni catalysts were obtained by a successive impregnation with nickel acetate aqueous solution. Catalysts samples were characterized by BET
surface area, XRD and temperature programmed reduction. The reaction was carried at 300-450°C, atmospheric pressure, GHSV = 15,000 h -1 , and H 2 O/C 2 H 5 OH
molar ratio = 3.0. In order to verify the formation of secondary products in the gas phase, the reactor outlet was analyzed online by a FT-IR multigas analyzer,
while the H 2 concentration was measured by a thermoconductivity analyzer.
The results showed that the nature of the support dramatically affects both activity and stability of Pt and Pt/Ni catalysts. Ethanol conversion was complete
and more stable on CeO 2 supported catalysts while decreased progressively for Al 2 O 3 support. The H 2 yield was higher and more stable over Pt/CeO 2 with respect
to Pt/Al 2 O 3 , even if for both supports it increased with metal loading. Moreover, for CeO 2 supported catalysts H 2 and CO 2 selectivity were higher and no CO
formation was detected for 5 % Pt loading. Finally, the high performance of Pt/CeO 2 was improved by nickel addition. In fact, the Pt/Ni/CeO 2 catalyst exhibited a
synergic effect of the active species, giving a H 2 and CH 4 rich stream without any catalyst deactivation. The effectiveness of the FTIR analysis system for
byproducts formation allowed to suggest a mechanism for coke formation.
Significance
The development of a catalyst highly active, selective to H 2 and CH 4 , and coke resistant is a critical issue for high efficiency energy production from ethanol,
an eco-friendly source.

POSTER
ABSTRACTS
Air and Water

106 Catalytic decomposition of CFC-12 on solid super acid Mo 2 O 3 /ZrO 2
T.-C. Liu a, c , P. Ning a, b,* , H.-J. Bart b , Y.-M Wang a , H. Gao a
a Department of Environmental Science and Engineering, Kunming University of Science and Technology, 650093 Kunming, People’s Republic of China
b Lehrstuhl für Thermische Verfahrenstechnik, TU Kaiserslautern, D-67653 Kaiserslautern, Germany
c Department of Chemical and Biological technology, Yunnan Nationalities University, 650031 Kunming, People’s Republic of China
*Corresponding author. Tel.: +49-631-2052414, Fax: +49-631-2052119, e-mail: ningping58@sina.com
Background: Chlorofluorocarbons (CFCs) emissions contribute to the stratospheric ozone depletion and the greenhouse effect [1,2]. According to the Montreal
Protocol, the use of CFCs has been banned in developed countries and will be stopped by 2010 in developing countries. Therefore, the accumulated CFCs are
waiting for final treatment. Catalytic decomposition of CFCs to CO 2 , HCl, and HF in the presence of water vapor and air on acidic catalysts is the most
commonly used, cost-effective method due to the simple process, high conversion and mild reaction conditions [3,4]. In the present work, the catalytic activity of
solid super-acid Mo 2 O 3 /ZrO 2 for CFC-12 decomposition was investigated.
Results: The MoZr series catalyst can decompose CFC-12 at above 250 °C in the presence of both oxygen and water vapor. Catalyst composition affected its
catalytic activity. The optimum composition of the catalyst is between 20 to 40% ZrO 2 . Calcination temperature influenced the solid super acid properties and
specific surface area simultaneously and thus the decomposition activity. Generally, catalytic properties and specific surface area are shrinking with at a high
calcination temperature, which is not desirable. As for the Mo 2 O 3 /ZrO 2 0.2 series catalysts the best calcination temperature is at 450 °C. The optimum
composition of the feed gas was studied. The oxygen concentration has no obvious effect on the decomposition activity. However, the concentration of water
vapor and CFC-12 significantly affected the reaction. Adopting low concentration of oxygen, CFC-12 and high concentrations of water vapor is preferable for the
achievement of a complete decomposition of CFC-12. Mo 2 O 3 /ZrO 2 0.2 calcined at 450 °C is a potent catalyst for the selective decomposition of CFC-12 in the
presence of both oxygen and water vapor from the viewpoint of practical usage. CFC-12 can be decomposed to CO 2 by hydrolysis at 250-300 °C. Catalytic
activity decreases slightly at the beginning of reaction and then reaches a steady state as been shown in a long time experiment of 100 h.
Justification for acceptance: Mo 2 O 3 /ZrO 2 catalysts possess a strong acidity and result in the higher rate in catalytic decomposition of CFC-12. This work
represents an important step forward and will gain the interest of the broad audience of scientists working in the field of heterogeneously acidic catalysis and
environment friendly decomposition.
References
[1] M.J. Molina, F.S. Rowland, Nature 249 (1974) 810.
[2] J.R. Hummel, R.A. Reck, Atmos. Environ. 15 (1982) 379.
[3] J. Moriyama, H. Nishiguchi, T. Ishihara, Y. Takita, Ind. Eng. Chem. Res. 41 (2002) 32.
[4] Y. Takita, J. Moriyama, H. Nishiguchi, T. Ishihara, F. Hayano, T. Nakajo, Catal. Today 88 (2004) 103.
108 Copper oxidation degree and catalytic activity in CO oxidation
V.Yu. Bychkov*, Yu.P. Tyulenin, A.A. Firsova, V.N. Korchak
Semenov Institute of Chemical Physics RAS, Kosygina 4, Moscow 119991, Russia
*Corresponding author. e-mail: bychkov@chph.ras.ru
Background
Supported copper systems were widely proposed as efficient catalysts for CO oxidation in a hydrogen excess and their characteristics were thoroughly
investigated. However, copper state in the course of catalytic reaction is still under discussion as well as an effect of the copper oxidation degree on catalytic
activity. In the present work an attempt has been made to conduct "in situ" study of several Cu-containing catalysts (6%CuO/-Al 2 O 3 , 6%CuO/-Al 2 O 3 ,
5%CuO/CeO 2 ) during CO oxidation in a flow of stoichiometric (2%CO+1% O 2 in He) and (1%CO+1%O 2 in H 2 ) mixtures by means of thermogravimetry
combined with "on line" mass-spectrometry. This set-up allows to investigate "in situ" the catalytic activity as a function of the copper oxidation state.
Results
Redox experiments have shown that in a case of CuO/-Al 2 O 3 sample variations of the catalyst weight exactly characterized an apparent degree of copper
oxidation. For CuO/-Al 2 O 3 and CuO/CeO 2 samples the observed effect of the strong oxide-support interaction was considered at the evaluation of copper
oxidation degree. For CuO/-Al 2 O 3 system three main oxidation states of Cu (CuO, Cu 2 O, Cu, confirmed by XRD) as well as intermediate states were observed
during CO oxidation. Transitions between these states could be stimulated by reaction temperature or reaction mixture composition. Oxidized CuO/-Al 2 O 3 and
CuO/-Al 2 O 3 samples demonstrated moderate catalytic activity in the mixture with H 2 excess (1%CO-1%O 2 -H 2 ). However, with increasing reaction temperature
up to 200C the total reduction of supported copper oxide (to Cu 0 ) was taking place. The completely reduced samples revealed a higher activity than that of the
oxidized samples. Furthermore, activity of the reduced catalyst was growing up to maximum values with decreasing reaction temperature to 140ºC and 100ºC for
CuO/-Al 2 O 3 and CuO/-Al 2 O 3 samples, respectively.
In stoichiometric mixture active Cu 0 state was unstable and after several minutes transformed into more oxidized state followed by drastic drop of
catalytic activity. Activity of this partially re-oxidized sample was lower than that of the fully oxidized catalyst. Heating of pre-reduced Cu/-Al in stoichiometric
mixture from 30º to ~200ºC was also resulted in low reactive, partially re-oxidized (~Cu 2 O) copper state.
Another dependence was found for CuO/CeO 2 catalyst. In contrast to Cu/-Al and Cu/-Al samples, the maximum catalytic activity over CuO/CeO 2
sample during CO oxidation in H 2 excess was observed at 120-130ºC for oxidized state of supported copper. However, at higher reaction temperature a
substantial decrease of catalytic activity has taken place due to CuO reduction accompanied by the sample weight drop.
The results obtained allow to propose different mechanisms for CO oxidation over copper-containing catalysts supported on alumina or ceria.
Justification for acceptance
Processes of CO removal through its selective oxidation, especially in a high hydrogen excess, are of great importance in the field of environmental catalysis and
the copper-containing systems are promising catalysts for this purpose. Fundamental understanding of copper behavior during the catalytic processes is very
important for the development of novel efficient catalysts.

119 Destructive adsorption of CF 4 over NaF-Si-MO ternary adsorbents
Jie Fan, Xian-Jun Niu, and Xiu-Feng Xu*
Institute of Applied Catalysis, School of Chemistry and Biology, Yantai University, Yantai Shandong 264005, China
*Corresponding author. Tel./Fax: 86-535-6902233, e-mail: xxf@ytu.edu.cn
The semi-conductor industry has used large amounts of perfluorocarbons (PFCs) such as CF 4 as etching and cleaning gases. The exhausted PFCs with high
global warming potential must be destructed before emission. Among the technologies for PFCs removal, the destructive adsorption over some metal oxides (MO)
is a promising method. In Figure 1, on the ternary adsorbent consisting of 21% NaF, 26% Si, and 53% MO, where MO indicates a metal oxide such as Al 2 O 3 , the
conversion of CF 4 reached 80% or higher levels at 850C of reaction temperature. After reaction, the deposited carbon was found in spent adsorbents, in addition,
new phases of NaMgF 3 and Na 3 AlF 6 were observed from the XRD patterns of used NaF-Si-MgO, and NaF-Si-Al 2 O 3 , respectively, while CaF 2 was formed and
NaF of free state remained in spent NaF-Si-CaO. As for the reaction mechanism, NaF acted as a catalyst in ternary adsorbent to produce sodium vapour and break
up the C-F bond of CF 4 , then the fluorine element was fixed by MO [1,2], so the formation of inert phases of Na 3 AlF 6 in NaF-Si-Al 2 O 3 and NaMgF 3 in NaF-Si-
MgO resulted in the loss of free NaF and thus the decrease of CF 4 conversion with time on stream isothermally at 850 C. Presently, we are searching for suitable
reaction conditions for stably high conversion of CF 4 before the MO is used up in fluorine-fixed reaction. This research provides a practical technology for the
abatement of PFCs exhausted from industrial processes and is significant for us to face the challenge of global warming.
CF 4
conversion / %
100
80
60
40
20
NaF-Si-Al 2
O 3
NaF-Si-MgO
NaF-Si-CaO
0
600 650 700 750 800 850
Reaction temperature / o C
Figure 1 CF 4 destructive adsorption conversion over NaF-Si-MO
Acknowledgement: We gratefully acknowledge the support from the National Natural Science Foundation of China (No.20573089).
References
[1] P.L. Timms, J. Chem. Soc., Dalton Trans. (1999) 815.
[2] M.C. Lee, W.Y. Choi, Environ. Sci. Technol. 36 (2002) 1367.
128 Effect of chlorine on the catalytic behavior of Ir/CeO 2 for preferential CO oxidation
Yanqiang Huang, Aiqin Wang, Lin Li, Xiaodong Wang, Tao Zhang*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China
*Corresponding author. Tel: 86-411-84379159, Fax: 86-411-84691570, E-mail: taozhang@dicp.ac.cn
Background
Ir/CeO 2 catalyst has been found to be efficient for removal of traces of CO from hydrogen through the so-called preferential CO oxidation (PROX) process [1-
2]. However, the presence of chlorine diminishes its activity towards the CO oxidation reaction. In the present work, the surface chemistry occurring on the Clfree
and Cl-containing surfaces is derived from HRTEM, XPS, and DRIFTS results which reveal the effect of chlorine on Ir/CeO 2 catalyst behavior for the
PROX reaction.
Results
For the PROX reaction, the catalytic performance of the Cl-free Ir/CeO 2 catalyst was considerably superior to that of the Cl-containing sample. From HRTEM
observation, it was found that Ir particles were highly dispersed on both samples. The higher metal dispersion of the Cl-containing catalyst may imply that the
presence of chlorine favors the dispersion of Ir metal particles on the ceria support. The replacement of the lattice oxygen by chloride ions would produce CeOCl
species, which was also confirmed by the HRTEM characterization. The XPS results indicated that the CeOCl species hindered the formation of surface hydroxyl
groups on the Ir/CeO 2 catalyst. It has been reported that the OH groups were highly active and played an important role in CO oxidation. The DRIFTS
characterization showed that the presence of Cl species greatly retards the kinetic rate of CO chemisorption on iridium. Moreover, chlorine hindered
the formation of carbonates during CO exposure, which was found to be the intermediates for CO oxidation. The possible mechanism for CO
oxidation in PROX mixture is proposed based on these experimental findings.
Justification for acceptance
The PROX process has been recognized as the most straightforward method for purification of H 2 fuel. Our previous activity test has shown that Ir/CeO 2 was
reasonably active and selective for this reaction. Therefore, detailed characterization on this catalyst to clarify the detrimental role of chlorine is helpful to gain
further insight into the reaction mechanism.
References
1. F. Mariño, C. Descorme, D. Duprez, Appl. Catal. B 54 (2004) 59.
2. Y. Q. Huang, A. Q. Wang, X. D. Wang, T. Zhang, Inter. J. Hydro. Energy. 32 (2007) 3880.

147 Effects of preparation conditions on gold/13X-type zeolite for CO oxidation
Qing Ye *, Caiwu Luo, Dao Wang, Shuiyuan Cheng
Department of Environmental Science, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022 (P.R.China)
* Corresponding author. Tel: +86-10-6739-1683, Fax:+86-10-67391983;e-mail: yeqing@bjut.edu.cn
Background
Since Haruta et al. [1] found that the inert gold with nanoparticle size possessed a dramatic activity for low-temperature CO oxidation, nano-particle gold catalysts
for this reaction have been investigated by many research groups. A known means for dispersing and stabilizing metal particles is to use zeolites [2, 3] because of
its high surface area, ion exchange ability, and the stabilization of small gold particles via inserting them into the small cages. In this work, we chose faujasite
13X zeolites with the large diameter of the pores as support and prepared by deposition-precipitation method. The effects of preparation conditions on Au/13X
for CO oxidation were studied.
Results
The effects of preparation conditions (i.e. solution temperature, pH of gold solution, and calcinations temperature) on gold supported on 13X-type zeolite
(Au/13X) for CO oxidation were studied. The catalysts were characterized by XRD, SEM and XPS, in order to understand the correlation of the preparation
conditions and the gold particles in 13X-type zeolite to the catalytic activity. It was found from the results of SEM and XRD that higher temperature would
deposit homogeneous and smaller gold clusters on the support 13X, which caused better CO activity. Moreover, From XPS analysis of Au/Si ratios on the
surface of Au/13X prepared in the solution at pH 6 and 9, respectively, the lower pH 6 would generate more amount Au loading on 13 X than that of pH 9. There
were least two different ionic gold species on Au/13X prepared in the solution at pH 6. One is Au(OH) 2 + monomer, and the other is Au 2 O 3 gold dimers. However,
only one ionic gold species, Au 2 O 3 , from pH 9. That may result from that Au(OH) 2 Cl 2 and Au(OH) 3 Cl can be exchanged effectively on a specific surface site of
zeolite under pH 6. As compared with the samples calcined at 200 C and 400 C, the sample calcined at 300 C show the highest activity, which may result from
that the sample calcinations under 300 C cannot decompose completely to metallic gold and the sample calcinations ablove 300 C get larger particles gold on
support and the sample calcinations at 300 C can get moderate gold size. It can be concluded from this study that Au/13X prepared from a gold solution with
initial gold solution pH at 6, solution temperature around 80 C, and calcinations temperature for 300 C would possess an optimum catalytic activity for CO
oxidation.
Justification for acceptance
CO oxidation has been a topic of immense importance recently to meet the stringent and continuously changing environmental regulations as well as in many
industrial applications such as indoor air cleaning, fuel cells, CO 2 lasers and automotive exhaust treatment. In order to obtain small supported Au particles for
effective catalysts of CO oxidation, we chose 13X zeolite with high surface area, the large diameter of the pores and ion exchange ability as support of Au/13X
for CO oxidation
References
[1]. M. Haruta, T. Kobayashi, H. Sano and N. Yamada, novel gold catalysts for the oxidation of carbon-dioxde at a temperature far below 0-degrees C, Chem. Lett., 1987.405.
[2] S. Qiu, R. Ohnishi, M. Ichikawa, formation and interaction of carbonyls and nitrosyls on gold(I) in ZSM-5 zeolite catalytically active in NO reduction with CO, J. Phys. Chem., 101 (1994)
2719.
[3] Y.M. Kang, B. Z. Wan, Gold and iron supported on Y-type zeolite for carbon monoxide oxidation , Catal. Today, 35 (1997) 379.
149 Catalytic blocks based on foam metals in some technology of air clearing
Makarov A.M. *, Makarov A.A., Makarov M.A. , Makarova N.P.
ZAO “ECAT Professora Pozdeeva st. 6, Perm, 614013, Russia,
*Corresponding author. Tel: +7 342 2714249, Fax : +7 342 2391277 ,
e-mail: makarov11@perm.ru
The main producing methods, spatial structure, the main properties and applications catalytic blocks based on foam metals with open porosity for polluted air
cleaning have been described. Application areas for the air cleaning have been specified.
The catalytic combustion of volatile organic compounds has been investigated over complex oxide with perovskite type structure supported on foam metal
blocks with Al 2 O 3 layer[1,2]. We have developed the synthesis methods of aluminium oxide, having a various porosity structure and the perovskite
structure oxides compositions on surface of foam metals. The catalytic combustion was carried out in air, at temperatures between 50 and 1000 O C. The
concept of the block catalyst in which the necessary temperature achieved by passing an electrical current through a foam metal also was developed. The
thermocatalytic cleaning from acrolein vapors on in vacuum of up to 150 Pa (the catalytic blocks were directly heated up to 500 0 with a current, purification
efficiency is 97 %); tricresol vapors in air (overall life time of catalytic blocks is 12000 hours with purification efficiency 99,9 %) in industry reactors was shown.
The combination of heterogeneous catalysis and low-temperature plasma technologies with use of catalytic blocks based on foam metals has allowed to creation
compact high-efficiency air cleaning device. Computer simulation of heat-exchange, electric fields, flow regime, temperature and pressure is carried out with use
of a finite elements method. Results of simulation have allowed to optimize a design and to improve efficiency of clearing and sterilization of air.
Catalytic blocks based on foam metals have shown high efficiency in complete decomposition of organic compounds to carbonic gas and water and can be
used in thermo-, photo- and plasmacatalytic technology of air clearing in industrial, public and household purposes.
References
[1] V.N. Antciferov, V.I. Ovchinnikova, A.M. Makarov Patent WO 95/11752
[2] Makarov A.M., Makarov A.A., Tzschatzsch A., Russian-Dutch Workshop “Catalysis for sustainable development”. Abstracts. Novosibirsk, 2002, 344.

153 An innovative preparation of heterogeneous metal nanoparticles catalysts for VOC abatement:
the onion-type multilamellar vesicles route.
D. P. Debecker a , M.-E. Meyre b , A. Derré b , C. Faure b and E. M. Gaigneaux a, *
a Unité de catalyse et chimie des matériaux divisés. Université catholique de Louvain. Croix du Sud, 2/17 1348 Louvain-La-Neuve, Belgium.
b Centre de Recherche Paul Pascal (CNRS), Avenue du Dr. Albert Schweitzer, 33600 Pessac, France.
*Corresponding author. Tel: +32 10 47 36 65, Fax : +32 10 47 36 49, e-mail: eric.gaigneaux@uclouvain.be
Background.
On one side, onion-type multilamellar vesicles (MLV), mainly known for their potential applications in biotechnology, can be used for the spontaneous and
controlled production of metal nanoparticles. [1] This process has the advantage of not requiring any thermal treatment. On another side, the control of air
pollutants (CO, VOC, dioxins, etc.) can be achieved with metal-based catalysts which usually demand small and stable metal particles. [2,3] However, classical
preparation methods always imply a thermal treatment (calcination, reduction) during which sintering phenomena are hardly controlled. [3] The use of preformed
and tailored metal nanoparticles in the preparation of an inorganic catalyst is thus worth investigated.
Results .
The synthesis of silver nanoparticles inside onions MLVs was performed spontaneously at room temperature using the
surfactant itself (Genamin T020) as the reductant. No thermal, chemical or electrochemical treatment was needed. Organicinorganic
hybrids consisting of silver nanoparticle-loaded onion MLVs were successfully and quantitatively transferred onto a
TiO 2 support and a V 2 O 5 /TiO 2 catalyst, as attested by TEM images, XPS and elementary analysis. The method (impregnation,
evaporation under vacuum and drying) did not involve any separation of the organic matter, which only accounts for ~5% of
the final mass of the fresh catalyst. In order to validate this new preparation method, the materials were tested in the total
oxidation of benzene, chosen as a model for industrial and domestic air pollutants. We evidence the activity of the Ag
nanoparticles on the TiO 2 and a synergetic effect between the vanadium catalyst and the added silver nanoparticles. We also
show that small nanoparticles survive high reaction temperature during which the surfactant is burned out. A protection
mechanism (vs. sintering) involving the surfactant is suggested.
Justification for acceptance
Our work is original both in the scientific approach (merging of the expertise in biotechnology and heterogeneous catalysis), and in the reported process to
produce metal nanoparticle-based heterogeneous catalysts. Our new “bio-inspired” concept should interest a large part of the environmental catalysis community
since the use of small, tailored and stable nanoparticles is still both needed and challenging.
References
[1] Faure, C.; Derré, A.; Neri, W. J. Phys. Chem. 107 (2003) 4738.
[2] M. Haruta, S. Tsubota, T. Kobayashi, H. Kageyama, M. J. Genet, B. Delmon, J. Catal. 144 (1993) 175.
[3] C. Cellier, S. Lambert, E. M. Gaigneaux, C. Poleunis, V. Ruaux, P. Eloy, C. Lahousse, P. Bertrand, J. P. Pirard, P. Grange, Appl. Catal. B. 70 (2007) 406.
156 Electrochemical treatment of Rhodamine 6G by using RuO 2 coated titanium electrode
Rita Farida Yunus, Yu-Ming Zheng, Shuai-Wen Zou, J Paul Chen *
Division of Environmental Science and Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260
* Corresponding author. Fax: +65-6872-5483, +1-831-303-8636, Email: esecjp@nus.edu.sg, jchen.enve97@gtalumni.org
Background
Dye-containing wastewater from colorants manufacturing industries has long been recognized as an important source of environmental pollution. This
wastewater presents a serious problem to the environment as well as to human health, due to its potential toxicity, carcinogenicity, mutagenicity, and poor
biodegradability. Electrochemical technologies appear to be promising, since these technologies are cheap and able to provide full decolourization of dyes [1]. In
this study, electrochemical degradation of dye using RuO 2 coated titanium mesh was investigated.
Results
In this study, an efficient electrochemical technology for the removal of Rhodamine 6G by using RuO 2 coated titanium mesh as dimensionally stable anode
(DSA) was developed and studied. The effects of operating factors that influence the removal of Rhodamine 6G were investigated in order to find an optimum
condition, as well as the energy consumption for the dye removal was analyzed. The results reveal that current intensity, electrolyte amount, distance between the
electrodes and solution pH influence significantly on the removal efficiency of the dye. Full decolourization of the dye and 78 % COD reduction can be achieved
within 5 min in the presence of 0.1 – 0.2 M of NaCl as electrolyte salt and a applied current intensity of 1.0 – 1.9 A at pH 2 – 6. The performance of
electrochemical degradation of Rhodamine 6G using Ti mesh/RuO 2 was also evaluated by studying the effect of initial dye concentration, dye working volume,
and recyclability of the electrodes. The results indicate that the developed electrochemical technology by using RuO 2 coated Ti mesh as anode is promising to be
used in the treatment of real dye-containing wastewater
Justification for acceptance
A novel material, RuO 2 coated Titanium mesh, was used as the dimensionally stable anode, which can effectively generate active chlorine in situ. By using the
developed technology, full decolourization of the dye can be achieved within 5 min under an optimum condition. It is a promising technology for dye wastewater
treatment.
References
[1] S.S. Vaghela, A.D. Jethva, B.B. Mehta, S.P. Dave, S. Adimurthy, G. Ramachandraiah. Environ. Sci. Technol. 39 (2005) 2848.

162 Plasma-catalytic decomposition of aromatic VOC
M. Magureanu a , D. Piroi a , N.B. Mandache a , V. Parvulescu b and V.I. Parvulescu b*
a National Institute for Laser, Plasma and Radiation Physics, Bucharest-Magurele, Romania,
b University of Bucharest, Department of Chemical Technology and Catalysis, Bd. Regina Elisabeta 4-12, 030016 Bucharest, Romania
*Corresponding author. Tel. +4021 4100241, Fax. +4021 4100241, e-mail v_parvulescu@yahoo.com
Background
The oxidation of volatile organic compounds (VOC) in a plasma is a relatively new approach towards the removal of highly diluted pollutants from contaminated
air streams. Non-thermal plasma offers great potential for the initiation of chemical reactions in the gas phase; due to the high-energy electrons generated in the
plasma, a highly reactive environment is created without heating the entire gas stream, as in thermal processes [1-3]. However, plasma activation is rather nonselective
and in order to obtain simultaneously high conversion as well as high selectivity towards the desired reaction, the addition of catalysts appears more
promising [2,4,5].
Results
The Ag colloid was obtained by reducing AgNO 3 in aqueous solution with sodium citrate and NaBH 4 under strong stirring. The black powder formed in solution
was filtered out and dried at room temperature under vacuum. The obtained dry silver powder was redispersible in water with the help of sonication and stirring.
The catalysts were prepared via a sol-gel route using Al(OBu) 3 , as precursor, and Pluronic 84, as surfactant, and different alcoxide:alcohol:water molar ratios.
The Ag colloid dissolved in water was added under a strong stirring during the gelification. From this preparation resulted samples containing 3 and 5wt% Ag.
The samples were calcined at 500 o C. Textural characterization of the corresponded to surface areas higher than 400 m 2 g -1 and a monomodal pore size
distribution centered at 7.5 nm. XRD patterns indicated that the samples are constituted in majority from -Al 2 O 3 , with a small percent of AlO(OH). 27 Al
CP/MAS NMR spectra, in line with XRD measurements indicated the presence of both tetra- and hexacoordinated Al. XPS analysis shown the preservation of
the Ag(0) state even after calcination, while TEM confirmed the preservation of the size of the colloids and the mesoporous texture.
The decomposition of p-xylene in contaminated air streams by using non-thermal plasma was investigated in the absence and in the presence of AlAg catalysts.
A dielectric barrier reactor packed with spherical quartz beads was used at room temperature and atmospheric pressure. The conversion of p-xylene increased
with increasing the specific input energy (SIE), reaching 70-80% at SIE of ~200 J/l. The main reaction products resulting from p-xylene decomposition were
carbon dioxide and carbon monoxide, with selectivities towards CO 2 of approximately 40%. The catalysts were placed either directly in the discharge zone (onestage
configuration), or downstream of the plasma reactor (two-stage configuration). It was found that the catalysts had little effect on the conversion of p-xylene
in either configuration. In the presence of the catalysts the selectivity towards CO 2 was improved as compared to the results obtained with the plasma alone,
reaching 50-60%. However, the position of the catalyst had little influence on the distribution of reaction products.
References
[1] U. Roland, F. Holzer, F.-D. Kopinke, Catal. Today 73 (2002) 315
[2] M. Magureanu, N.B. Mandache, P. Eloy, E.M. Gaigneaux, V.I. Parvulescu, Appl. Catal. B: Environ. 61 (2005) 12
[3] M. Magureanu, N.B. Mandache, V.I. Parvulescu, Plasma Chem. Plasma Process. 27 (2007) 679
[4] J. Van Durme, J. Dewulf, C. Leys, H. Van Langenhove, Appl. Catal. B: Environ. 78 (2007) 324
[5] Th. Hammer, Th. Kappes, M. Baldauf, Catal. Today 89 (2004) 5
172 Promotion effect of lanthanum in Pd/Al 2 O 3 -La 2 O 3 catalysts prepared by sol-gel
on the catalytic activity in the CH 4 + O 2 reaction
A. Barrera a, , G. Díaz b , A. Gómez-Cortés b , F. Tzompantzi c , A. López-Gaona c , F. J. Moscoso a , S. Fuentes d
a Universidad de Guadalajara, Centro Universitario de la Ciénega, Ocotlán, Jalisco, C.P. 47820, México
b Instituto de Física - UNAM, México D.F., C.P. 01000, México
c Universidad Autónoma Metropolitana – Iztapalapa,Depto. de Química, México D.F., 09340
d Centro de Ciencias de la Materia Condensada, UNAM, Ensenada B.C., C.P. 22800, México
*Corresponding author. Tel: +52 392 92 59416 , Fax: +52 392 92 53099 ; e-mail: arturobr@cuci.udg.mx
Background
The catalytic activity of Pd supported on Al 2 O 3 -La 2 O 3 binary oxides prepared by sol-gel was studied in the methane oxidation. The catalysts were characterized
by N 2 physisorption, XRD, Raman, UV-Vis and TPO. It was found that lanthanum species promotes the improvement of catalytic activity of palladium at lower
temperatures. This improvement is correlated with a higher S BET and depended on the support composition. The crystalline and chemical structure revealed that
LaOCl species were present in the catalysts. In these materials, La 3+ promoted the methane oxidation at lower temperatures due to their enhanced properties to
adsorb and desorb oxygen at lower temperatures.
Results
The catalytic activity of the Pd catalysts supported on Al 2 O 3 -La 2 O 3 binary oxides prepared by sol-gel is improved for the 6 and 15 wt% of La 2 O 3 with respect to
that of Pd/- Al 2 O 3 . For these catalysts, the % CH 4 conversion increased for about 170% and 165% at temperatures of 400 and 500ºC respectively. Textural
characterization of the catalysts showed that there is an improvement in the S BET for about 46 and 37% with respect to that of Pd/- Al 2 O 3 for these La 2 O 3
concentrations. These findings suggest that lanthanum is a chemical and textural promoter of Pd catalysts supported on -Al 2 O 3 . Structural studies indicated that
there is an increase in the crystallinity of the materials with La 2 O 3 concentration. Surprisingly, the XRD patterns of the Pd/Al 2 O 3 -La 2 O 3 showed reflexions peaks
corresponding to the LaOCl phase. The presence of LaOCl species is also confirmed by Raman and UV-Vis spectroscopies. In addition, temperature
programmed oxidation data suggest that La 3+ promotes a rapid adsorption and desorption of oxygen at lower temperatures.
Justification
Methane is a potent greenhouse and is important to reduce its amount emmitted to the atmosphere. One of the most active catalysts for oxidation of CH 4 is Pd/-
Al 2 O 3 1. However, this catalyst has poor stability and a high light-off temperature resulting in rapid deactivation. In this work we try to improve the catalytic
properties of palladium catalysts by supporting on Al 2 O 3 -La 2 O 3 binary oxide prepared by the sol-gel method.
References
[1] K. Persson, K. Jansson, S. Järås, J. Catal., 245 (2003) 401.

173 Metal-substituted hexaaluminates for high-temperature N 2 O abatement
Marta Santiago a and J. Pérez-Ramírez a,b, *
a Institute of Chemical Research of Catalonia, Avinguda Països Catalans 16, 43007 Tarragona, Spain.
b Catalan Institution for Research and Advanced Studies, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
*Corresponding author. Tel: +34 977 920236, Fax : +34 977 920224, e-mail: jperez@iciq.es
Background
Policies are being enforced to develop and implement technology for mitigation of N 2 O, a major greenhouse gas and an indirect ozone layer depletor. Relevant
sources of nitrous oxide (nitric acid and caprolactam plants as well as fluidized-bed combustors) contain N 2 O (

194 Comparative Analysis of Measurement of Indoor Radon Concentration Using Active and Passive Measurement Techniques
Rohit Mehra a* , Surinder Singh b
a Department of Physics, Dr. B. R. Ambedkar National Institute of Technology, Jalandhar-144011, India.
b Department of Physics, Guru Nanak Dev University, Amritsar-143005, India.
* Corresponding author. Tel.: +91-98885-34590
E-mail address: rohit_mimit@rediffmail.com (R. Mehra).
Background
A comparison has been made between the results of active and passive techniques for the measurement of radon concentration. For this measurements have been
taken for Malout area of Muktsar district of Punjab for nearly two months. Defined solid angle absolute beta counting (DSAABC) technique has been used as an
active method to measure the equilibrium equivalent concentration (EEC) of radon and thoron from the filtered aerosol samples in the summer season.
Results
The minimum and the maximum values measured with active technique for EEC of 222 Rn are 2.29 Bq m –3 and 12.96 Bq m –3 respectively with an arithmetic mean
and geometrical mean of 5.83 Bq m –3 and 5.37 Bq m –3 respectively. The 220 Rn EEC determined for same measurements vary from 0.058 Bq m –3 to 1.799 Bq m –3
with geometrical mean of 0.43 Bq m –3 and arithmetic mean of 0.62 Bq m –3 . The radon concentration has been calculated for active measurements by using the
equilibrium factor of 0.4 as the ratio of EEC over radon concentration (ICRP, 1993).
Passive Indoor radon measurements in same dwellings of Malout have been carried out, using LR-115 type II cellulose nitrate films in the bare mode. The indoor
radon value in the study area varies from 63 Bqm -3 to 120 Bqm -3 with an average value 87.50 Bqm -3 . The results shows that the radon concentration is less when
it is measured by using active techniques as it gives an instantaneous measurement as compared to the passive measurements which are for long duration and
take into consideration the meteorological variables also.
Justification for acceptance
The detailed investigations for the measurement of natural radioactivity have been carried out for the first time. In general these values are 2 to 3 times more than
the world average of 40 Bq m -3 (UNSCEAR, 2000). This may be due to the difference in the concentration of radioactive elements viz. uranium and radium in
the soil and building materials of the study area. radon concentration is less when it is measured by using active techniques as it gives an instantaneous
measurement as compared to the passive measurements which are for long duration and take into consideration the meteorological variables also.
195 Bimetallic Fe/Me - zeolite catalysts for decomposition of N 2 O
K. Jíša, A. Vondrová, D. Kaucký, J. Nováková, Z. Sobalík
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-182 23
Prague 8, Czech Republic, e-mail: kamil.jisa@jh-inst.cas.cz
Background
During the last decade, the urgency of N 2 O abatement further increased because of the increasing awareness of the role of N 2 O as a greenhouse gas and the
anticipated regulations for its emission. The last decade witnessed substantial progress in understanding the nature of the N 2 O reaction over metallo zeolites and
for understanding the potential and limitations of the process. The synergetic effects found for Ru and Fe [1] and Rh-, Pt-Fe in FER [2] would probably provide
for higher practical impact of these catalysts.
The screening study with a set of noble metals and analysis of the mechanism of their influence is presented.
Results and discussions
The Fe-ferrierites, Pt-, Rh-, Ru-ferrierites and Fe/Me-ferrierites were prepared by a sequence of noble metal and Fe loading. The noble metals were loaded by an
ion-exchange from aqueous solution and the Fe by a treatment in FeCl 3 solution in acetylacetone [3]. The N 2 O decomposition was carried out in a microreactor
using a mixture of N 2 O in He under GHSV of 90,000h -1 . The analysis of the gas stream was enabled by N 2 O and NO x analyzers (Advance Optima ABB co.,
Germany and MLU Model 200AH TELEDYNE co., U.S.A.). The addition of noble metal to Fe-ferrierite caused a boosting of catalytic activity and the resulting
conversions over bimetallic ferrierites exceeded a sum of the individual monometallic samples, evidencing a strong synergetic effect between iron and noble
metal active sites. This feature has been analyzed and the mechanism providing for such behaviour is proposed. The model is based on alternation between two
processes, i.e. direct recombination of oxygen atoms, including zeolite framework (characteristic for Fe-ferrierite), and enhancement of the formation of the NO x
ad-species, playing the role of co-active site.
Justification for acceptance
The decomposition of N 2 O is intended to be applied for control of emissions from chemical industry and similar sources. The understanding of N 2 O
decomposition mechanism on Fe-zeolite and boosting effects is crucial for efficient catalyst development.
References:
[1] J.A.Z.Pieterse, G.Mul, I.Melian-Cabrera, R.W.van den Brink, Catal. Lett. 99 (2005) 41.
[2] Z.Sobalík, K. Jíša, D.Kaucký, A.Vondrová, Z.Tvaržková, J.Nováková, Catal. Lett. 113 (2006) 124.
[3] Z.Sobalík, B.Wichterlová, M.Markvart, Z.Tvaržková, CZ Patent 293 917 (2004).

204 The promotion of carbon monoxide oxidation by hydrogen on platinum
S. Salomons 1 , R.E. Hayes 1* and M. Votsmeier 2
1 Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada T6G 2G6
2 Umicore AG & Co. KG, Automotive Catalysis Division, Research and Development, Hanau, Germany
*Corresponding author. Tel. 780-492-3571 Fax. 780-492-2881 email: bob.hayes@ualberta.ca
Background
The oxidation of carbon monoxide on platinum is an important reaction is the automotive catalytic converter. Hydrogen is present in the exhaust gas, however, its
role, and the interactions with CO oxidation, are not understood. It has been observed that hydrogen oxidation is inhibited by the presence of CO, and that the
presence of hydrogen can enhance the rate of CO oxidation. Although these effects have been observed, there have not as yet been any successful attempts to
model them. This work reports on an experimental and modelling study on the oxidation of CO and hydrogen mixtures on supported platinum catalyst.
Results
Experimental light-off curves for the oxidation of CO and hydrogen were performed on a monolith reactor 25.4 mm in diameter and 76.2 mm long. The Pt
catalyst with a loading of 80 g/ft 3 was supplied by Umicore AG & Co. KG. The monolith had hexagonal channels with a channel density of 400 CPSI and a wall
thickness of 109 microns. All experiments were performed at a space velocity of 25 000 h -1 . The primary observations made are that (a) hydrogen reduces the
light-off temperature of CO, and (b) when hydrogen and carbon monoxide are both present, the CO begins to oxidise first, and when the conversion is about 50
%, the hydrogen rapidly is converted. The experiments show a promotion effect, where CO lights off at a lower temperature in the presence of hydrogen. This
effect has diminishing marginal returns, where the influence of additional H 2 does not have a correspondingly large effect as the initial hydrogen. The first 1000
ppm H 2 has a greater marginal impact than an additional 1000 ppm H 2 .
A single channel monolith simulator was used to simulate the experiments with mechanistic kinetics. Several proposed reaction mechanisms were tried in
an effort to model the enhancement effect. It was found that a model in which adsorbed hydrogen gave a reduction in the activation energy of desorption for CO
was able to reproduce the experimental results. In this model, hydrogen is allowed to adsorb to sites unavailable for CO or oxygen, the extent of such adsorption
depends on the hydrogen partial pressure. The reduction in activation energy of desorption of CO was set as linearly dependant on the extent of this hydrogen
adsorption.
Justification for Acceptance
Automotive catalysis is obviously an important environmental issue. The combined oxidation of CO and hydrogen is also relevant in fuel cell applications.
205 Hybrid catalyst composed of zeolite and Pt/Al 2 O 3 for VOCs combustion
Y. Takamitsu * and W. Kobayashi
Nanyo Research Laboratory, Tosoh Corporation, Shunan, 746-8501 Japan
*Corresponding author. Tel: +81 834 63 9912, Fax: +81 834 63 9932, e-mail: y_takami@tosoh.co.jp
Backgrounds
Catalytic combustion has been one of the most promising method to reduce volatile organic compounds (VOCs) emissions. Because of the strict
legislation of air pollution control, highly active catalysts are required. We have developed the hybrid catalyst composed of zeolite and Pt/Al 2 O 3 , which
can easily oxidize 1,2-dichloroethane. 1, 2 In this study, the oxidation tests of other VOCs were carried out with the hybrid catalyst.
Results
Catalytic activities were tested with various VOCs (toluene, alcohols, esters, ketones).
The hybrid catalyst oxidized the alcohols and the esters at much lower temperature than
Pt/Al 2 O 3 . For example, the required temperature for 50% conversion (T50) of ethyl
acetate was about 40 o C lower with the catalyst than with Pt/Al 2 O 3 (Figure 1). From GC
analysis, it was indicated that zeolite acid sites converted the alcohols and the esters to
other compounds which was easily oxidized.
100%
80%
60%
40%
20%
0%
zeolite hybrid catalyst
Pt/Al2O3
Catalytic durability was evaluated at 600 o C. The catalyst showed almost no change of
150 200 250 300 350
light off activity (T50) for at least 200 hr.
Justification for acceptance
temperature [degree C]
Figure 1. Catalytic oxidation of ethyl acetate.
GHSV = 40,000/hr, ethyl acetate = 500ppm
The hybrid catalyst can oxidize alcohols and esters to CO 2 at much lower temperature
than Pt/Al 2 O 3 . Since these VOCs are used as solvent in a large quantity, the catalyst is an effective tool for air pollution control.
References
[1] W. Kobayashi, Y. Ito, M. Nakano, Science and Technology in Catalysis 2002 (2002) 411.
[2] W. Kobayashi, M. Nakano, EP Patent EP1013332B1, 2005.
conversion to CO2 [%]

222 Feasibility of catalytic wet hydrogen peroxide oxidation process for the treatment of industrial wastewaters
J.A. Melero, J.A. Botas, F. Martínez, M.I. Pariente *
Department of Chemical and Environmental Technology, ESCET, Rey Juan Carlos University, 28933 Móstoles, Madrid, Spain
*Corresponding author. Tel: +34 91 664 74 93, Fax: +34 488 70 68, e-mail: isabel.pariente@urjc.es
Background
Many wastewater streams in chemical, petrochemical or pharmaceutical plants containing organic pollutants in high concentration exhibit a low biodegradability
and/or increased toxicity. Several studies have proposed Advanced Oxidation Processes (AOPs) for the treatment of wastewaters coming from different industrial
activities [1,2,3]. The aim of this work is the assessment of a continuous catalytic wet oxidation system using hydrogen peroxide (CWPO) for the treatment of
real industrial wastewater with different physico-chemical properties.
Results
Catalytic wet oxidation experiments in presence of hydrogen peroxide were carried out in a continuous up-flow fixed bed reactor. Iron oxide supported over
mesoporous SBA-15 silica was used as catalyst in form of agglomerated particles (1.8 mm of average diameter) [4]. A catalyst weight of 2.9 g was placed within
the tubular reactor (1.2 cm internal diameter and 15 cm length) operating at 80 °C under atmospheric pressure. The residence time was set to 11.6 g cat·min/g liq .
This experimental set-up was used for the treatment of three different wastewaters coming from pharmaceutical, refinery and petrochemical plants.
The activity in terms of TOC conversion and the stability of the catalyst in terms of iron concentration in the outlet effluents at steady-state conditions are shown
in Table 1. Further studies are being carried out to optimize the best operation conditions for each wastewater.
Pharmaceutical and refinery wastewaters seem to be more easily degraded by the continuous catalytic wet peroxide oxidation process. In addition, these
wastewaters are less harmful for the catalyst deactivation by metal leaching.
Justification for acceptance
Most of CWPO processes have been carried out in batch reactors and focused on the study of model pollutants. Hence, this research is not only addressed to the
continuous treatment of industrial wastewaters, but also, it is dealing with the potential application of this technology for the treatment of real wastewater
effluents coming from different industrial processes.
References
[1] E. Neyens, J. Baeyens, M. Weemais, B. De Heyder, J. Hazard. Mater. 98 (2003) 91.
[2] D. Mantzavinos, Water Air Soil Poll. 3 (2003) 211.
[3] H. Tekin, O. Bilkay, S.S. Ataberk, T.H. Balta, I.H. Ceribasi, F.D. Sanin, F.B. Dilek, U. Yetis, J. Hazard. Mater. B136 (2006) 258.
[4] F. Martínez, J.A. Melero, J.A. Botas, M.I. Pariente, R. Molina, Ind. Eng. Chem. Res. 46 (2007) 4396.
Table 1. TOC degradation and leached iron for the treated effluents under steady-state conditions.
Wastewater X TOC (%) [Fe] leaching (mg/L)
Pharmaceutical 40 0.05
Refinery 48 0.05
Petrochemical 18 13
228 New synthesis for Pt containing porous material for high temperature oxidation of volatile organic compounds
M. Hutt a,* , A. Tissler a , H.C. Schwarzer a and T. Turek b
a Süd Chemie AG,. Waldheimer Str. 13, 83052 Bruckmühl, Germany
b
Institute of Chemical Process Engineering, Clausthal University of Technology, Leibnizstr. 17, 38678 Clausthal-Zellerfeld, Germany
*Corresponding author. Tel: +49 8061 4903 833, Fax: +49 8061 4903 704, e-mail: Markus.Hutt@sud-chemie.com
Background: Catalysts, containing small metal clusters on the outer surface of a support material are well known in the chemical industry. Furthermore, they are
used in the exhaust gas after treatment of combustion engines. The activity of such catalysts is influenced by metal particle size. The state of art metal catalysts,
are not suitable for high temperature applications because their activity decreases rapidly with increasing temperature due to sintering of the metal particles. The
aim of the developed synthesis is to encapsulate platinum-particles inside the pore system of a micro-porous material. The inclusion leads to reduced sintering
and therefore ensures high temperature stability of the catalytic system.
Results: The catalyst used as benchmark show good activity in the beginning of the catalytic test but have a short lifetime and deactivate rapidly after thermal
aging. Despite to this, the catalyst prepared by the newly developed method does hardly deactivate after thermal treatment at 700°C and above. The increased
thermal stability is an evidence for the encapsulation of the platinum clusters. Latest results show that the synthesis can be applied for zeolites as well as for other
microporous systems. Additionally it is possible to encapsulate platinum clusters in porous materials which already contain metal oxides. The formation of mixed
metal oxides inside the pores provides the possibility to adjust the chemical properties of the platinum clusters. The modification of the electronic structure can
be used to enhance the catalytic activity, the thermal and hydrothermal stability [1] and the resistance against poisons such as sulphur [2].
Justification for acceptance: In order to reduce the emission of gas-fired power plants, it is of great importance to provide new catalysts which are able to
operate in the temperature range required and provides a reasonable lifetime. Furthermore, the temperature stable noble metal catalyst can be used in vehicle
exhaust gas treatment for example as diesel oxidation catalyst or in diesel particulate filter.
References:
[1] A.Yu. Stakeev, L.M. Kustov, Appl. Catal. A 188 (1999) 3.
[2] J. Zheng, T. Schmauke, E. Roduner, J.L Dong, Q.H. Xu, J. Mol. Catal. A 171 (2001) 181.

236 Catalysis by phthalocyanines of chlorophenols oxidation
T. M. Fedorova*, E.G. Petrova, S.A. Borisenkova, O.A.Yuszakova, V.M.Negrimovskiy, O. L. Kaliya
Organic Intermediates and Dyes Institute, ¼ B.Sadovaya str., 123995, Moscow, Russia
*Corresponding author. Tel: (007)(495) 25 49 866 , Fax : (007)(495) 25 47 015, e-mail: noshul@yandex.ru
Background
As it is known phenol and chlorophenols are among the most recalcitrant pollutants, which possess toxic, carcinogenic and mutagenic properties. That is why
degradation of these compounds is an important environmental research field. Different methods are developed to remove phenols from wastewater. These
include biological degradation, incineration, wet air oxidation, electrochemical and photochemical treatment and others. Bioinspired oxidation of chlorophenols
using hydrogen peroxide as oxidant has been widely investigated recently, in which iron salts (Fentons reagent), porphyrines, phthalocyanins and other
complexes have been applied as models of peroxidases.
Results
The present study reports on catalytic oxidation of phenols (phenol, 2- and 4-chlorophenols, 2,4- and 2,6-dichlorophenols, 2,4,6-trichlorophenol) by hydrogen
peroxide. Water soluble iron phthalocyanins (FePc(SO 3 H) 4 and FePc(N + R 3 ) n , where n=8 or 16) were used as catalysts. It has been found that oxidation of
phenol, 2- and 4-chlorophnols, 2,6-dichlorophenol in water solution of FePc(SO 3 H) 4 ([substrate]=2·10 -3 M, [HCl]=[H 2 O 2 ]=6·10 -3 M, 5% alcohol) results in
polymeric compounds (yield from 60% to 95%), which are separated by filtration. Filtrate contains small amount of quinines and low-molecular weight products.
In the case of 2,4-dichlorophenol only an increase in turbidity was observed.
Bearing positively charged substituents complexes FePc(N + R 3 ) n were proved to be also effective catalysts in phenols oxidation. The reaction has been initiated by
H 2 O 2 addition to mixture of FePc and substrate solutions at the room temperature. Conversion of phenol and products identification was performed by using
HPLC-UV. The oxidation reaction depends on pH medium considerably. For example, phenol conversion in water and phosphate buffer (pH 6.8) is equal to 10-
15% whereas in acidic medium (pH 5.4) it is increased to 67%. Oxidation other substrates is undergoing analogical influence of pH. The reaction does not occur
in alkaline solution (pH 9.18). Phenols containing Cl in p-position are more active than o-chloroderivatives.
2,4,6-Trichlorophenol is the most active in oxidation by H 2 O 2 . Conversion of this substrate reaches to about 100% at pH 6.8 and 5.4. 2,6-Dichlorophenol is the
main product of the reaction. This one is rather stable in acidic solution and destroys in buffer with pH 6.8. The dependence of conversion on catalyst and
substrate concentration as well as influence of salts (H 2 PO 4 - , HPO 4 -2 , SO 4 2- , ClO 4 - ) was studied.
Noteworthy that H 2 O 2 can be produced within catalytic oxidation (FePc, CoPc) of ascorbic acid by air and used in 2,4,6-trichlorophenol oxidation.
Heterogeneous catalysts formed by supporting substituted FePc on different carriers were obtained and tested.
The data reported show that high conversion of mono- and dichlorophenols can be achieved by using system FePc-H 2 O 2 at room temperature. Non water soluble
coupling products of chlorophenols oxidation are easy removed by filtration. Oxidation of 2,4,6-trichlorophnol is attended by dechlorination (1 Cl/1 mole) and
destruction to small biologically degradable molecules.
240 EnviNOx ® process for the abatement of nitrous oxide emissions from nitric acid tail gases
M. Schwefer a , R. Siefert a , H.C. Schwarzer b , A. Tissler b , C. Perbandt c and T. Turek c, *
a Uhde GmbH,Friedrich-Uhde-Str. 15, 44141 Dortmund, Germany.
b Sued-Chemie AG, Waldheimer Str. 1, 83052 Heufeld, Germany.
c Institute of Chemical Process Engineering ‚Clausthal University of Technology, Leibnizstr. 17, 38678 Clausthal-Zellerfeld, Germany.
*Corresponding author. Tel: +49 5323 72 2184, Fax : +49 5323 72 2182, e-mail: turek @icvt.tu-clausthal.de
Background: Nitrous oxide (N 2 O) forms during the catalytic oxidation of ammonia as by-product in the manufacture of nitric acid by the Ostwald process. An
ideal N 2 O abatement technology should be combined with the reduction of NO x emissions, since this is also required in nitric acid plants. Uhde has recently
commercialized the EnviNOx process for the simultaneous removal of N 2 O and NO x using EnviCat iron zeolite catalysts developed by Sued-Chemie AG.
Depending on the tail gas temperature N 2 O can either be decomposed to N 2 and O 2 or reduced by hydrocarbons while NO x is reduced to N 2 by NH 3 [1].
Results: In the present contribution we report on experimental investigations of iron zeolite catalysts used for the decomposition and reduction of N 2 O with
hydrocarbons as well as the reduction of NO x with ammonia. The kinetics of N 2 O decomposition will be discussed in detail as an example. Not only temperature
and the concentrations of N 2 O, NO and H 2 O, but also mass transfer resistances have to taken into account for a quantitative description of the decomposition rate
under industrially relevant conditions. Using adequate kinetic and reactor models, the design of technical reactors based on laboratory data is possible. We
furthermore present results for the catalytic reaction of nitrous oxide with reducing agents such as ammonia, methane and propane, the use of which allows for
N 2 O conversion at considerably lower temperature than required for decomposition. However, while the presence of nitric oxide is highly desirable during the
decomposition of N 2 O, it plays a detrimental role when reducing agents are present. Mechanistic aspects of the positive or negative functions of nitric oxide as
well as consequences for technical process options are discussed. Finally, operating results from several commercial scale implementations of this EnviNOx TM
technology are presented. Both technically realized process variants – the high temperature option using N 2 O decomposition and the low temperature variant
employing catalytic reduction – allow for very high nitrous oxide conversions of up to 99%, combined with NO x reduction to less than 5 ppm.
Justification for acceptance: The contribution deals with mechanistic aspects of nitrogen oxides reactions over iron exchanged zeolites, a catalyst system that
has been intensively studied during the last years. Since N 2 O is a potent greenhouse gas, and nitric acid plants now represent the largest single industrial process
emitting around 400 kt N 2 O equivalent to 125 Mt CO 2 per year, there is a need for industrially viable abatement technologies.
References:
[1] M. Groves, R. Maurer, M. Schwefer, R. Siefert, Proceedings of the Nitrogen 2006 Conference, Vienna, Austria (2006) 121.

250 N 2 O decomposition mechanism on Rh catalyst studied by isotopic gases
S. Parres Esclapez, A. Bueno López*, M.J. Illán Gómez, C. Salinas Martínez de Lecea
Department of Inorganic Chemistry, University of Alicante,Ap.99, E-03080 Alicante (Spain).
*Corresponding author. Tel: +34965903400 (2226), Fax: +34965903454, e-mail: agus.@ua.es
Background
The environmental impact of N 2 O has attracted strong public attention because of its assumed contribution to global warming and ozone depletion in the upper
atmosphere. The catalytic decomposition has been proposed for N 2 O abatement. The aim of this study is to probe the contribution of the lattice oxygen of CeO 2 in
the N 2 O-decomposition reaction pathway on a Rh/CeO 2 catalyst, and to analyse the causes of the inhibiting O 2 effect.
Results
N 2 O decomposition experiments were carried out in a fixed bed reactor between 200 and 500ºC with 1000 ppm N 2 O and 1000 ppm N 2 O / 5% O 2 gas flows. The
catalysts studied were Rh/CeO 2 and Rh/Al 2 O 3 . Experiments were also conducted with the unloaded supports. Rh/CeO 2 is more active than Rh/Al 2 O 3 , however, no
decomposition of N 2 O is observed on the bare supports. Isotopic exchange experiments consist of heating the catalysts at a given temperature (50, 200, 250, 300,
350 and 400 ºC) in a carrier inert gas (He, 10 ml/min) and then pulsing 18 O 2 or 15 N 2 18 O onto the sample. Prior to the transient experiments the catalysts were pretreated
at ambient pressure in a flow of oxygen (30 ml/min) at 400 ºC for 30 min. Both Rh catalysts yield 15 N 2 and 16 O-containg O 2 ( 16 O 18 O and/or 16 O 2 ) in
transient experiments. In the case of Rh/Al 2 O 3 , the amount of 16 O corresponds to that of Rh 2 O 3 while 16 O from CeO 2 is clearly involved in the case of Rh/CeO 2 .
O 2 has an inhibiting effect on the N 2 O decomposition reaction. Transient experiments with 18 O 2 pulses evidenced 16 O 18 O and/or 16 O 2 formation, so, the inhibiting
effect can be attributed to the competition of both gasses (N 2 O and O 2 ) for the oxygen exchange sites on the catalysts. The promoting effect of CeO 2 and the N 2 O-
decomposition reaction pathway will be discussed.
Justification for acceptance
N 2 O abatement technologies have become quite relevant in recent times, mainly because N 2 O is a powerful greenhouse gas and given the recent interest to curb
global warming. Due to its simplicity and the innocuousness of the reaction products, a decomposition catalyst would be the ideal approach to this problem.
Probing the reaction mechanism would improve the development of N 2 O decomposition catalysts.
253 Activation of hydrotalcite-like materials containing nickel for catalytic decomposition of nitrous oxide
P. Kutrowski * , L. Chmielarz, R. Dziembaj
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland
Corresponding author. Tel: +48 12 6632006, Fax: +48 12 6340515, e-mail: kustrows@chemia.uj.edu.pl
Background
An emission of N 2 O from nitric and adipic acids production units is a real environmental problem, which has to be eliminated due to the Kyoto protocol. The
catalytic decomposition of nitrous oxide to molecular oxygen and nitrogen is the simplest and cheapest way to limit an amount of produced N 2 O. Mixed oxides
including NiO-modified systems have been found to be promising catalysts of this process.
Results
Hydrotalcite-like precursors with various cationic (different amounts of Ni 2+ dispersed in Mg 2+ - and Al 3+ -containing brucite-like sheets) and anionic (carbonate or
benzoate anions intercalated in an interlayer space) compositions were prepared by the coprecipitation method. XRD and UV-vis-DR spectroscopy confirmed the
successful synthesis of the hydrotalcite-like structure. An influence of chemical composition on values of lattice parameters and the interlayer anions orientation
was discussed. The thermal stability of the synthesized layered materials was studied by TGA and SDTA. Moreover, gaseous products evolved during a thermal
treatment were analyzed by mass spectrometer connected on-line to the TG instrument. The mechanism of decomposition of the differently modified
hydrotalcite-like compounds was proposed. The studied precursors were transformed into mixed metal oxides by a thermal activation at 550°C. The resulting
catalysts were examined with respect to textural (BET) and redox (TPR) properties. The chemical environment of transition metal was additionally determined
by UV-vis-DRS. It was found that the anionic modification of the hydrotalcite structure strongly influenced the features of the calcined materials. The
hydrotalcite-derived catalysts were tested in the decomposition of N 2 O in the absence and presence of oxygen. It was observed that the catalytic activity
depended on the Ni loading. The reaction mechanism was postulated. Finally, a stability of the examined catalysts in the presence of H 2 O, being a typical
component of flue gases, was shown.
Justification for acceptance
The presented work exhibits a lot of interesting results, which can allow to evaluate a possibility of application of hydrotalcite-derived mixed oxides as catalysts
of N 2 O decomposition. The catalytic performance of the Ni-modified catalysts has been deeply analyzed in relation to the solid properties.

257 Rapid elimination of methylene blue dye in wastewater by
adsorptive and photocatalytic activities of structurally modified and supported TiO 2
M.A. Zanjanchi*, H. Golmojdeh
Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 1914, Rasht, Iran
*Corresponding author. Tel: +98-131-3226643, Fax: +98-131-3220066, e-mail: zanjanchi@guilan.ac.ir
Background
The extensive use of dyes causes environmental problems in the ecosystem. Introducing dyes compounds into the environment is through effluent water of
many industries. The complex aromatic structures of dyes make them more stable and more difficult to remove from the wastewater sources. Removal of dye
from industrial effluents using the adsorption process has been generally considered to be an efficient method for lowering the concentration of dissolved dyes in
an effluent. However, in recent years photocatalytic degradation and heterogeneous photocatalysis has been developed for pollutant elimination [1,2]. In this
contribution, we describe preparation of an active adsorbent-photocatalyst by incorporation of H 3 PW 12 O 40 -TiO 2 composite into MCM-41. This catalyst is used
for adsorption and photodegradation of methylene blue.
Results
The H 3 PW 12 O 40 -TiO 2 composite was prepared from titanium tetraisopropoxide and tungstophosphoric acid. The MCM-41 was synthesized by a room
temperature synthesis method. The photocatalyst was made by incorporating H 3 PW 12 O 40 -TiO 2 into MCM-41 via an impregnation method. A homemade
photochemical reactor consisting of a beaker containing the suspension of methylene blue (MB) solution and solid photocatalyst was magnetically stirred before
and during irradiation.with a UV 400 W lamp. The progress of adsorption and degradation of MB was checked by the Uv-vis spectrophotometer. The aqueous
dye/catalyst suspension was prepared by addition of 0.1g catalyst to a 100 mL aqueous solution of MB with initial concentration of 30mgl -1 . Our results show
that the rate of elimination of MB in a 100 ml solution with initial concentration of 30 mg/l of the dye is so high that all of the dye is removed within 15 min. The
amount of adsorption of MB within first 5 min stirring in the dark is also high and this could be related to the negative charge of the catalyst surface at our
experimental conditions.
Justification
The electrical charge of the solid surface of the photocatalyst would strongly affects adsorption of cationic MB + dye molecules. The amount of conversion
within 15 min is much lower for bare TiO 2 (3%) or pure MCM-41(23%) and this indicates the great improvement attained by using our prepared photocatalyst
for elimination of MB as a cationic dye. Absence of UV irradiation requires a longer time (60 min) for complete removal of MB solely based on adsorption in
the dark.
References
[1] A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C, 1 (2000) 1.
[2] M. Anpo, M. Takeuchi, J. Catal. 216 (2003) 505.
262 CO Oxidation on Pd/Al 2 O 3 : Correlation between Pd- oxidation state and activity
Katrin Zorn a* , Suzanne Giorgio b , Claude R. Henry b and Günther Rupprechter a
a Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria
b Centre National de la Recherche Scientifique (CNRS), Campus de Luminy, Marseille, France
* Corresponding author. Tel : +43 1 25077 3815, Fax : +43 1 25077 3890, email : kzorn@imc.tuwien.ac.at
Background
Supported Pd catalysts are of great practical importance and used in commercial 3-way-catalysts to reduce automotive emission (oxidation of CO and unburned
hydrocarbons and reduction of NO x ). The nature of the active phase (metallic Pd vs. PdO x ) for these processes is still controversially discussed in the literature.
The aim of this study is to investigate the oxidation of CO on a technical Pd-Al 2 O 3 catalyst, with the Pd oxidation state being varied by applying different
oxidizing or reducing activation procedures. In order to correlate the oxidation state with the catalytic activity the catalysts were characterized by IR spectroscopy
(using CO as probe molecule), HRTEM, XRD and XPS.
Results
“Mild” oxidation conditions up to 400°C did not change the properties of the catalyst, whereas stronger oxidation (450°C, 1 bar oxygen) reduced the CO
adsorption capacity and a new adsorption band corresponding to CO adsorbed on Pd + was observed by IR. This suggests the formation of substoichiometric
PdO x but catalytic tests showed that a pre-oxidized catalyst exhibited only slightly lower catalytic activity for CO oxidation. IR spectroscopy (with CO as probe
molecule), XRD and HR-TEM measurements before and after reaction, as well as in situ IR spectroscopy measurements during reaction indicated that the high
activity is most likely due to a fast reduction of PdO x under reaction conditions. Therefore, metallic palladium is again responsible for the high catalytic activity.
Total oxidation to PdO was only obtained by pre-oxidation at temperatures around 800-1000°C. PdO is stable against reduction under reaction conditions and
turned out to be quite inactive at reaction temperatures below 200°C. XPS measurements are currently performed to further characterize the palladium phases
present.
Justification for acceptance
Palladium catalysts are widely used in environmental catalysis: reducing the emission of CO, NO x , unburned hydrocarbons or safe conversion of chlorinated
waste (hydrodechlorination). This comprehensive study leads to a deeper insight on the ongoing processes (especially under reaction conditions) which is
necessary to improve catalyst performance.

263 Catalytic oxidation of isopropanol/o-xylene mixture on zeolite catalysts
R. Beauchet*, J. Mijoin, P. Magnoux
Université de Poitiers, LACCO UMR CNRS 6503, 40, av. du Recteur Pineau, 86022 Poitiers cedex, France
* corresponding author: Tel: 0033549453914, email: romainbeauchet@hotmail.com
Background: If catalytic oxidation of pure VOCs has been widely studied, there are, however, few articles about their treatement in mixture[1.2], although
VOCs are mainly emitted under this form. In this study, an evaluation of various zeolites performances with or without platinum (NaX, HFAU(5), 0.5PtNaX,
0.5PtHFAU(5) has been realised for oxidation of different isopropanol/o-xylene mixtures : (1360/210 ppm, 210/1360 ppm, 1360/1360 ppm). Experiments have
been realised in presence of water (11000 ppm) and with a high WHSV (18000 h -1 ). Stability during reaction time and humidity effect were also studied.
Results: Catalytic oxidation of the isopropanol in mixture with o-xylene shows that VOCs could react differently if they are oxidised alone or in mixture. The
presence of isopropanol seems to improve the destruction of o-xylene on HFAU(5) (in the o-xylene/isopropanol 210/1360 ppm and 1360/210 ppm mixtures).
This promoting effect could be the result of the combustion of an intermediary product (isopropyldimethylbenzene) formed from isopropanol and o-xylene [3].
On NaX and 0.5PtNaX, isopropanol destruction is inhibited with the addition of o-xylene. On the other hand, no effects of mixture have been observed on
0.5PtHFAU(5). Results show the formation of different intermediary products depending on the catalyst used. On acid catalyst, formation of propene and
isopropyldimethylbenzene are observed. On basic catalyst, formation of acetone is mainly observed. However, with the increase of o-xylene amount in the
mixture, destruction of isopropanol leads to more formation of propene (probably because of competitive adsorption). The addition of platinum on these catalysts
enables to lower reaction temperature. Thus, isopropanol and o-xylene mixture can be totally destroyed from 200°C. In all experiments, the acidic zeolite
(HFAU(5)) is the worst catalyst, probably due to the high amount of coke formation during catalytic oxidation. Stability and humidity effects were studied on
NaX for the oxidation of the isopropanol/o-xylene (210/1360 ppm) mixture. Results show the importance of humidity for the total destruction of this mixture. In
fact, humidity has a promoting effect on the oxidation (10 % of CO 2 under air without humidity instead of 35% of CO 2 under wet air at 250°C). Stability study
shows, at 250°C, a rapid deactivation of NaX during the first hours and then a slow decrease. At the end of the reaction (103 hours) CO 2 yield is equal to 34%.
Justification for acceptance: This work has been carried out to give a better understanding of isopropanol and o-xylene destruction in mixture as they are used
in industrial processes. Promoting or inhibiting effects on the oxidation (due to intermediary products, competitive adsorption…) has been observed. Results
show the high activity of zeolites and Pt/zeolites for the total destruction of isopropanol and o-xylene in mixture.
References
[ 1 ]N. Burgos, M. Paulis, M. Mirari Antxustegi, M. Montes, Appl. Catal. B 38 (2002) 251-258
[ 1 ]R.W.Van Den Brink, P Mulder, R. Louw, Catal. Today, 54 (1999) 101-106
[ 1 ]R. Beauchet, P. Magnoux, J. Mijoin, Catal. Today, 124 (2007) 118-123
271 Ultrasound activated catalytic systems for waste water denitrification
A. Gavrilenko, A. Sidorov*, M. Sulman, V. Matveeva, E. Sulman,
Dept. Biotechnology and Chemistry, Tver TechnicalUniversity, Tver, Russia
*Corresponding author. Tel/Fax: +74822449317, e-mail: sulman@online.tver.ru
Background
Nitrates are one of the most dangerous pollutants. Long consumption of drinking water and food-stuffs containing considerable amount of nitrates (25-100
mg/dm 3 ) can cause intoxication. The nitrate concentration in ground water, which is the main source for drinking water, is still rising throughout the world.
Removal of nitrates from waste wter is rather complicated due to their high solubility. The existing methods of water purification cannot completely solve the
problems of decreasing nitrates concentration [1 – 3]. Thus the catalytic method of denitrification one seems to be the most promising one. This work is directed
to the nitrates catalytic reduction by molecular hydrogen using Pd-containing heterogeneous catalysts.
Results
During the process of catalytic denitrification by hydrogen, depending on the reaction conditions, various intermediates and end-products can be formed (NO,
N 2 O, N 2 , NH 4 OH and NH 4 + ) under the influence of various parameters (temperature, hydrogen pressure, nature of the catalyst). It is important to emphasize that
the aim of selective nitrate reduction is to completely convert the nitrate-ions and intermediates to harmless nitrogen. The search of optimal reaction conditions
(temperature, pressure) as well as catalytic system (metal, type of support) is of crucial importance. Palladium-containing catalytic systems are the most often
used ones as they provide high activity.
In this study the reduction of nitrates in a water solution was investigated using the following catalytic systems: Pd/ -Al 2 O 3 (0.5% Pd), Pd-Zn (1:3) / –
Al 2 O 3 (0.5% Pd), Pd-Cu (4:1) / –Al 2 O 3 (4.7% Pd) and Pd-Sn (4:1) / –Al 2 O 3 (4.7% Pd). Reaction was carried out in a constant-temperature glass reactor with a
tube for the constant supply of hydrogen as a reducing agent. NO 3 - ions concentration has been determined by a potentiometric method using combined nitrateselective
electrode. For all catalysts physicochemical investigations (XPS, XFA, and BET) were conducted.
As a result of the investigation the optimal reaction conditions (temperature, stirring rate, catalyst loading) were found. As a catalytic system providing
the most effective nitrates reduction in an aqueous solution Pd-Cu (4:1) / –Al 2 O 3 was chosen. For this catalyst nitrates conversion reached up to 99% during the
first 40 min of the reaction at 14 o C.
According to the experimental results the description of the process of nitrates catalytic reduction to nitrogen by the method of formal kinetics with the
calculation of the numerical values of the parameters of mathematical description equation was suggested.
During the investigation it was found that the ultrasound treatment of the catalyst, depending on the parameters, can lead either to the increase or to the
decrease of catalytic activity. The best results regarding to the nitrate-ion conversion at the same duration of the experiment were obtained at the following
parameters of ultrasound pretreatment: intensity – I = 3 Wt/cm 2 , duration – 15 s.
References
[1] Möller, W. R., Möglichkeiten und Verfahren der mikrobiellen Denitrifikation zur Aufbereitung von nitratbelastetem Rohwasser zu Trinkwasser. Erich Schmidt
Verlag: Berlin, 1989.
[2] J. Schmidt, Brunnenbau - Bau von Wasserwerken - Rohrleitungsbau 3 (1997) 29.
[3] K. Daub, G. Emig, M.-J. Chollier, M. Callant, R. Dittmeyer, Chem. Eng. Sci. 54 (1999) 1577.

272 Novel catalyst on a basis of immobilized oxidoreductases for wastewater purification from phenols
Sidorov A. * , Tikhonov B., Lakina N., Sulman E.
Dept. Biotechnology and Chemistry, Tver TechnicalUniversity, Tver, Russia
*Corresponding author. Tel/Fax: +74822449317, e-mail: sulman@online.tver.ru
Background
In recent years the use of the immobilized enzymes in industrial catalysis has considerably increased. There are the following major reasons for attaching
enzymes to various supports: multiple or repetitive use of a single batch of enzymes; the ability to stop the reaction rapidly by removing the enzyme from the
reaction solution; enzymes are usually stabilized by bounding, etc. While creating the reusable catalytic systems on the basis of enzymes one of the main
problems is the choice of the firm carrier for immobilization of enzyme, which will provide its best stabilization [1, 2].
Results
In this work various catalytic systems were investigated. Cation-exchange resin with SO 3 H active group (diameter – 0.4-1 mm, exchange capacity – 1.8 mol/cm 3 ,
surface area – 13.46 m 2 /g) and anion-exchange resin with the active vynilpyridine group (diameter – 0.6-1 mm, exchange capacity – 2.77 mol/cm 3 , surface area –
32.5 m 2 /g) on the basis of styrenedivynilbenzene were used as the carriers. Ion exchange resins were treated with sodium alginat, chitosan, glutaric dialdehyde
and carbodiimide. Two methods of chitosan and activating agent deposition on ion exchange resin – consecutive deposition and deposition of components
mixture – were studied.
For the investigated catalysts the optimal conditions of phenols oxidation process with achievement of a high degree of conversion (more than 95 %) were
found: temperature – 25 º, intensity of mixing – 300 min -1 , 6.5 and 7 – for peroxidase and tyrosinase, respectively. The optimal ratio of the components of
catalytic systems was determined, and physicochemical investigations (FTIR spectroscopy, XPS, nitrogen physicosorption) of optimal biocatalytic systems were
carried out. Experiments shown, that consecutive deposition of chitosan and glutaric aldehyde on cation-exchanger provides the strongest and stablest bounding
of enzyme with the carrier. During the experiments it was shown that glutaric aldehyde provides better stabilization of enzyme on the carrier in comparison to
carbodiimide. Activity of synthesized catalyst was found to remains practically constant during repeated use in reaction of phenols (catechol, phenol etc.)
oxidation.
Kinetic and physicochemical investigations shown, that for the most active biocatalytic systems biopolymer (chitosan) is distributed on the surface of the
carrier as separate molecules or bidimentional clasters, without formation of 3D structures. Such distribution promotes minimization of intradiffusive limitation
during oxidation.
Synthesized biocatalytic systems on the basis of horseradish peroxidase and field mushroom tyrosinase were found to be highly active and stable in
catalytic oxidations of phenols including at sewage treatment and industrial waste products.
References
[1] L.V.Bindhu, E.T.Abraham. Inc. J. Appl. Polym. Sci. 88 (2003) 1456-1464.
[2] M.S. Ibrahim, H.I.Ali, K.E Taylor., N.Biswas, J.K.Bewtra. Water Environ. Res. 73 (2001) 165-172.
277 Activated carbon and ceria as catalysts for the ozonation of organic compounds in the aqueous phase
P.C.C. Faria * , J.J.M. Órfão, M.F.R. Pereira
Laboratório de Catálise e Materiais, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*Corresponding author. Tel: +351 225 081 998, Fax : +351 225 081 449, e-mail: pfaria@fe.up.pt
Background
Heterogeneous catalytic ozonation processes are being intensively studied in the scope of wastewater treatment, with the aim of increasing the mineralization of
highly refractory compounds. The goal of the present work is to evaluate the catalytic activity of ceria in ozonation reactions and to investigate a possible
synergic effect between activated carbon and ceria in the ozonation of selected organic compounds.
Results
The present work reports data on the ozonation of model aromatic compounds (benzenesulfonic acid, sulfanilic acid and aniline) and carboxylic acids (oxalic and
oxamic acids), catalyzed by cerium oxide and a ceria-activated carbon composite material, and compares the corresponding results with those obtained in the
presence of activated carbon [1,2]. The ceria containing catalysts were characterized by XRD, SEM and XPS in order to correlate the catalysts activity with their
chemical structure and surface properties. Both ceria containing catalysts were found to be effective ozonation catalysts. Comparatively to the performance of the
commercial activated carbon, an enhanced mineralization extent was achieved, particularly in the case of benzenesulfonic and oxalic acids, where complete
mineralization was obtained. A strong synergic effect was observed between activated carbon and ceria in the prepared composite, leading to enhanced
mineralization degrees for all the studied compounds. The mechanism of the ozonation catalyzed by the ceria-activated carbon composite is believed to comprise
both surface reactions, similar to what occurs with activated carbon promoted ozonation, and also liquid bulk reactions involving HO • radicals, resultant from the
catalytic decomposition of ozone on the surface of the activated carbon and mainly in the presence of ceria.
Justification for acceptance
The development of highly effective catalysts for the application in ozonation processes and the understanding of the inherent mechanisms are of great
importance. No data have been found in the literature reporting the use of activated carbon/cerium oxide composites as ozonation catalysts. The results of the
present work show that the mechanistic cooperation between ceria and activated carbon in the composite enables the improvement of the mineralization degree of
highly refractory compounds.
Acknowledgements: Fundação para a Ciência e a Tecnologia - BD/18169/2004 and POCTI/FEDER (POCTI/1181).
References
[1] P.C.C. Faria, J.J.M. Órfão, M.F.R. Pereira, Appl. Catal. B-Environ. 79 (2008) 237.
[2] P.C.C. Faria, J.J.M. Órfão, M.F.R. Pereira, Appl. Catal. B-Environ. (2007) doi:10.1016/j.apcatb.2008.02.010.

281 Phenol degradation by Fenton system with in-situ generated H 2 O 2 over supported-Pd catalysts
M. S. Yalfani*, S. Contreras, F. Medina and J. E. Sueiras
Department of Chemical Engineering, Universitat Rovira i Virgili, Av. Països Catalans 26, 43007, Tarragona, Spain.
*Corresponding author. Tel: +34 977 558535, Fax : +34 977 559667, e-mail: ms.yalfani@urv.cat
Background Fenton reaction, based on the generation of hydroxyl radicals by means of the decomposition of H 2 O 2 with Fe 2+ , has been used for many years
for the treatment of wastewaters containing organic pollutants [1]. In this process, H 2 O 2 is the main reagent and means the main operating cost. The direct
generation of H 2 O 2 from H 2 and O 2 [2], or using other substances as source of hydrogen [3] has received an increasing interest in recent years [4]. Recently, we
have studied the in-situ H 2 O 2 formation from formic acid as hydrogen source and oxygen, at ambient conditions and in aqueous medium, using heterogeneous
supported-Pd catalysts (Pd/Al 2 O 3 , Pd/C, Pd/TiO 2 ) [5]. This catalytic system has been tested in the oxidation of phenol (as model compound) by means of the
Fenton reaction (Fe 2+ /H 2 O 2 ).
Results According to the results obtained during the generation of H 2 O 2 reactions, Pd5%/TiO 2 showed the highest productivity of H 2 O 2 at short time (5
min), 132 mmol H 2 O 2 .(g (Pd) .h) -1 , while over Pd5%/Al 2 O 3 the productivity was more stable at long time. No H 2 O 2 was detected when Pd/C was used. Fenton
experiments were performed with this catalytic system (supported-Pd catalyst, 25 mmol formic acid, 20 mL/min oxygen) in presence of phenol (50 ppm) and
Fe 2+ (10 ppm). The Pd5%/Al 2 O 3 and Pd5%/TiO 2 catalysts showed ability to degrade phenol at 25C up to 40% and 30%, respectively, after two hours reaction.
Blank experiments to test the effect of adsorption and stripping were also performed, showing that this effect was negligible in the case of Pd/Al 2 O 3 and Pd/TiO 2
catalysts. The effect of temperature was also studied with Pd5%/Al 2 O 3 . At 50C, nearly 90% of initial phenol was degraded within 2 hours. Hydroquinone,
catechol and benzoquinone were identified among intermediates produced (confirmed by the brown color observed) and monitored their concentration
throughout the reaction. Catechol is the intermediate produced in higher concentration, while benzoquinone is the one showing most recalcitrance to oxidation.
The efficiency of this process was compared with conventional Fenton system (with 10 ppm Fe 2+ and 180 ppm commercial H 2 O 2 added stepwise through the
reaction). In the conventional Fenton process a faster degradation of phenol was observed, but intermediates remained for longer time. Further optimization of
our catalytic system is subject of future work.
Justification for acceptance The use of in-situ generated H 2 O 2 from formic acid and oxygen in the Fenton process can be considered as a new, safe, clean and
environment-friendly process which is able to overcome several drawbacks related to bulk generation of hydrogen peroxide such as cost and storage. In
particular, formic acid presents advantages in comparison with other hydrogen sources found in literature, like hydrazine [4].
References
[1] J. J. Pignatello, E. Oliveros, A. Mackay, Crit. Rev. Environ. Sci. Technol. 36 (2006) 1.
[2] J. H. Lunsford, J. Catal. 216 (2003) 455.
[3] V. R. Choudhary, C. Samanta and P. Jana, Chem. Commun (2005) 5399.
[4] J. M. Campos-Martin, G. Blanco-Brieva and J. L. G. Fierro, Angew. Chem. Int. Ed 45 (2006) 6962.
[5] M. S.Yalfani, S.Contreras, F. Medina, J.Sueiras, Chem. Commun. (2008) submitted.
284 Catalytic removal of propene in air over Pd oxide catalysts
M. Ousmane a, c , L. Retailleau a , A. Giroir-Fendler a * , L. F. Liotta b , G. Di Carlo c , G. Pantaleo b G. Deganello b,c ,
a Université de Lyon, Lyon, F-69003, France, Université Lyon 1, Villeurbanne, F-69622, France, CNRS, UMR 5256, IRCELYON, 2 avenue Albert Einstein,
Villeurbanne, F-69622, France.
b Istituto per Lo Studio dei Materiali Nanostrutturati (ISMN)-CNR via Ugo La Malfa, 153, 90146 Palermo, Italy.
c
Dipartimento di Chimica Inorganica e Analitica “Stanislao Cannizzaro”, Università di Palermo, Viale delle Scienze, Parco d’Orleans II - 90128 Palermo, Italy.
*Corresponding author: tel/fax 00(33)472431586, email: anne.giroir-fendler@ircelyon.fr
Background
The advantage of low oxidation temperature is the reduction of fuel consumption, particularly for large volumes of diluted VOC polluted air. Noble metal
catalysts present higher activity than other metal catalysts, but in many cases the hydrothermal stability of the support is not sufficient. An interesting way to
obtain more active and stable catalysts is through the use of oxide supports stabilized with some percentage of dope. In the present study, Pd/Ce/Al 2 O 3 catalysts
have been investigated as precursors of VOCs oxidation catalysts and compared to Pd/Al 2 O 3 and Pd/CeO 2 .
Results
A series of Pd (1 wt.%) over alumina, ceria and ceria(5-10 mol %)/alumina catalysts has been prepared by classical impregnation method [1]. Characterizations
by BET, XRD, TEM-EDX were carried out. The catalytic activity measurements were carried out under a reactive mixture containing 1000 ppm of C 3 H 6 and 9%
O 2 with a flow rate of 7.2 L/h. The general behaviour of the Pd catalysts is in good agreement with the light curves which could be obtained in the combustion of
VOC’s traces. As a function of the support, propene oxidation started at low temperature between 100°C and 150°C and is nearly complete between 150°C and
250°C. Among the investigated catalysts Pd/Ce(5%)/Al 2 O 3 is the most efficient, under our operating conditions achieving a 50% of propene conversion at 150
°C. The higher efficiency of the Pd catalyst is likely related to the chemical properties of the mixed oxide and to the localisation, the dispersion and the nature of
the palladium particles.
Justification for acceptance
The catalytic results in propene conversion suggest that the Pd ceria-alumina catalysts are promising for VOCs oxidation at low temperature.
References
[1] Denton P, Giroir-Fendler A, Praliaud H, et al. J. of Catal. 189 (2000) 410

298 Performance of SBA-type catalysts in degradation of polypropylene
Z.Obali*, N.A.Sezgi and T.Dogu
Chemical Engineering Department,Middle East Technical University, Ankara, Turkey
*Corresponding author. Tel:+90 312 2104363, Fax:+90 312 2102600, e-mail: z_obali@yahoo.com
Background
Consumption of plastic products has increased drastically over the past few decades. This has a negative effect on the environment as it causes a rapid increase in
the amount of plastic waste. To overcome this, several disposal methods have been offered such as landfilling, incineration and recycling. Landfill space is
becoming scarce and expensive due to the fact that plastic waste is more voluminous than other waste type and incineration produces toxic gaseous products,
which only shifts a solid waste problem to an air pollution one. Recycling of plastic waste by chemical recovery is considered as an attractive approach to the
solution of waste problem. In this method, the waste plastics are thermally non-catalytically or catalytically degraded into gases and liquids. Non-catalytic
thermal degradation requires higher temperature and produces heavy products which need further processing for their quality to be upgraded, on the other hand,
the presence of catalyst reduces the reaction temperature and forms better quality products. The most commonly used catalysts are zeolites, amorphous SiO 2 -
Al 2 O 3 and acidic mesoporous catalysts (MCM-41, SBA-15, etc.).
Results
In this study, SBA-type catalysts (pure and aluminum containing) were synthesized by using hydrothermal synthesis route [1,2] in order to be tested in catalytic
degradation of polypropylene. Tetraethyl orthosilicate and aluminum isopropoxide were used as the Si and Al sources, respectively. It was observed that these
materials had high surface area in the range of 600-850 m 2 /g and exhibited isotherm of type IV. From XRD analysis, the structure of synthesized materials was
considered as SBA-15. The activities of these catalysts in the degradation reaction of polypropylene were investigated by TGA and the results showed a marked
reduction in the degradation temperature in the presence of aluminum containing SBA-type catalyst. This catalyst caused a significant decrease in the activation
energy of the reaction from 172 kJ/mol to a value of 73.0 kJ/mol.
Justification for acceptance
Much less is known about the catalytic activity of SBA-type catalysts in the degradation of polypropylene. Novel aluminum oxide containinig SBA-like catalytic
materials synthesized here showed high activity in the degradation of polypropylene. The scientific results obtained here will contribute to the knowledge and
skill in this subject and to the development of a technology to produce petrochemicals and fuels from waste plastics.
References
[1] P.F. Fulvio, S.Pikus, M. Jaroniec, J.Coll.Inter.Sci, 287 (2005) 717.
[2]G.M. Kumaran, S. Garg, K. Soni, M. Kumar, L.D. Sharma, G.M. Dhar, K.S.R. Rao, Appl.Catal.A:General, 305 (2006) 123.
299 Activated carbon supported metal catalysts Pd-Cu, Pt-Cu and Rh-Cu for nitrate reduction in water
O.S.G.P. Soares*, J.J.M. Órfão, M.F.R. Pereira
Laboratório de Catálise e Materiais, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto,
Portugal
*Corresponding author: Tel: + 351 225 081 998, Fax: + 351 225 081 449, salome.soares@fe.up.pt
Background
A recent report from the European Environment Agency refers that the presence of nitrates in water is actually a common problem across Europe. The catalytic
reduction is one of the most promising alternatives for nitrates removal. This process consists in the reduction of nitrate to nitrogen over bimetallic catalysts in
the presence of a reducing agent [1]. Previous studies have demonstrated that monometallic catalysts are not efficient in the reduction by hydrogen. Nitrite as
intermediate and ammonium as by-product are considered the major limitations of this process [2].
Results
In the present work the activities and selectivities of three pairs of bimetallic catalysts (Pd-Cu, Pt-Cu and Rh-Cu) supported on activated carbon were studied in
order to optimize the metal loading for the reduction of nitrate in water with hydrogen. The catalysts were prepared by co-impregnation. The amount of noble
metal was maintained constant at 1%wt and the Cu loadings tested were 0.1, 0.3, 0.6 or 1%wt. The composition 2% of noble metal and 1% of Cu was also
checked. The catalytic tests were carried out in a semi-batch reactor, working at room temperature and pressure, with nitrate solutions of 100ppm and using
hydrogen as reducing agent. Most of the work in the area of catalytic nitrate reduction has been done using Pd-Cu and Pt-Cu bimetallic catalysts on different
supports. In this study, we found that Rh-Cu bimetallic catalysts were more active than Pd-Cu or Pt-Cu. However, significant amounts of ammonium are
obtained with all these catalysts. Under the experimental conditions used, it was confirmed that the monometallic catalysts are inactive for the reduction of
nitrate. The activity of the catalysts is quite different depending on the copper amount. The maximum activity for the catalysts with 1% of the noble metal was
obtained for 1%Rh-0.6%Cu, 1%Pt-0.3%Cu, and 1%Pd-1%Cu, with nitrate conversions of 98%, 56% and 52%, respectively, after 5h of reaction. However, all
the catalysts with 2% of the noble metal were still more active. The pairs Pd-Cu and Pt-Cu are more selective in the transformation of nitrate towards nitrogen
compared to the Rh-Cu pair.
Justification for acceptance
The increasing pollution of natural sources of drinking water encourages the development of emerging technologies and novel processes for water remediation.
In this scope, the catalytic reduction of nitrates is an important area of research mainly in order to develop efficient catalysts for clean water. The presented
results are relevant in this context.
Acknowledgements: Fundação para a Ciência e a Tecnologia (FCT) - BD/30328/2006 and POCTI/FEDER (POCTI/1181).
References
[1] A. Pintar, Catal. Today, 77 (2003) 451.
[2] K.D. Vorlop, T. Tacke, Chem. Ing. Tech., 61 (1989) 836.

300 Study of the effect of different pretreatments on Pt/CeO 2 catalysts for the hydrodechlorination of trichloroethylene (TCE)
N. Barrabés a,b, *, A. Dafinov a , K. Föttinger b , G. Rupprechter b , F. Medina a and J.E.Sueiras a
a Dep. Chemical Engineering, Rovira i Virgili University, Campus Sescelades, Tarragona, 43007 Spain.
b Inst. of Materials Chemistry, Vienna University of Technology, Veterinaerplatz 1, Vienna, 1210, Austria.
*Corresponding author. Tel: +34 977558535, Fax : +34 977559621, e-mail: noelia.barrabes@urv.cat
Background
The feasibility of a catalytic technology to remediate waste streams of halogenated compounds improving the selectivity toward more useful or environmentally
benign products is nowadays of great interests. Previous studies focused on the use of noble metal catalyst for the full hydrodechlorination of TCE to C 2 H 6 which
is industrially less useful than ethylene [1]. Several authors reported that CeO 2 exhibits different kinds of interaction with the noble metals affecting the catalytic
activities, depending on the method of synthesis, pre-treatment etc [2-5]. These parameters were studied for Pt-CeO 2 catalysts in order to examine the catalytic
behaviour in the hydrodechlorination of TCE to ethylene, aiming at an understanding of how the interaction between platinum and ceria affects catalytic
performance.
Results Pt-ceria catalysts exhibit a much higher selectivity to ethylene than Pt-alumina (full hydrogenation to ethane is observed for Pt-alumina). In all cases
the conversion increases for higher platinum loadings. Two different synthesis procedures of Pt-ceria catalysts were applied, a co-combustion route [ref] and a
standard impregnation method. The catalysts obtained via combustion and by impregnation show similar activity, but the selectivity towards ethylene is higher
for combustion derived catalysts. This can be attributed to a different Pt-ceria interaction. Whereas via impregnation Pt is deposited on the surface, via the
combustion method Pt is incorporated in the ceria matrix. Depending on the pretreatment conditions/atmosphere the selectivity towards ethylene changes both on
combustion and impregnation catalysts. This effect was not observed when using Cl-free Pt precursors for catalyst preparation. FTIR spectra of CO adsorption
after the different pretreatment procedures show differences in nature of carbonate-type species, which are present before CO adsorption and additionally form
upon CO addition. This could indicate different surface chemistry and reactivity or the presence of different defective sites.When using PtCl 4 as precursor
Kepinski et al. [5] found that a CeOCl phase is formed during the reduction process whereas this CeOCl phase decomposes slowly in oxidizing atmosphere. This
could be related with the formation of different reactive sites influencing the formation of different kinds of carbonates species [6]. It was shown that [4] some
pretreatments produce surface carbonates which may block the active sites and cause changes in the catalytic behavior. In this work we will discuss in details
the interaction of platinum and the ceria support which plays an important role in activity, selectivity and stability of the catalysts.
Justification for acceptance The present work shows an environmental and useful alternative to remove chloride organics compounds from waste streams in
the field of air pollution. In addition this technology could be applied for water streams too.
References
[1] Ordoñez, S.,H. Sastre and F.V. Diez,Applied Catalysis B-Enviromental 29(4) (2001) 263-273.
[2] Parthasarathi B., et al., Journal of Catalysis 196 (2000) 293-301.
[3] Jacobs G., Ricote S. and Davis B.H., Applied Catalysis A: General 302 (2006) 14-21.
[4] Shekhtman S.O., Goguet A., Burch R., Hardacre C. and Maguire N., Journal of Catalysis 253 (2008) 303-311.
[5] L.Kepinski and J.Okal., Journal of Catalysis 192 (2000) 48-53.
[6] Föttinger K., Schlögl R. and Rupprechter G., Chem. Communications 3 (2008) 320-322.
307 Catalytic oxidation of ethyl acetate over different metal-doped cryptomelane catalysts
V.P. Santos * , M.F.R. Pereira, J.J.M. Órfão, J.L. Figueiredo
Laboratório de Catálise e Materiais, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal
* Corresponding author: Tel: (+351) 22 508 1998, Fax: (+351) 22 508 1449, e-mail: santos.vera@fe.up.pt
Background
Increasing concern about environmental and health effects resulting from emission of volatile organic compounds (VOC) has led to more stringent regulation
standards, which require efficient and economic methods for VOC abatement. Catalytic oxidation is a very efficient and cost-effective technology for VOC
removal. The performance of this process critically depends on the type of catalyst used. In this work we study the catalytic oxidation of ethyl acetate over
modified tunnel structured Mn (IV) oxide with the cryptomelane structure.
Results
The OMS-2 catalyst was synthesized by the reflux method developed by Luo et al. [1]. Small amounts of cerium (7 %) or cesium (4 %) were introduced into the
manganese oxide structure by ion-exchange. According to the results of X-ray diffraction and SEM/EDS, all the synthesized materials have nanofibrous
morphology and a cryptomelane structure. Free CeO 2 phase was also detected in the XRD pattern of Ce-K-OMS-2. ICP analysis suggests that cesium species
may be located inside the tunnels, while some cerium may be incorporated into the OMS-2 framework. The oxidation of ethyl acetate (a model VOC) was
performed in a fixed bed reactor under atmospheric pressure, with an inlet VOC concentration of 1600 ppmv and a space velocity of 16,000 h -1 . The activity of
the catalysts was tested by raising the temperature stepwise from 160 to 240 ºC (steps of about 10 ºC). The reactor was maintained at each temperature for 30
minutes in order to obtain experimental values at steady state. The ignition curves of ethyl acetate on the prepared catalysts show the following activity sequence:
Cs-K-OMS-2 > K-OMS-2 > Ce-K-OMS-2. In the presence of the OMS-2 catalyst, complete oxidation of ethyl acetate into CO 2 occurs at 220 ºC, while on Cs-K-
OMS-2 this temperature is decreased to 200 ºC and on Ce-K-OMS-2 it increased to 235 ºC. The catalytic activities of these catalysts may be correlated with their
chemical composition and surface properties (e.g surface acidity and basicity and average oxidation state of manganese).
Justification for acceptance
The performance of catalytic oxidation critically depends on the type of catalyst used. It is well known that ethyl acetate is a very important VOC, used in the
printing industry, and is one of the most difficult to oxidise. This work shows that cryptomelane represents a good alternative for emission control, and it is
possible to improve the performance by ion-exchange with small amounts of cesium.
Acknowledgements: Fundação para a Ciência e Tecnologia (FCT) and FEDER - BD/23731/2005, POCTI/1181 and PTDC/AMB/69065/2006.
References
[1] J. Luo, Q. Zhang, A. Huang and S.L. Suib, Micropor Mesopor Mat, 35-36 (2000) 209.

310 Fe containing silica gel catalysts for catalytic wet peroxide oxidation processes
H. T. Gomes a,b* , A. C. Barbosa a , C. A. Amaro a , C. M. Oliveira a , R. G. Sousa a , J. L. Faria b and B. F. Machado b
a Departamento de Tecnologia Química e Biológica, Escola Superior de Tecnologia e de Gestão, Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-857
Bragança, Portugal.
b Laboratório de Catálise e Materiais, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto,
Portugal.
*Corresponding author. Tel: +351 273 303 110, Fax: +351 273 313 051, e-mail: htgomes@ipb.pt
Background
The degradation of pollutants by catalytic wet peroxide oxidation (CWPO) using the Fenton’s reagent is a well known process, the major drawback being the
need to recover the iron catalyst at the end of treatment. To overcome this, new heterogeneous catalysts have been developed and studied since some years ago,
which involve the incorporation of iron species into a solid matrix [1-2]. In this work we aimed to develop Fe containing silica gel catalysts (5wt. % Fe) using
sol-gel techniques and to test their suitability for the CWPO of azo dye Chromotrop 2R aqueous solutions.
Results
The catalysts were prepared by hydrolysis and polycondensation of tetraethylorthosilicate, incorporating the Fe element in the solid matrix of the material during
the sol-gel procedure, and were characterized by thermogravimetric analysis, N 2 adsorption, Fourier Transform Infrared Spectroscopy (FTIR) and optical
microscopy. The oxidation reactions were performed in a glass reactor equipped with pH meter, temperature controller and magnetic stirrer. Dye concentration
was monitored during the reaction by UV-Vis spectrophotometry. The developed materials show high activity in the removal of the azo dye, complete
conversions being obtained after one hour of reaction in a large range of process operating conditions ([dye] 0 = 40 mg/L, 50ºC, pH between 3 and 7, catalyst
concentration between 0.1 g/L and 0.5 g/L and hydrogen peroxide concentration between 7.1 mM and 35.3 mM). The effect of a thermal post-treatment over the
catalyst was studied and the activity was found to decrease with post-treatment temperature. This is explained in terms of a structural modification of the silicagel
matrix during heat treatment, as supported by FTIR analysis. Catalyst stability under the studied reaction conditions was assessed by measuring (atomic
absorption) the amount of iron present in the treated solutions, which can only result from catalyst leaching. Catalyst attrition and pH were found to be the main
factors influencing catalyst stability. This study indicates that Fe containing silica gel materials are promising catalysts for CWPO processes.
Justification for acceptance
To the best of our knowledge, this work reports for the first time the preparation and characterization of iron containing silica gel catalysts and their application
to the degradation of an azo dye in aqueous solution by CWPO, being thus an important contribution to the field of catalysis for clean water.
References
[1] A. Quintanilla, A.F. Fraile, J.A. Casas, J.J. Rodriguez, J. Hazard. Mater. 146 (2007) 582.
[2] J.A. Melero, G. Calleja, F. Martinez, R. Molina, K. Lazar, Micropor. Mesopor. Mater. 74 (2004) 11.
320 Catalytic oxidation of 1-methylnaphthalene, a PAH representative molecule - influence of PAH and steam concentrations
S.C. Marie – Rose a* , J. Mijoin a , P. Magnoux a , E. Fiani b , M. Taralunga c and X. Chaucherie c
a
Université de Poitiers, LACCO UMR 6503, 40 avenue du Recteur Pineau, 86022 Poitiers Cedex, France
b
ADEME, 20 avenue du Grésillé - BP 90406 – 49004 ANGERS cedex 01, France
c VEOLIA, 291 avenue Dreyfous Ducas, 78520 Limay, France
* Corresponding author. Tel : (+33)5 49 45 35 26, Fax : (+33)5 49 45 37 79,e-mail :
stephane.marie.rose@etu.univ-poitiers.fr
Background
In the field of air pollution control, catalytic oxidation is a very promising technology for the destruction of pollutants at low concentrations and at low
temperature. The main oxidation catalysts are TiO 2 based V 2 O 5 /WO 3 [1], noble metals supported by various oxide [2] and zeolites [3-5]. Zeolites have shown
their potential for the destruction of Persistent Organic Pollutants (hydrocarbons and chlorinated compounds) [4-5]. The objectives of this work are to evaluate, in
experimental conditions that are representative of the industrial process, the performance of PtUSHY catalyst during the catalytic oxidation of 1-
methylnaphthalene (1-MN), a PAH representative molecule, and the influence of various parameters on the efficiency of the catalytic process (1-MN
concentration, steam concentration).
Results
The oxidation of 900 ppm 1-MN was achieved in the presence of steam (14667 ppm) and for a VVH of 20 000 h -1 on the 0,8%PtUSHY catalyst. The total
oxidation of 1-MN into CO 2 was obtained from 300°C. The presence of products other than CO 2 and H 2 O has not been observed whatever the reaction
temperature. At 200°C, in the absence of water in the reaction mixture, the destruction rate of 1-MN is 97%. When water (14 667 ppm) is added to the mixture
this rate decreases down to 20%. The presence of steam has a significant inhibitory effect on the reaction. The effect of the concentration of 1-MN (100 to 900
ppm) has also been studied on the 0,8%PtUSHY catalyst in the temperature range 200 to 350°C in the presence of water. Whatever the 1-MN concentration, the
catalyst is able to completely destroy the pollutant from 300°C. However, when 1-MN concentration is below 300 ppm, a temperature of 250°C is sufficient to
oxidize completely it into CO 2 without by-products formation.
Justification for acceptance
This study demonstrates the potential of platinum exchanged zeolites for the destruction of PAHs emissions from stationary sources in industrial conditions. The
effect of pollutant and steam concentrations on the oxidation reaction has a great interest in the development of a new air pollution control device based on
zeolite catalysts.
Acknowledgments: S.C. Marie-Rose gratefully acknowledges the “Agence de l’environnement et de la maîtrise de l’énergie “ (ADEME) and the “Région
Poitou-Charentes” for a scholarship.
References
[1] R. Weber, T. Sakurai, H. Hagenmaier, Applied Catalysis B: Environmental 20 (1999) 249-256.
[2] X.-W. Zhang, S.-C. Shen, L.E. Yu, S. Kawi, K. Hidajat, K.Y. Simon Ng, Applied Catalysis A: General 250 (2003) 341-352.
[3] A. Kalantar Neyestanaki, L.E. Lindfors, T. Ollonqvist, J. Vayrynen, Applied Catalysis A: General 196 (2000) 233-246.
[4] M. Taralunga, B. Innocent, J. Mijoin, P. Magnoux, Applied Catalysis B: Environmental 75 (2007) 139-146.
[5] L. Pinard, J. Mijoin, P. Ayrault, C. Canaff, P. Magnoux, Applied Catalysis B: Environmental 51 (2004) 1-8.

326 Alkali metal modified Pd-MgAlO x catalyst for hydrodechlorination of chloro-aromatic pollutants: activity and reactivation study
M. T. Beteley a , A. M. Segarra, F. Medina a* , J. E. Sueiras a , Y. Cesteros b , P. Salagre b
a Departament d’Enginyeria Química, Universitat Rovira i Virgili, P.O.Box 43007, Tarragona, Spain
b Departament de Química Inorgánica, Universitat Rovira i Virgili, P.O.Box 43007, Tarragona, Spain
*Corresponding author: M.T. Beteley; e-mail: beteley.meshesha@urv.cat
Background: Catalytic hydrodechlorination (HDCL) has proved to be one of the most reliable method for detoxification of the hazardous chloro-aromatic
pollutants, like Polychlorobenzene, which have carcinogenic and mutagenic properties. 1-4 Palladium based catalyst appeared to be effective for selective
elimination of chloride from the aromatic molecule. 2 However, one of the problems associated with catalytic HDCL is the strong deactivation of the catalyst
either by the acidic environment created due to HCl formed 1 or cocking. 4 In order to avoid these problems, palladium catalyst supported on basic materials like
Mg-Al mixed oxide (Pd-HT), as well as the addition of alkali metals (Li, Na, K, and Cs) using different precursors have been studied. The mixed oxides were
prepared by calcination of the Mg-Al hydrotalcite with Mg/Al ratio of 4 at 450ºC and the introduction of alkali metals and palladium (1%) were performed by
impregnation. The activities of the prepared catalysts were assessed by HDCL of 1,2,4-trichlorbenzene (TCB) model reaction in flow reactor working at
atmospheric pressure and between 100-200 ºC. The catalysts were characterized by XRD, N 2 Physisorption, FT-IR, SEM and TEM.
Results : The Pd-HT catalyst showed a total conversion and total selectivity to benzene at 200ºC during the first hour of reaction. However, the activity and
selectivity to benzene decreased with time. The addition of basic alkaline metals in form of hydroxide or nitrate precursor improves the activity, selectivity and
stability in the hydrodechlorination reaction of TCB. Li and Na doped Pd-HT catalysts showed the highest activity. The addition of alkaline in the form of nitrate
salts increased the activity with respect to the use of alkaline hydroxide precursors. Besides, an important increase in the stability was observed for these
catalysts. However, after a period of reaction time of 60 hours some deactivation was observed. The reactivation of the catalysts can be performed by treating the
catalysts in O 2 flow at 350ºC. After this oxidation process and then reduction the catalysts recovered the initial activity, selectivity and improved stability. In
conclusion, we propose a new and efficient catalyst for hydrodechlorination of TCB that presents a high stability and simple to reactivate.
Justification for acceptance: It is well known the negative impacts of organohalogenated compounds on the environment. Several efforts have been done in
order to remove these pollutants in clean and safe way. In the present work, we achieved in the preparation of efficient, clean and easy to prepare catalyst that
converts the TCB pollutants into benzene that can be used as a raw material for other processes. Moreover this catalyst can be reactivated by a simple method and
reused again achieving similar behavior.
References:
[1] M. A. Aremendía, R. Burch, I. M. García, A. Marinas, J. M. Marinas, B. W. L. Southward, F. J. Urbano, Appl. Cat. B: Environm. 31 (2001) 163.
[2] J. M. Moreno, M. A. Aramendia, A. Marinas, J. M. Marinas, F. J. Urbano, Appl. Catal. B: Environm. 76 (2007) 34.
[3] G. Yuan, M. A. Keane, J. Catal. 225 (2004) 510.
[4] M.Legawiec-Jarzyna, A. Srebowata, W. Juszczyk, Z. Karpinski, J. Mol. Catal. A: Chemical 224 (2004) 171.
327 Methane combustion over Pd-doped LaFeO 3 perovskites: where is the palladium?
A. Eyssler, * , P. Hug, P. Lienemann, A. Weidenkaff, D. Ferri
Empa, Lab. for Solid State Chemistry and Catalysis, CH-8600 Dübendorf, Switzerland
*Corresponding author. Tel.: +41 44 823 4334, FAX: +041 044 823 4041
e-mail: arnim.eyssler@empa.ch
Background
‘Intelligent catalysts’ for automotive emission control distinguish themselves for their long-term stability in the abatement of NO x , CO and unburned
hydrocarbons. La-Fe-Pd perovskites can prevent sintering of the precious metal under operating conditions through a continuous incorporation/segregation
process [1]. Intrigued by the reports on this process, we aimed at preparing Fe-perovskites containing Pd aiming at engineering the position (surface/lattice) of
Pd. Oxidation-reduction cycles at different temperatures prior to methane combustion should help in understanding the ‘intelligent catalyst’ phenomenon and its
relevance for methane combustion.
Results
Perovskites of the formula LaFe 1-x Pd x O 3 (x = ca. 0.05, 2 wt.% Pd) were prepared according to the citrate method [2] by adding the Pd salt to the precursors
solution so that either Fe had been partially substituted (LaFe 0.954 Pd 0.046 O 3 ) or that Pd was in excess with respect to La+Fe (Pd@LaFeO 3 ). Additionally, LaFeO 3
was also impregnated (Pd/LaFeO 3 ). X-ray diffraction of all calcined samples (SSA: 14 m 2 /g) showed only the typical LaFeO 3 -reflections. XRF measurements
presented different intensities in the Pd-L -fluorescence line caused by matrix- and surface effects, Pd in the LaFeO 3 -matrix exhibiting lower intensity than on the
surface. This could be an indication of the partial incorporation of Pd within LaFeO 3 . An additional hint to the incorporation of Pd is provided by the activity data
toward methane combustion (1 vol.% CH 4 -20 vol.% O 2 -He, 200-600°C). The highest catalytic activity was found for the impregnated sample and the order of
activity was: 2 wt.% Pd/LaFeO 3 (T 50% : 430°C) > Pd@LaFeO 3 (480°C) > LaFeO 3 (507°C) > LaFe 0.954 Pd 0.046 O 3 (518°C). Methane combustion on the impregnated
sample following an oxidation (500°C) and reduction (200°C) cycle exhibited lower activity (445°C) compared to the unreduced sample but was still more active
than LaFe 0.954 Pd 0.046 O 3 and Pd@LaFeO 3 . The data indicate that Pd significantly improved the activity of LaFeO 3 ; however, the Pd that could be incorporated into
the perovskite lattice did not promote methane combustion. The spectroscopic characterization of the structure of LaFe 0.954 Pd 0.046 O 3 and Pd@LaFeO 3 following
oxidation and reduction cycles should provide information on the structure and state of Pd with the aim at clarifying whether an ‘intelligent catalyst’ is active in
the methane combustion.
Justification for acceptance
Methane combustion in CNG vehicles and in stationary sources is a high temperature process imposing stability issues to catalytic systems. Perovskite-supported
catalysts are promising materials for this application because of their intriguing ability to incorporate precious metals and preventing sintering.
References
[1] H. Tanaka, Catal. Surveys Asia 9 (2005) 63; Y. Nishihata, J. Mizuki, T. Akao, H. Tanaka, M. Uenishi, M. Kimura, T. Okamoto, N. Hamada, Nature 418
(2002) 164.
[2] M.S.G. Baythoun, F.R. Sale, J. Mater. Sci. 17 (1982) 2757.

332 Catalytic wet peroxide oxidation of phenolic solutions over a LaMeO 3 perovskites
O. P. Pestunova , *, L. A. Isupova
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
*Corresponding author. Tel: +7 383 3307563, Fax : +7 383 3308056, e-mail: oxanap@catalysis.ru
Background The systems composed of homogeneous transition metal ions (Cu, Mn and specially Fe) as a catalysts and hydrogen peroxide are
efficient in oxidation of various organic wastes in aqueous solutions [1,2]. However homogeneous systems have well-known drawbacks, e.g. the
production of metal-containing waste sludges, catalyst deactivation by some agents and a limited pH range. That is why the development of
heterogeneous catalysts that causes no disposal problem and has a similar activity and stability to leaching of active metal is a paramount interest
for catalytic wasterwater treatment. LaMeO 3 perovskite-like oxides, including LaFeO 3 , are among the first for a role of catalysts for wet peroxide
oxidation (CWPO) owing to their high catalytic activity in oxidative reactions and high stability in a very aggressive media [3].
Results LaFeO 3 , LaCuO 3 , LaNiO 3 , LaMnO 3 and LaCoO 3 perovskite-like oxides were tested in CWPO of phenol in aqueous solution. Samples
were characterized with XRD and BET adsorption. Phenol was oxidized using a batch reactor with a reflux condenser at atmospheric pressure in
temperature range 30-50 o C. Initial conditions: [PhOH] = 0.01 mol/L, [H 2 O 2 ] = 0.7 mol/L, C cat = 5 g/L, initial pH = 3. The concentrations of phenol
and products of its oxidation were detected with Shumadzu LC-20 HPLC. TOC in solutions was analyzed with Shumadzu TOC-VCSH Analyzer.
Noticeable catalytic activity was found only for LaCuO 3 and LaFeO 3 . In presence of LaNiO 3 , LaMnO 3 and LaCoO 3 it has appeared not possible to
obtain pH value lower than 7 probably therefore oxidation of phenol did not occur. Long-term experiments for Fe-containing catalyst were curried
out as for more ecological benign catalyst. We observed an induction period during of 15 minutes in phenol consumption when we used the fresh
catalyst. The rate of phenol oxidation was virtually equal for 2-50 cycles of catalyst testing. Leaching of metals in each cycle was found to be 0.5-
2% for Fe and 0.5-1% for La in relation to amount of corresponding metal in the catalyst. The kinetics of phenol and TOC consumption in presence
LaFeO 3 and homogeneous Fe 3+ was compared. Phenol oxidation initially is faster in presence of Fe 3+ -ions. However reaction was observed to stop
at phenol conversion about 70 percents while over Fe-perovskite we reached full conversion. The termination of the reaction in presence of Fe 3+ -
ions could be explained by their complexing with some oxidation products. To clarify a question that is the catalyst - homogeneous Fe 3+ -ions or a
surface of the catalyst following experiment has been carried out. Fresh portion of phenol and 2 2 have been added into a filtrate after 10-th cycle.
Oxidation of phenol was not observed. All samples after reaction were characterized with XRD. Perovskite structure very close to initial was
revealed for all samples.
Justification for acceptance This work is devoted to development of the active, stable to the leaching and containing no noble metal catalyst for
one of very important ecological catalytic processes - CWPO. This work was fulfilled at a high experimental level with use of modern and
appropriate methods of research.
References
[1] R. Andreozzi, V. Caprio, A. Insola, R. Marotta, Catalysis Today 53 (1999) 51–59.
[2] S. Caudo, G. Centi, C. Genovese, S. Perathoner, Topics in Catalysis 40 (2006) 207-219.
[3] V. A. Sadykov, L. A. Isupova, I. A. Zolotarskii et al., Applied Catalysis A: General 204 (2000) 59-87.
336 Effects of preparation conditions on gold/13X-type zeolite for CO oxidation
Qing Ye *, Caiwu Luo, Dao Wang, Shuiyuan Cheng
Department of Environmental Science, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022 (P.R.China)
* Corresponding author. Tel: +86-10-6739-1683, Fax:+86-10-67391983;e-mail: yeqing@bjut.edu.cn
Background Since Haruta et al. [1] found that the inert gold with nanoparticle size possessed a dramatic activity for low-temperature CO oxidation, nano-particle
gold catalysts for this reaction have been investigated by many research groups. A known means for dispersing and stabilizing metal particles is to use zeolites [2,
3] because of its high surface area, ion exchange ability, and the stabilization of small gold particles via inserting them into the small cages. In this work, we chose
faujasite 13X zeolites with the large diameter of the pores as support and prepared by deposition-precipitation method. The effects of preparation conditions on
Au/13X for CO oxidation were studied.
Results The effects of preparation conditions (i.e. solution temperature, pH of gold solution, and calcinations temperature) on gold supported on 13X-type zeolite
(Au/13X) for CO oxidation were studied. The catalysts were characterized by XRD, SEM and XPS, in order to understand the correlation of the preparation
conditions and the gold particles in 13X-type zeolite to the catalytic activity. It was found from the results of SEM and XRD that higher temperature would
deposit homogeneous and smaller gold clusters on the support 13X, which caused better CO activity. Moreover, From XPS analysis of Au/Si ratios on the
surface of Au/13X prepared in the solution at pH 6 and 9, respectively, the lower pH 6 would generate more amount Au loading on 13 X than that of pH 9. There
were least two different ionic gold species on Au/13X prepared in the solution at pH 6. One is Au(OH) + 2 monomer, and the other is Au 2 O 3 gold dimers. However,
only one ionic gold species, Au 2 O 3 , from pH 9. That may result from that Au(OH) 2 Cl 2 and Au(OH) 3 Cl can be exchanged effectively on a specific surface site of
zeolite under pH 6. As compared with the samples calcined at 200 C and 400 C, the sample calcined at 300 C show the highest activity, which may result from
that the sample calcinations under 300 C cannot decompose completely to metallic gold and the sample calcinations ablove 300 C get larger particles gold on
support and the sample calcinations at 300 C can get moderate gold size. It can be concluded from this study that Au/13X prepared from a gold solution with
initial gold solution pH at 6, solution temperature around 80 C, and calcinations temperature for 300 C would possess an optimum catalytic activity for CO
oxidation.
Justification for acceptance CO oxidation has been a topic of immense importance recently to meet the stringent and continuously changing environmental
regulations as well as in many industrial applications such as indoor air cleaning, fuel cells, CO 2 lasers and automotive exhaust treatment. In order to obtain small
supported Au particles for effective catalysts of CO oxidation, we chose 13X zeolite with high surface area, the large diameter of the pores and ion exchange
ability as support of Au/13X for CO oxidation
References
[1]. M. Haruta, T. Kobayashi, H. Sano and N. Yamada, novel gold catalysts for the oxidation of carbon-dioxde at a temperature far below 0-degrees C, Chem.
Lett., 1987.405.
[2] S. Qiu, R. Ohnishi, M. Ichikawa, formation and interaction of carbonyls and nitrosyls on gold(I) in ZSM-5 zeolite catalytically active in NO reduction with
CO, J. Phys. Chem., 101 (1994) 2719.
[3] Y.M. Kang, B. Z. Wan, Gold and iron supported on Y-type zeolite for carbon monoxide oxidation , Catal. Today, 35 (1997) 379.

351 Catalytic reduction of nitrates in water solution over Pt-Ag/AC
A. Aristizábal a *, N. Barrabés, S. Contreras a and F. Medina a
a Dep. Chemical Engineering, Rovira i Virgili University, Campus Sescelades,Avda Països Catalns 26, Tarragona, 43007 Spain.
*Corresponding author. Tel: +34 977558535, Fax: +34 977559621, e-mail: adriana.aristizabal@estudiants.urv.cat
Background The increasing pollution with nitrates of natural sources of drinking water encourages the development of new emerging technologies and
processes for water remediation. Catalytic denitrification is emerging as the most promising and flexible technique for an efficient solution of the problem.
Bimetallic catalysts Pt,Pd-Cu are the most studied ones and show a high activity in this process. The high cost of platinum and palladium is an important
drawback of these types of catalysts. The aim of this work is to deposit by redox reaction platinum on the surface of silver nanoparticles to minimize the noble
metal content in the catalyst. The catalytic activity for the reduction of nitrates in water using a continuous reactor is performed. The influence of the
morphology of the silver nanoparticles in the activity and selectivity of the catalysts is also studied.
Results Several Pt-Ag/AC catalysts with different atomic ratios of metal and noble metal, were prepared to determine the optimum ratio and the
minimum amount of platinum to avoid the catalysts deactivation. Two different preparation methods were used for these purposes, first the traditional incipientwetness
impregnation method with the corresponding metal salts, and secondly silver nanoparticles were synthesized by polyol method [3] and then Pt was
deposited on the surface by redox reaction and then the Pt-Ag nanoparticles were deposited by impregnation on the support (active carbon, AC). Some
characterization techniques like scanning electron microscopy (SEM), nitrogen physisorption, hydrogen chemisorption, TPR and X-ray diffraction (XRD) have
been applied. The catalytic results, for the reduction of nitrate in water, show that the use of silver nanoparticles improves both the activity and the selectivity to
nitrogen compared with the traditional catalyst.
Justification for acceptance This research work is clearly an application of environmental catalysis to clean water for human drinking purposes. As the
maximum concentration limits for nitrates in drinking water are becoming stricter, research on this field is essential to assure their fulfillment.
References
[1] R. Rodríguez, C. Pfaff, L. Melo and P. Betancourt. Catalysis Today 107-108, (2005) 100.
[2] N. Barrabés, J. Just, A. Dafinov, F. Medina, J.L.G. Fierro, J.E. Sueiras, P. Salagre and Y. Cesteros. Applied Catalysis B: Environmental 62 (2006) 77
[3] .J. Chimentaoa, I. Kirm, F. Medina, X. Rodríguez, Y. Cesteros, P. Salagre, J.E. Sueiras, and J.L.G. Fierro.
Applied Surface Science 252 (2005) 793
352 Novel electrochemical catalyst for the electrochemical promotion of the deep oxidation of methane: Pd deposited on YSZ monolith
V. Roche ab* , T. Pagnier b , R. Revel c , L. Rodriguez-Perez c , E. Comte c , A. Lambert c , P. Vernoux a
a Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), UMR 5256 CNRS Université Claude Bernard Lyon 1, 69626 Villeurbanne, France
b Laboratoire d’Electrochimie et de Physico-chimie des Matériaux et des Interfaces de Grenoble (LEPMI), UMR 5631 CNRS-INPG-UJF, ENSEEG, BP 75, 38402 St Martin
d’Hères, France
c IFP-Lyon,Rond-point de l'échangeur de Solaize, BP3 - 69360 Solaize
* Corresponding author: tel +33 472431587, Fax: +33 472431695, mail: virginie.roche@ircelyon.univ-lyon1.fr
Background
Natural gas appears to be a fuel of great interest as a major source of thermal energy. During the last few years, the catalytic deep oxidation of methane was
widely studied and the most effective materials for this reaction are palladium-based catalysts [1]. The use of electrochemical promotion to modify the activity of
such catalysts for methane deep oxidation has already been evidenced on Pd/YSZ [2, 3]. Electrochemical promotion of catalysis (EPOC) is an innovative concept
introduced and widely developed by Vayenas et al. [2]. This concept involves the use of an electrochemical catalyst composed of a catalyst and an inert counter
electrode both deposited as thin films on an ion conducting solid electrolyte. The application of a potential or current through the catalyst/electrolyte interface
could modify the activity of the catalyst, in a reversible manner. The applied polarisation is expected to result in a pronounced rate enhancement, superior to the
electrochemical rate of supplied ions or ionic current. A key parameter for the use of EPOC at an industrial scale is now the design of efficient reactors and
electrochemical catalysts.
Results
In this study, for the first time, the use of a monolith of YSZ (yttria stabilized zirconia) as a solid electrolyte to perform electrochemical promotion is reported.
The goal of this study was to validate the concept of EPOC on palladium thin films interfaced with a monolithic O 2- conducting solid electrolyte for the deep
oxidation of methane. The YSZ monolith was a 30 mm high 32 mm diameter cylinder. It was composed of about 600 1 mm x 1 mm channels with 0.3 mm wall
thickness. Isolated Pd catalyst particles were deposited on the channels’surface using electroless deposition [4]. A continuous palladium film was deposited on
the surface of the inner channels at the centre of the monolith in order to act as an electrode. Gold paste was painted on the external surface of the cylinder to act
as a second catalytically inert electrode. The monolithic electrochemical catalyst was polarized between these electrodes in a single chamber reactor.
First of all, catalytic activity measurements under open circuit conditions were carried out for methane deep oxidation between 300 and 500°C. The reactive
mixture was composed of 2% of methane and 10% of oxygen in helium with a total flow rate of 10 L.h -1 . The Pd catalyst was found to be an effective material
since the conversion of methane reached 20% at about 320 °C. The catalytic properties for methane deep oxidation of the monolithic electrochemical catalyst
were investigated under polarization at 400 and 500°C and various CH 4 /O 2 ratios. Non faradaic effects were observed both under positive and negative
polarization. These experiments report, for the first time, the ability of in-situ activation and control of the catalytic performances by the polarization of a
monolithic YSZ substrate.
References
[1] M.F.M. Zwinkels, S.G. Jaras, P.G. Menon, Cat. Rev. - Sci. Eng., 35(3) (1993) 319
[2] C.G. Vayenas, S. Bebelis, C. Pliangos, S. Brosda, D. Tsiplakides, in: Electrochemical Activation of Catalysis: Promotion, Electrochemical Promotion, and Metal-Support
Interactions, Kluwer Academic/ Plenum Publishers, New-York (2001)
[3] V. Roche, R. Karoum, A. Billard, R. Revel, P. Vernoux, J. Appl. Electrochem., submitted (2008)
[4] K.L. Yeung, S.C. Christiansen, A. Varna J. Membr. Sci. 159 (1999) 107

353 Wet air oxidation of acetic acid over ruthenium catalysts supported on cerium based materials –
influence of metal and oxide crystallite sizes
J. Mikulová a,* , J. Barbier Jr. b , S. Rossignol c , D. Mesnard b , D. Duprez b and C. Kappenstein b
a Czech Academy of Sciences, ICPF, Rozvojová 135, Prague 16502, Czech Republic
b University of Poitiers, LACCO UMR 6503, 40 Avenue du Recteur Pineau, F-86022 POITIERS Cedex, France
c University of Limoges, France
* Corresponding author. Tel: +420 220 390 294, Fax: +420 220 920 661, e-mail: mikulova@icpf.cas.cz
Background
Ruthenium catalysts (1.25 wt.-%), prepared by anionic exchange of ruthenium on sol-gel mixed oxides Zr 0.1 (Ce 0.75 Pr 0.25 ) 0.9 O 2 and Zr 0.1 Ce 0.9 O 2 as well as on
commercial CeO 2 , were used for catalytic wet air oxidation (CWAO) of acetic acid. The influence of sintering (treatment under O 2 or H 2 ) was studied for those
catalysts in order (i) to modify the oxygen transfer from the gaseous phase onto the metallic active site of the catalyst and (ii) to determine the effect of these
treatments on the catalytic activity and stability. The characterization of the catalysts, before and after CWAO reaction, was carried out by different analytical
methods.
Results
In order to compare to similar, previously studied platinum catalysts [1], further samples were prepared on two supports calcined at 800 °C (CeO 2 and
Zr 0.1 (Ce 0.75 Pr 0.25 ) 0.9 O 2 ). They have demonstrated a good intrinsic activity, a higher resistance versus poisoning by carbonate species during CWAO experiments,
but a poor variety of metallic crystallite sizes (low Ru dispersion ranging from 1 to 9 %). Better dispersions were obtained after calcination of supports at lower
temperatures. The ruthenium exchanged catalysts reveal better activity than their impregnated homologues. Zr 0.1 Ce 0.9 O 2 support seems to be a good alternative. It
exhibits elevated oxygen transfer ability and permits to conserve high intrinsic activity by limitation of carbonates species formation. These species are present in
low amounts after CWAO of acetic acid only at the surface of catalysts.
Justification for acceptation
This research is situated right in heart of the main congress topic. The considered catalysts for water treatment are very stable in reaction conditions and allow
eliminating the most refractory molecules such as acid acetic with conversion rate close to 100%. Furthermore, the fundamental approach demonstrates
interesting correlations between OSC values and amount of carbonates species and between this amount and catalytic activity.
References
[1] J. Mikulová, J. Barbier Jr., S. Rossignol, D. Mesnard, D. Duprez, C. Kappenstein, J. Catal. 251 (2007) 172
354 Nitrate removal from water by catalytic hydrogenation
J. V. Pande, A. Shukla, V. Kumar, A. Bansiwal, S. Rayalu, R. B.Biniwale*
National Environmental Engineering Research Institute, Nagpur 440020, India
*Corresponding author, Phone: +91-9822745768, email: rb_biniwale@neeri.res.in
Background
Nitrate in groundwater originate primarily from fertilizers, septic system and manure storage or spreading operations. Excess fertilizer’s nitrogen volatilised or
carried away by surface run off leaches to the groundwater in the form of nitrate. This higher level of nitrate affects infants under six months of age by forming
methemoglobin. The resulting condition is referred to as methemoglobinemia, commonly called ‘blue baby syndrome’. More severe impact is continuous
exposure to nitrate forms nitrosamine in stomach, a carcinogenic precursor. The catalytic reduction of nitrate to nitrogen is the most appropriate method as it
directly convert nitrate into nitrogen.
Results
Nitrate is a stable and highly soluble ion and thus it is difficult to remove by simple methods such as adsorption, ion-exchange etc. A more suitable method is to
convert nitrate to the nitrogen is by way of catalytic hydrogenation. Several catalysts particularly alumina supported Pd based monometallic and bimetallic
catalysts have been reported for catalytic hydrogenation of nitrate. Ni/alumina and formic acid as reducing agent have been used in the present study.The
selective catalytic reduction of nitrate is greatly influenced by the nature of the support and the loading of the metal. In the present study, we have discussed the
catalytic activity of Ni supported on alumina. The extent of metal loading on the support is vital for the catalytic performance in this reaction. Different catalysts
were synthesized keeping the metal loading as 5 wt%, 10 wt% and 40 wt% of Ni supported on alumina. The catalyst 5 wt% Ni/alumina has been observed to
show relatively better catalytic activity for nitrate reduction as compared with the other catalysts. This may be attributed to the uniform dispersion of Ni over the
support and also due to the synergistic effect of support i.e. alumina. Ni was also supported on high surface area activated carbon (ca. 800 m 2 /g) which shows
poor activity than Ni supported on alumina (ca. 200 m 2 /g). The effect of initial concentration of the nitrate solution was studied. It was observed that when initial
concentration was 100 ppm the reduction was about 60 % and for 50 ppm initial concentration the reduction was about 75%. It is observed that there is no major
difference of change in initial concentration. The concentration of treated water is below the prescribed limit of 45 mg/l. Overall nitrate removal using 5 wt%
Ni/alumina was ca. 580 mg/g of catalyst. Catalyst was characterized using XRD, SEM-EDAX. Issues needs to be addressed are selectivity of catalysts and
release of metal catalysts into water.
Justification for acceptance
While addressing the environmental issues, catalysis is a most ecological or green route. It is important to discuss recent results for removal of aqueous phase
nitrate, which may find application in water and wastewater treatment. ICEC surely will help to identify the direction for advancement of science in this field.
Reference:
Jacinto Sa, Hannelore Vinek, Applied Catalysis B:Environmental 57 (2005) 247-256.

356 Effect of potassium in layered double hydroxide-related Co-Mn-Al mixed oxide catalyst on deep oxidation of VOC
K. Jirátová a,* , J. Mikulová a , J. Klempa a , T. Grygar b , Z. Bastl c and F. Kovanda d
a InstituteofChemicalProcessFundamentalsCAS,Rozvojová135,Prague,CzechRepublic
b Institute of Inorganic Chemistry CAS, 250 68 ež at Prague, Czech Republic
c J. Heyrovský Institute of Physical Chemistry CAS, Dolejškova 3, 182 23 Prague, Czech Republic
d InstituteofChemicalTechnology,Prague,Technická5,16628Prague,CzechRepublic
* Corresponding author. Tel: +420 220390295, e-mail: jiratova@icpf.cas.cz
Background
The Co-Mn-Al mixed oxides doped with various metals (Pd, Pt, Ce, La, K, and Li) have been recently examined by our group as catalysts for deep oxidation of
volatile organic compounds. The research has revealed that the catalyst properties were considerably improved by potassium promoter. Therefore, a series of
mixed oxides containing different amounts of K (0.5 – 5 wt %) was prepared by thermal treatment (500 °C) of the Co-Mn-Al layered double hydroxide precursor
with Co:Mn:Al molar ratio of 4:1:1. The effect of various K content on physical chemical properties were studied, as well as the activity and selectivity of these
materials in oxidation of toluene and ethanol.
Results
The highest catalytic activity in toluene oxidation was performed with the catalyst containing of about 1 wt% K, while in ethanol oxidation such maximum was
observed for the catalyst having nearly 3 wt% K. Reaction temperatures T 50 necessary for achieving the conversion of 50 % decreased by 15 °C for toluene and
by 35 °C for ethanol. The greatest effect of K on Co4MnAl catalyst was found out in selectivity of ethanol oxidation: Addition of K suppressed formation of
undesirable reaction byproducts, i.e. acetaldehyde and acetic acid, more than 10 times. It can be concluded that both high catalytic activity and selectivity (in
ethanol oxidation) can be achieved by addition of an optimum amount of potassium promoter. It changes size of crystallites, redox and acid-base properties of the
mixed oxide catalyst as revealed by various techniques (XRD, BET, TPR, Raman spectroscopy, XPS, TPD(NH 3 ) and TPD(CO 2 )).
Justification for acceptance
It is necessary to reduce emissions of waste gases arising from chemical industry and emissions coming from increased number of cars using ethanol as a fuel.
Therefore, effective oxidation catalysts avoiding generation of harmful reaction byproducts, which contribute to smog formation and show negative effect on
human health, are required. Optimization of the catalyst composition represents a suitable way how to reach this aim.
Acknowledgements
This work was supported by the Czech Science Foundation (104/07/1400) and by the Ministry of Education, Youth and Sports of the Czech Republic (MSM
6046137302).
361 TCE dechlorination over zero-valent iron aerogels
Jihye Ryu a,b , Young-Woong Suh a , Young-Kwon Park b , Dong Jin Suh a,*
a Clean Energy Research Center, Korea Institute of Science and Technology, Seoul, 136-791, Korea
b Department of Environmental Engineering, University of Seoul, Seoul, 130-743, Korea
*Corresponding author. Tel: +82 2 958 5192, Fax: +82 2 958 5205, e-mail: djsuh@kist.re.kr
Background
Removal of trichloroethylene (TCE) by chemical reduction has been a challenging task for several decades. Among various technologies for the dechlorination of
TCE, zero-valent iron (ZVI) particles appear to be one of the most promising technologies. Since micro-sized Fe 0 particles showed low TCE reduction rates, a
great deal of attention has been paid on the increase of ZVI surface area or the synthesis of Fe-based bimetallic particles to enhance the dechlorination rate [1].
For this purpose, we have prepared ZVI aerogels using supercritical drying and gas-phase reduction for TCE dechlorination.
Results
Zero-valent iron aerogels have been synthesized by sol-gel method and supercritical CO 2 drying, followed by H 2 reduction in the temperature range of 350–500
°C. When applied to TCE dechlorination, ZVI aerogels reduced at 370–380 °C showed the highest performance in the conditions employed in this study. Thus,
the effect of reduction temperature in preparing ZVI aerogels have been investigated by several characterizations such as BET, XRD, TPR, and TEM analyses.
As reduction temperature decreased from 500 to 350 °C, the BET surface area of the resulting aerogels increased from 6 to 30 m 2 /g whereas their Fe 0 content
decreased up to 64%. It was also found that H 2 reduction at low temperatures such as 350 and 370 °C leads to the formation of ZVI aerogel particles consisting of
both Fe 0 and FeO x in the particle cores with a different amount ratio, where FeO x is a mixture of maghemite and magnetite. It is, therefore, suggested that
reduction at 370 or 380 °C for ZVI aerogel preparation yielded particles homogeneously composed of Fe 0 and FeO x in the amount ratio of 87/13, resulting in high
TCE dechlorination rate.
Justification for acceptance
We have clearly found that in terms of the TCE dechlorination activity, ZVI aerogels are much better than commercial Fe 0 and are comparable to nano-sized ZVI
particles. Hence, we are considering that our ZVI aerogels would be one of the most powerful materials for removal of various organic chlorinated compounds
including TCE.
References
[1] C. Wang, W. Zhang, Environ. Sci. Technol. 31 (1997) 2154.

362 Novel catalytic method for ammonia removal from waste gases
T. Maunula * and M. Härkönen
Ecocat Oy, Typpitie 1, Fi-90650 Oulu, Finland.
*Corresponding author. Tel: +358-10-6535586, Fax, +358-10-6535700, e-mail: teuvo.maunula@ecocat.com
Background
Ammonia as harmful pollutant is emitted from different sources related to soil purification, farming and different processes. Ammonia is forming nitrogen oxides
in combustion and common oxidation processes. Ammonia is also used beneficially to reduce NO x by selective catalytic reduction (SCR) in power plant and
vehicles. In the literature, various catalysts are reported to be active in ammonia decomposition or selective oxidation to harmless N 2 in rich or lean conditions.
However, the common problem is the limited efficiency (

375 Ce and Ti as promoters of Au/Al 2 O 3 catalyst in the VOCs oxidation
G. Di Carlo a* , L.F. Liotta b , G. Pantaleo b , A.M. Venezia b , G. Deganello a,b , M. Ousmane a,c , A. Giroir-Fendler c , L. Retailleau c
a Dipartimento di Chimica Inorganica e Analitica “Stanislao Cannizzaro”, Università di Palermo, Viale delle Scienze, Parco d’Orleans II - 90128 Palermo, Italy.
b
Istituto per Lo Studio dei Materiali Nanostrutturati (ISMN)-CNR via Ugo La Malfa, 153, 90146 Palermo, Italy.
c Université de Lyon, Lyon, F-69003, France, Université Lyon 1, Villeurbanne, F-69622, France, CNRS, UMR 5256, IRCELYON, 2 avenue Albert Einstein, Villeurbanne,
F-69622, France.
*Corresponding author. Tel: +39 0916809366, Fax: +39 0916809399, e-mail: dicarlo@pa.ismn.cnr.it
Background
Volatile organic compounds (VOCs) are among the main contributors to air pollution and their release begins to be severely regulated. Therefore, the interest in
new active catalysts for the VOCs combustion has increased enormously. Noble metal catalysts (Pt, Pd and recently Au) and metal oxides (Cu, Co, Mn) are
successfully used in VOCs oxidation. In the present study the use of gold over Ce and Ti modified alumina is explored in the oxidation of propene. Particular
attention is addressed to the support effect.
Results
Gold catalysts (2 wt% Au) supported over Al 2 O 3 doped with Ce and Ti (5 and 10 mol % with respect to Al 2 O 3 ) were prepared by deposition precipitation method
and dried overnight at 120 °C. For comparison reason, Au catalysts over pure oxides, Al 2 O 3 , TiO 2 and CeO 2 were also prepared. BET, XRD, XPS and TEM
measurements were performed on fresh and used samples. The catalytic activity was evaluated under a reactive mixture containing 1000 ppm of C 3 H 6 and 9% O 2
at WHSV of 36 000 mL g -1 h -1 . The activity of gold catalysts over the pure oxides decreases in the order Au/CeO 2 > Au/TiO 2 > Au/Al 2 O 3 . In accord with our
recent results [1], Au/CeO 2 is a very promising catalyst and it shows the highest activity in propene oxidation achieving the 50% of conversion at 158 °C. The
Au/Al 2 O 3 is able to reach a 50% of conversion at 312 °C. It is worth noticing that the activity of Au/Al 2 O 3 is highly improved by the addition of small amount of
Ce and, to a lesser extent, of Ti. Au/Ce10mol%-Al 2 O 3 allows to achieve a performance quite close to pure Au/CeO 2 . The mobility of the lattice oxygen and the
nature and stability of gold species will be discussed in detail.
Justification for acceptance
The addition of Ce and Ti to the Au/Al 2 O 3 catalyst leads to a substantial improvement of the propene oxidation activity, making these catalysts quite promising
for VOCs removal at low temperature.
References
[1] A.M. Venezia, G. Pantaleo, A. Longo, G. Di Carlo, M.P. Casaletto, L.F. Liotta, G. Deganello, J. Phys. Chem. B, 109 (2005) 2821.
376 Development of Zeolite Monoliths by Paste Extrusion for ClVOCs Emissions Control by Catalytic Oxidation
M. Romero-Sáez, A. Aranzabal*, J.A. González-Marcos, J.R. González-Velasco
Chemical Technologies for Environmental Sustainability Group, Department of Chemical Engineering, Faculty of Science and Technology, University of Basque Country,
P.O. Box 644, E-48080 Bilbao (Spain)
*Corresponding author. Tel: +34 94 601 5554, Fax : +34 94 601 5963, e-mail: asier.aranzabal@ehu.es
Background
Chlorinated volatile organics compounds (ClVOCs), are widely used in industry and their environmental risks makes them necessary to eliminate. Catalytic
oxidation using H-zeolites is one of the most promising methods for the destruction of chlorinated hydrocarbons, because of its low energy consumption [ 1 ,2].
The industrial application of this technology requires the use of monolithic structures to diminish the pressure drop of the fixed bed reactors. To prepare the
monolith, the washcoat method or direct synthesis of zeolite on cordierite monoliths show problems of adhesion, which are avoided by the direct extrusion of
zeolitic paste.
Results
The preparation of zeolite monoliths was carried out in several stages. First, zeolite, temporary binder and
permanent binder are mixed. Methylcellulose was chosen as temporary binder to provide suitable rheologic
properties for the extrusion stage. The role of the permanent binder is to keep the zeolite particles linked
and give good mechanical strength. Then, its composition should be similar to zeolite. Among tested
binders, colloidal silica 40 %wt. has been selected. After homogeneity of the dry raw materials mixture ,
water was added to get a homogeneous, cohesive and easily extrudable paste in a Branbender 350-E mixer.
During the kneading process temperature and torque are controlled. A stable torque value indicates that the
mass good rheologic properties for the extrusion process has been achieved. Then the paste is ready to be
extruded in through a circular die of 160 cell/in 2 mounted in the 19/20DN head of the Brabender extruder,
controlling the temperature and the extrusion speed. The monolith samples are firstly dried under precisely
controlled temperature, and wetness and secondly calcined also under controlled temperature, to avoid
Conversion, %
100
80
60
40
20
0
200 250 300 350 400 450
Temperature, ºC
Figure. 1. Conversion over H-BEA () and H-ZSM-
5 () monoliths as function of reaction temperature
superficial defects. The present communication shows that success in zeolitic monolith depends on the optimization of several variables, as presented. The
obtained monoliths (H-BEA and H-ZSM-5) were tested under 1000 ppm of DCA at 5700 kg.s.mol -1 and 1 atm, as shown in Figure 1.
Justification for acceptance
The work shows an innovative procedure to prepare monolith of zeolites. This procedure provides higher durability and homogeneity of the active phase, and
makes the monolith to support small losses of superficial zeolite without loss of effectiveness.
References
[1] R. López-Fonseca, A. Aranzabal, J.I. Gutiérrez-Ortiz, J.I. Álvarez-Uriarte, J.R. González-Velasco. Appl. Catal. B, 30 (2001) 303-313.
[2] G. Centi, P. Ciambelli, S Perathoner, P. Russo. Catal. Today, 75 (2002) 3-15.

378 Decomposition of tristearin by ozonolysis over heterogeneous catalysts under moderate conditions
Kaori Kunisawa, Kohei Urasaki, Shigeru Kato, Toshinori Kojima and Shigeo Satokawa *
Department of Materials and Life Science, Faculty of Science and Technology, Seikei University
3-3-1 Kichijoji-kitamachi, Musashino-shi, Tokyo 180-8633, Japan
*Corresponding author; Tel: +81-422-37-3749, Fax: +81-422-37-3871, e-mail: satokawa@st.seikei.ac.jp
Background
Biodiesel fuels produced by transesterification of vegetable oils with methanol have received much attention as candidates for alternative diesel fuels [1] .
However, development of alternative biodiesel fuel production processes are expected because the methylesterification process requires a large amount of
washing water to remove an alkali catalyst in the products and an equivalent amount of glycerol with the raw oil is produced as a by-product. We have reported
the evidence for hydrocarbon production by ozonolysis of oils over heterogeneous catalysts [2] . The object of this study is to investigate the effects of
heterogeneous catalysts on ozonolysis of oils and to make clear the reaction pathways to obtain hydrocarbon-rich products.
Results
Tristearin (glycerol tristearate, C 57 H 110 O 6 ) was used in this study as a model of raw oil. Decomposition of tristearin was promoted by the synergistic effect
with the zeolite catalyst and ozone. The products obtained by ozonolysis of tristearin were strongly dependent on the properties of catalyst. H-Y type zeolite
(HY5.3: SiO 2 /Al 2 O 3 = 5.31, Na 2 O = 1.1 wt %) was the most effective on ozonolysis of tristearin to form hydrocarbons. The ozonolysis of tristearin was carried
out at 393-433 K (0.1 MPa). Many compounds with low boiling points containing hydrocarbons (n-C 9 - n-C 17 ), aldehydes, ketones, fatty acids and lactones were
obtained accompanied with un-reacted tristearin and intermediates (diacylglycerols and monoacylglycerol). When the reaction temperature increased, the
contents of non-reacted tristearin decreased. Tristearin was completely decomposed after the reaction at 423 K for 10 h and 433 K for 6 h. And the decomposed
products changed from solid phase to liquid phase at room temperature. The yields of hydrocarbons in the liquid products obtained by the ozonolysis of tristearin
over HY5.3 were about 10 wt %.
Many kinds of chemical compounds were obtained by the ozonolysis of tristearin. It is difficult to investigate the reaction pathways of these reactions.
Ozonolysis of some model chemical compounds including hydrocarbons, fatty acids and aldehydes were carried out to make clear the reaction pathways. We
would like to present the results of the ozonolysis reaction pathway over heterogeneous catalysts at the conference.
Justification for acceptance
The decomposition of vegetable oils by ozonolysis over heterogeneous catalysts is our original investigations in the field of renewable energy production. We
confirm that this study will be accepted to present in this conference.
References
[1] B. Feedman, E. H. Pryde, T. L. Mounts, J. Am. Oil Chem. Soc., 61 (1984) 1638.
[2] S. Kato, K. Kunisawa, T. Kojima, S. Murakami, J. Chem. Eng. Jpn., 37 (2004) 863.
379 Adsorptive removal of tert-butanethiol on Ag and Cu exchanged Y-zeolites under ambient conditions
Takuro Ohnuki, Tmoki Takahiro, Shigeru Kato, Toshinori Kojima and Shigeo Satokawa*
Department of Materials and Life Science, Faculty of Science and Technology, Seikei University
3-3-1 Kichijoji-kitamachi, Musashino-shi, Tokyo 180-8633, Japan
*Corresponding author; Tel: +81-422-37-3749, Fax: +81-422-37-3871, e-mail: satokawa@st.seikei.ac.jp
Background
Fuel cell is paid to attention by its high efficiency of energy conversion. Organic sulfur compounds contained in city gas as odorant have to be removed to
produce hydrogen from city gas. High adsorption capacity on Ag-Y zeolite has been reported in previous paper for removal of a mixture of dimethylsulfide
(DMS) and tert-butanethiol (TBT). However, adsorption capacity of TBT (single component) was much lower than that of DMS on Ag-Y zeolite. [1] In this study,
sulfur adsorption properties of TBT on Ag and Cu exchanged Y zeolite were compared under dry and wet gas conditions.
Results
Ag-Y and Cu-Y zeolites were prepared by ion exchange method using Na-Y zeolite. Sulfur adsorption capacity was evaluated by breakthrough curves of
reaction gas flow (20 ppm TBT in N 2 ) using a fixed-bed flow tubular reactor. Sulfur adsorption capacity on Ag-Y increased with an increase in the amount of
silver ion in zeolite under wet gas condition (1000 ppm H 2 O), however sulfur adsorption capacity decreased with an increase in the amount of Ag ion in zeolite
under dry condition (> 10 ppm H 2 O). From the results of FT-IR, it was understood to be caused by the decomposition of TBT and formation of silver sulfide
clusters in zeolite under dry condition. TBT decomposes to hydrogen sulfide and isobutylene on Ag-Y. Hydrogen sulfide becomes a silver sulfide and an increase
in the concentration of silver sulfide monomers results in dimerization of them to form silver sulfide clusters in zeolite. [2] It is speculated that the cause of
decreasing in the amount of sulfur adsorption capacity was the blockage of zeolite pore entrance by the increase in silver sulfide clusters.
On the other hand, sulfur adsorption capacity on Cu-Y increased with an increase in metal ion in zeolite under both wet and dry conditions. It was
confirmed from the result of FT-IR that the interaction between copper ion in zeolite and TBT was weaker than that between silver ion and TBT under dry gas
condition. As a results, it is considered that Cu-Y have a good performance as desulfurization material of TBT in fuels because the sulfur adsorption capacity on
Cu-Y is larger than that on the other adsorbents under both wet and dry conditions.
Justification for acceptance
Sulfur adsorption capacities are strongly dependent on the properties of sulfur compounds and adsorbents. It is very interesting that the existence of water
vapor in gas affects the TBT removal capacity on Ag-Y zeolite. This is very important finding to develop the city gas fueled fuel cell systems.
References
[1] S. Satokawa, Y. Kobayashi, H. Fujiki, Appl. Catal. B, 56 (2005) 51.
[2] K. Shimizu, N. Kobayashi, A. Satuma, T. Kojima, S. Satokawa, J. Phys. Chem. B, 110 (2006) 22570.

380 Carbon monoxide (CO) removal using activated carbon (AC) supported oxide catalyst derived from waste
Snigdha Sushil a* and Vidya S Batra a
a TERI University, DS Block, Habitat Place, Lodhi Road, New Delhi 110 003, India
* Corresponding author: Tel: +91-11-2468 2100 Fax: +91-2468 2144 email: snigdhasushil@gmail.com
Background
Oxides of transition metals like Fe, Cu, Cr are known to be highly active in the catalytic conversion of environmental pollutants like hydrocarbons, nitrogen
oxides, carbon monoxide. Use of industrial wastes containing these catalytically active metals as a substitute to commercial catalyst can help reduce the
associated cost. Red mud from the aluminium industry contains high percentages of Fe 2 O 3 in addition to Al 2 O 3 , TiO 2 , SiO 2 and other minor components like
V 2 O 5 , Na 2 O and CaO. It is possible to extract the metal from red mud by acid digestion and use the solution containing the active component for precipitation on
activated carbon as catalyst support.
Results
This study reports the characterization and performance of activated carbon supported catalyst from red mud. Activated carbon derived from bagasse ash and
commercially available activated carbons were used for the study. The surface area and dispersion of the activated carbon supported metal oxides were analyzed
using nitrogen adsorption and scanning electron microscopy and was compared with virgin activated carbon. From the result it is seen that the difference in the
BET surface area is not significant. A decrease in the range of 20 to 30% was observed in the surface area of the loaded activated carbon compared to the
original. The SEM micrograph indicated the presence of iron oxides and hydroxides on the surface of the carbon. SEM-EDS confirmed primarily the presence of
iron and oxygen on the carbon surface. The AC- supported iron oxide was studied for carbon monoxide oxidation and the results are discussed.
Justification
CO is a highly toxic gas and therefore its removal is an important environmental application. Catalytic oxidation is a commonly used method for CO removal;
however the use of expensive precious metals is a limiting factor. Metal oxides too are active for CO oxidation, however they are less active than the precious
metals. By supporting the metals/oxides on support material their activity can be increased. Activated carbon support helps in high catalyst dispersion, lower
oxidation temperature and higher activity. This study reports on an alternative catalyst derived from wastes, which may enable replacement of the existing
precious metal commercial catalysts. Thus, it is important from both an economic and environmental viewpoint.
397 Microwave-assisted adsorptive-catalytic removal of VOC from air.
I.M. Sinev a *, A.V. Kucherov a , L.M. Kustov a and M.Yu. Sinev b
a Zelinsky Institute of Organic Chemistry, R.A.S., 47 Leninsky prospect, Moscow 119991, Russia
b Semenov Institute of Chemical Physics, R.A.S., 4 Kosygina str., Moscow 119991, Russia
*Corresponding author. Tel: +7 495 137 6617, Fax : +7 495 137 2935, e-mail: sinevi@gmail.com
Background
Catalytic oxidative removal of volatile organic compounds (VOC) of different chemical nature from air is a challenging problem nowadays. If VOC
concentration in the mixture is low (< 1000 ppm) the total heat evolution during oxidation is not enough to conduct the process in autothermal regime and an
external heating is required. Unlike convectional conductive heating, microwave (MW) irradiation allows one to supply energy directly to the reaction zone and
provides with very high heating rates. The latter opens the possibility of efficient VOC removal based on combined periodic adsorption-oxidation regimes.
Results
In this study methanol oxidative removal was chosen as a model VOC abatement process. MW
activation was studied using a quartz tubular reactor irradiated by magnetron based system
continuously operated at frequencies ranging from 3.4 to 3.8 GHz and incident power 20-50 W.
Activated carbon (an efficient VOC adsorbent) and mixed Cu-Mn oxide (low-temperature oxidation
catalyst) layers were placed one-by-one into the reactor. Methanol content at the outlet was
continuously monitored using an on-line flame-ionization detector (FID). It a typical experiment the
mixture containing 500 ppm of methanol in air was supplied into the reactor. After 15 min. the MW
power was turned on causing the adsorbent heating and VOC desorption followed by its oxidation on
the catalyst. Some examples given on Fig. 1 demonstrate how FID signal (methanol concentration)
depends on the reactor temperature at different MW generator and air flow parameters. These data
show that combination of VOC adsorption with subsequent oxidation assisted with MW heating can
lead to an efficient pollutant removal.
100
3 (x5)
2
0
0 100 200 t, o C
Justification for acceptance
An efficient and energy saving VOC removal from air can be carried out in a combined adsorptive-catalytic system in periodic mode if MW irradiation is used as
a heating agent and appropriate materials interacting with MW field are used as adsorbents and catalysts.
I, a.u.
400
300
200
4
1
1 - 30W; 100 ml/min
2 - 30W; 20 ml/min
3 - 50W; 20 ml/min
4 - methanol desorption
(no catalyst)
Fig. 1 FID response vs. adsorbent/catalyst layer
temperature at different MW generator and air
flow parameters

406 The influence of cooling atmosphere after reduction on the catalytic properties
of Au/Al 2 O 3 and Au/MgO catalysts in CO oxidation
E. Gy. Szabó*, A. Tompos, M. Hegeds, J. L. Margitfalvi
Chemical Research Center, Hungarian Academy of Science, 1525 Budapest, POB 17, Hungary
*Corresponding author. Tel: 0063 1 3257747, email: szervin@chemres.hu
Background
Supported gold catalysts have obtained great scientific interest due to their unique activity in different oxidation reactions. They are used in catalytic CO
oxidation for removal of CO from different process gases and air.
It is known that the activity of gold catalysts strongly depends on the atmosphere used for thermal treatment before the reaction. Au/TiO 2 catalysts show high
activity after oxygen treatment, while Au/MgO had higher activity after reduction.
Results
During our temperature programmed CO oxidation measurements we have observed an additional new phenomenon, namely the influence of the atmosphere
(reductive or inert) of cooling after reductive pretreatment at 350 o C, on the activity of magnesia and alumina supported gold catalysts.
We have found that the Al 2 O 3 , MgO/Al 2 O 3 and MgAl 2 O 4 supported gold catalysts show higher activity after cooling in hydrogen atmosphere, while the
Au/MnO x /Al 2 O 3 and Au/MgO catalysts were found to be more active after cooling in helium atmosphere. Usually the effect of the cooling atmosphere was more
pronounced with increasing gold content. The iron modified catalysts in the lower temperature region show higher activity after cooling in He atmosphere, while
at higher temperature they were more active after cooling in H 2 . The cobalt modifier resulted in higher activity after cooling in hydrogen atmosphere [1].
The FTIR measurements revealed a CO adsorption shift towards lower wavenumbers when the catalysts were cooled in helium. This suggests an increasing
strength of CO adsorption and a decrease of partial positive charge on the gold nanocluster.
Justification for acceptance
The CO concentration in the hydrogen feed into PEM fuel cells must be kept under 100 ppm. The development of catalysts for the elimination of CO from the
hydrogen feed is considered as the key issue in developing an economically feasible hydrogen production technology for PEM application.
Another application of low temperature CO oxidation is air cleaning. Various air-conditioning devices and gas helmets contain gold catalysts. The applicability of
gold catalysts in gas helmets is greatly enhanced by the fact that the activity of supported gold catalysts increase in the presence of moisture.
References
[1] E. Gy. Szabó, A. Tompos, M. Hegeds, Á. Szegedi, J. L. Margitfalvi, Appl. Catal. A: Gen. 320 (2007) 114.
407 Effect of the Au chemical state on the synergistic performance of Au-VO x /TiO 2 catalysts
in the total oxidation of chlorobenzene.
R. Delaigle, A. Coget, P. Eloy, E.M. Gaigneaux*
Unité de catalyse et de chimie des matériaux divisés, Université catholique de Louvain,
Louvain-la-Neuve, Belgium
*Corresponding author. Tel: +32 10 47 36 65, Fax: +32 10 47 36 49, email: eric.gaigneaux@uclouvain.be
Background
Recently, some authors have reported a synergistic effect between gold and vanadia supported on titania in the total oxidation of VOCs [1-3]. Even though some
explanations were proposed, this synergy is not yet completely understood. Therefore, we studied and characterised two kinds of Au-VO x -based catalysts in the
total oxidation of chlorobenzene in order to correlate the catalytic performances with the chemical state of Au in the catalysts.
Results
TiO 2 (Degussa P25) was used as support. Gold was loaded by a deposition-precipitation method and VO x was introduced via a wet impregnation method and
subsequent conventional drying and calcination. The two Au-VO x -based catalysts differ only in the order of deposition of the two species. Two well-defined
catalysts (Au/TiO 2 and V 2 O 5 /TiO 2 ) were used as reference for the comparison of catalytic performances and physico-chemical properties (XPS, XRD, BET,
TEM…). The two Au-VO x -based catalysts exhibit quite different catalytic activity in the total oxidation of chlorobenzene. An interesting correlation is found
between catalytic performances and XPS data: gold appears in a more oxidized state in the catalyst which showed the highest catalytic activity while gold is in a
more metallic state in the other catalyst. In the first case, gold was deposited firstly. This result gives an explanation to the conclusions of Andreeva and al [1].
XPS data give additional information on the needed oxidation state of the Au promoter to obtain an optimal synergistic effect. This is surely one facet of the
understanding of the mechanism of the synergy between Au and vanadia as the optimal Au state is as surely related to other parameters as location of Au (respect
to VO X ) and its dispersion. This communication will additionally report on these other correlations.
Justification for acceptance
A better understanding of the synergistic effect between gold and VO x enables us to optimize Au-VO x -Ti systems. Our investigations showed that Au must be
more oxidized than the metallic state to have an optimal synergistic effect with vanadia. Furthermore, our study confirms that the sequence in the deposition
order of the two metals influences the extent of the synergy, and suggests that an appropriate choice of the preparation, namely chosing methods leaving Au in
the optimal state, will be of relevance.
References
[1] D. Andreeva, T. Tabakova, L. Ilieva, A. Naydenov,D. Mehanijev, M.V. Abrashev, Appl. Catal. A: Gen. 209 (2001) 291- 300.
[2] V. Idakiev, L. Ilieva, D. Andreeva, J.L. Blin, L. Gigot, B.L. Su, Appl. Catal. A: Gen. 243 (2003) 25-39.
[3] C. Della Pina, N. Dimitratos, E. Falletta, M. Rossi, A. Siani, Gold Bull. 40 (2006) 67-72.

409
The selectivity of the noble metal catalysts on the oxidation of chlorinated hydrocarbons
S. Pitkäaho * , S. Ojala and R. L. Keiski
University of Oulu, Department of Process and Environmental Engineering,
P.O. Box 4300, FIN-90014 University of Oulu, Finland
* Corresponding author. Tel: +358 8 5532387, Fax: +358 8 5532369, e-mail: satu.pitkaaho@oulu.fi
Background
Because of their harmful properties to health and environment, the release of CVOCs (chlorinated volatile organic compounds) is being controlled by
increasingly stringent regulations [1]. Based on literary review [2-5] and on our earlier studies [6] it can be concluded that there are noble metal catalysts
available for CVOCs to be fully oxidized to the desired products: CO 2 , H 2 O, and HCl. However, optimal reaction conditions to limit the formation of harmful and
even toxic by-products are essential in CVOC oxidation. In this study several hydrogen sources and optimal conditions were tested to improve the selectivity of
reaction towards HCl production.
Results
The complete catalytic oxidation of dichloromethane (DCM) and perchloroethylene (PCE) over several noble metal catalysts supported on Al 2 O 3 were studied at
the laboratory scale. The HCl formation was studied with several reactant mixtures of DCM, PCE, dimethylformamide (DMF) and oxitol. Ethanol, ethylene and
H 2 O were used as hydrogen sources. In general, Pt -catalyst showed the best selectivity towards HCl formation. The results showed also that even though the
presence of DMF enhanced the DCM conversion, it deteriorated the yield of HCl especially at low temperatures. DMF had no effect on the PCE conversion but it
affected the yield of HCl negatively. Oxitol had no effect on conversions but it slightly decreased the HCl yields when mixed with DCM and PCE. From the
hydrogen sources tested, water proved to be the most efficient.
Justification for acceptance
CVOCs are among the most harmful and difficult pollutants to be destroyed. Therefore, it is essential to find selective and effective catalysts and optimal
conditions to actually destroy the compounds instead of causing more damage due to incomplete oxidation, resulting harmful by-products.
References
[1] Directive 99/13/EC. Official J of the European Communities 29.3.1999.
[2] J. Corella, J. M. Toledo, A. M. Padilla, Appl Catal B Environ 27 (2000) 243.
[3] B. Chen, C. Bai, R. Cook, J. Wright, C. Wang, Catal Today 30 (1996) 15.
[4] J. R. Gonzáles-Velasco, A. Aranzabal, J. I. Gutiérrez-Ortiz, R. López-Fonseca, M. A. Gutiérrez-Ortiz, Appl Catal B Environ 19 (1998) 189.
[5] L. Wang, M. Sakurai, H. Kameyama. J Hazard Mater xxx (2007) (in press).
[6] S. Pitkäaho, Catalytic incineration of chlorinated volatile organic compounds, Master’s Thesis, University of Oulu, Finland (2006) 129 p.
417 Oxygen Isotopic Exchange from CO 2 over Pd/Al 2 O 3 catalyst
S. Ojala a , * N. Bion b , D. Duprez b , and R. Keiski a
a Dept. of Process and Environmental Engineering, POB 4300, 90014 University of Oulu, Finland.
b Lab. de Catalyse en Chimie Organique, LACCO-UMR 6503, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France
*Corresponding author. Tel: +358 8 553 2318, Fax : +358 8 553 2318, e-mail: satu.ojala@oulu.fi
Background
The role of lattice oxygen is of major importance for the comprehension of oxidation reaction mechanisms over oxide and metallic supported oxide catalysts. To
characterize the oxygen mobility at the surface of the catalysts, isotopic exchange of oxygen is generally used [1,2]. This work shows that the utilization of
isotopic CO 2 exchange instead of isotopic O 2 exchange presents an important advantage to study the lability of oxygen species occurring during oxidation
reaction of hydrocarbon. This information is needed for the development of more active, selective and durable catalysts in environmental applications, e.g., VOC
abatement and automobile exhaust gas treatment.
Results
The isotopic oxygen exchange from CO 2 experiments were performed over Pd/Al 2 O 3 and correlated to results obtained during the isotopic O 2 exchange with or
without the presence of CH 4 . The catalyst was prepared by incipient wetness impregnation with Pd-nitrite complex formation from NaNO 3 and Pd(NO 3 ) 2 H 2 O
aqueous solutions [3]. The oxygen exchange between a gas phase molecule and the solid catalyst differs significantly if oxygen is exchanged from 18 O 2 or from
C 18 O 2 . The rate of oxygen exchange over the Pd/Al 2 O 3 catalyst is higher in the case of C 18 O 2 . Oxygen exchange rate over pure alumina is near to the values of
Pd/Al 2 O 3 . It shows that the exchange occurs mainly on alumina. However the first isotopomers appearing in the gas phase show that O from PdO are the first
atoms exchanged. This was also confirmed with experiments carried out over the Pd/SiO 2 catalyst. Similar exchange was not seen to take place from 18 O 2 . These
observations were corroborated with the results obtained in the O 2 exchange rate over Pd/Al 2 O 3 catalysts in the presence of methane.
Justification for acceptance
The oxygen exchange rates over Pd/Al 2 O 3 are higher from gas-phase CO 2 than from O 2 . The results obtained give information to understand why palladium
catalysts, which are active in CH 4 oxidation reaction, are not very active in isotopic O 2 exchange. It is of a major interest for catalytic oxidation applications but
also for automobile exhaust gas treatment applications.
References
[1] V.V. Popovskii, G.K. Boreskov, V.S. Muzykantov, V.A. Sazanov, S.G. Shubnikov, Kinetica I Kataliz., 1 (1969) 240.
[2] D. Duprez, Isotopes in Catalysis. Imperial College Press, Catalytic Science Series 4 (2006) 133-181.
[3] M. Benkhaled, S. Morin, Ch. Pichon, Cu. Thomazeau, C Verdon, D. Uzio, Applied Catalysis A: General, 312 (2006)1-11.

420 Study of thermal and chemical stability of Ce/Zr mixed oxides for Cl-VOC oxidation
B. de Rivas, R. López-Fonseca, J.I. Gutiérrez-Ortiz*, M.A. Gutiérrez-Ortiz
Chemical Technologies for Environmental Sustainability Group, Department of Chemical Engineering,
Faculty of Science and Technology, Universidad del País Vasco/EHU, P.O. Box 644, E-48080 Bilbao, Spain.
Phone: +34-94-6012683; Fax: +34-94-6015963; E-mail address*: joseignacio.gutierrez@ehu.es
Background
Catalytic combustion is widely accepted as an attractive approach for the destruction of volatile organic compounds found in air emissions to keep them in
compliance with increasingly stringent environmental regulations. The success of this technology depends not only on the efficiency of the selected catalyst in
terms of low-temperature activity and selectivity to deep oxidation products but also on the stability during extended time on stream in the presence of HCl
and/or Cl 2 . The main scope of this work is to evaluate the behaviour of a series of Ce/Zr oxides submitted to a previous chlorination and calcination at high
temperature in the oxidation of 1,2-dichloroethane.
Results
Previous studies on the catalytic behaviour of fresh Ce/Zr mixed oxides (calcined at 550 ºC) evidenced that surface acidity and accessible lattice oxygen play a
key role in the catalytic combustion of chlorinated compounds. Hence, the Ce 0.5 Zr 0.5 O 2 composition exhibited an appropriate combination of both properties
leading to a better activity. Thermal aging (750 ºC for 4h) led to a noticeable decrease in the surface area and a marked sintering, as evidenced by an increase in
crystallite size. In addition, acid and redox properties were negatively impacted [1]. This was especially relevant for pure ceria but the incorporation of zirconia
into the ceria lattice limited the effect to a lower extent. Thus Ce 0.15 Zr 0.85 O 2 sample showed the highest thermal resistance. Even though, the aged catalysts
required significantly higher combustion temperatures (increases by 10 ºC for Ce 0.15 Zr 0.85 O 2 and 40 ºC for CeO 2 ). As for thermally and chemically aged samples,
in addition to catalyst modifications due to high temperature calcination, remarkable changes in acidity and redox properties were distinctly attributed to
chlorination. Again pure ceria was the most affected catalyst by chlorine poisoning. However as the zirconia content increased these differences were less
noticeable. Indeed no significant shift towards higher combustion temperatures were noticed for Ce 0.15 Zr 0.85 O 2 after chlorination. The formation of acid, easily
reducible CeOCl species limited the negative impact of sintering at high temperature [2]. It could be therefore concluded that Zr-rich Ce/Zr catalysts resulted
significantly resistant to deactivation by sintering and chlorine poisoning, thereby showing a great potential for this environmental application.
Justification for acceptance
Chemical and thermal stability of catalysts for Cl-VOC combustion under realistic operating conditions is paramount importance since they determine the
industrial application.
Reference
[1] G. Colón, F. Valdivieso, M. Pijolat, R.T. Baker, J.J. Calvino, S. Bernal, Catal. Today 50 (1999) 271.
[2] J. Soria, A. Martínez-Arias, J.M. Coronado, J.C. Conesa, Top. Catal. 11/12 (2000) 205.
425 The removal of carbon monoxide over CuO-Fe 2 O 3 /SiO 2 catalysts
M. Zieliski a,b , S.Monteverdi a , M.M.Bettahar * a
a
UMR 7565, Catalyse Hétérogène, Faculté des Sciences, Université Henri Poincaré, Nancy-I, BP 239, 54506 Vandoeuvre-lès-Nancy Cedex, France.
b Adam Mickiewicz University, Department of Chemistry, Grunwaldzka 6, 60-780 Pozna, Poland
Background
Precious metals work very well with the high catalytic activity and stability on CO oxidation at low temperature [1]. Transition metal oxides such as copper or
iron oxides are less costly alternatives to the precious metals-based catalysts for carbon monoxide oxidation [2,3]. Due to the synergistic effect, the composite
oxides of transition metals exhibit higher catalytic activity on CO oxidation than those of individual transition metal oxides. Only few studies were reported on
the CuFeOx system [4]. This prompted us to investigate co-precipitated CuO-Fe 2 O 3 system supported on SiO 2 .
Results
All catalysts exhibited stable activity with time on stream after initial activation. The weight ratios of
copper to iron and calcination temperature have important effect on the catalytic activity of the
catalysts. The catalyst with weight ratio of 1:1 exhibited highest catalytic activity on CO oxidation
with lowest T 100% of 480K (Figure). For the catalyst with Cu:Fe ratio 1:1, the best activity is obtained
when the calcination temperature was 573 K. These results were ascribed to formation of CuFeOx
species when copper is incorporated in the iron matrix. Catalysts H 2 -TPR profiles (not shown)
confirmed this synergistic effect since the catalysts reduction temperature decreased with Cu:Fe ratio
down to a minimum corresponding to Cu:Fe=1.Other investigations (XRD, TEM, X-mapping) are in
hand and preliminary results indicate correlations between particle size, Cu:Fe ratio and catalytic
activity.
Justification for acceptance
The results obtained show that the supported CuFeOx system exhibit very high activity and stability in
the CO oxidation at low temperature. These performances, which depend on the Cu:Fe ratio and
calcination temperature, are attributed to presence of easily reducible CuFe species. Other
investigations in hand confirm this conclusion and we expect further improvement of the catalytic
performances observed.
References
[1] S.D. Gardner, G.B. Hoflund, B.T. Upchurch, D.R. Schryer, E.J. Kielin, J. Schryer, J. Catal., 129 (1991) 114.
[2] T.J. Huang, D.H. Tsai, Catal. Lett., 87 (2002) 173.
[3] P. Li, D.E. Miser, S.Rabiei, R.T. Yadav, M.R. Hajaligol, Appl. Catal. B., 43 (2003) 151.
[4] E. Boellaard, F.Th. van de Scheur, A.M. van de Kraan, J.W. Geus, Appl. Catal. A 171 (1998) 333.
reaction temperature (100%), K
600
585
570
555
540
525
510
495
480
465
450
435
420
405
0 1:4 1:2 1:1 2:1 4:1
weight ratio (Cu:Fe)
Reaction temperature (at 100% conversion ) of the
Cu-Fe/SiO 2 catalysts as a function of the Cu:Fe ratio.
Air activation: 2h, 573 K; Feed: 5%CO/air; 40 mL min -1 .

426 Catalytic combustion of toluene on Cu and Pt MFI zeolites supported on cordierite foams
E.R. Silva a , J.M. Silva a, b , M.F. Vaz c , F.A Costa Oliveira c, d , F.R. Ribeiro a , M. F. Ribeiro a*
a Instituto Superior Técnico, IBB-Centre for Biolog. and Chem. Eng., Av. Rovisco Pais, 1049-001 Lisboa, Portugal,
b
Instituto Superior de Engenharia de Lisboa, Chem. Eng. Dept., R. Cons. Emídio Navarro, 1959-007 Lisboa, Portugal.
c
Instituto Superior Técnico,Dept. Materials Eng. ., ICEMS, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
d
Instituto Nacional de Engenharia, Tecnologia e Inovação, Dept. Materials and Production Technologies, Estrada Paço do Lumiar, 1649-038 Lisboa, Portugal
*Corresponding author. fax: (+351)218419198, e-mail: filipa.ribeiro@ist.utl.pt
Background
The emission of volatile organic compounds (VOCs) to the atmosphere is an important environmental problem. Catalytic oxidation is one of the most suitable
ways for VOCs removal from numerous gas effluents [1]. Recently, ceramic foam catalyst supports have revealed potential improvements on the catalytic
efficiency [2]. In this work cordierite foams, produced by replication method, have been washcoated with Cu and PtMFI zeolites. The catalytic properties of
zeolite based foams were evaluated in the deep oxidation of toluene.
Results
Cu and Pt MFI zeolites supported on cordierite foams prepared by an improved washcoating method, involving a cationic polymer and powder metal zeolite
suspensions, revealed uniform catalyst layers, with thicknesses in a range of 25-50 m for catalyst contents between 5-20 wt.%. Negligible weight losses, after
1h ultrasounds, show good adherence of the coatings onto the foam’s surface. CuMFI (2 wt.% Cu) and PtMFI (0.1 wt.% Pt) coated cordierite foams, with catalyst
contents around 5-8 wt.%, have been evaluated in the toluene total oxidation (800 ppm in air). They show higher catalytic activity than their bulk-form
counterparts. High oxidation rates and a decrease of about 50 ºC in the light-off temperature (temperature at which 50% of toluene conversion into CO 2 is
attained) were obtained with foam based catalysts. Bulk-form catalysts require the use of higher catalyst contents (about 2 - 3 times more) to obtain similar
toluene conversions. Besides the activity increase, for Cu based foams, the dispersion of metal zeolites into thin coatings also provides higher selectivities into
CO 2 (negligible CO formation). The enhanced performance of the structured catalysts can be attributed not only to good catalyst dispersion, but also to a better
mass and heat transfer phenomena promoted by the foam tortuosity.
Justification for acceptance
Ceramic foams represent a very promising type of structured catalyst carriers in comparison with monoliths. High radial and axial heat transfers provided by 3D
open-cell structure of foams make them suitable for exothermic reactions, namely for VOCs combustion. This work confirms that good catalytic properties, for
toluene combustion, are achieved with metal based zeolites supported on cordierite foams.
References
[1] R. M. Heck, R. J. Farrauto, S. T. Gulati, Catalytic Air Pollution Control, Wiley Interscience, 2 nd edition, 2002.
[2] M. V. Twigg, J. T. Richardson, Ind. Eng. Chem. Res. 46 (2007) 4166.
434 Noble metals supported on Cu-hydrotalcites for selective reduction of chlorinated contaminants
K. Föttinger a, *, N. Barrabes a,b , D. Cornado a,b , A. Haghofer a , F. Medina b and G. Rupprechter a
a Inst. of Materials Chemistry, Vienna University of Technology, Veterinärplatz 1, Vienna, 1210, Austria.
b Dep. Chemical Engineering, Rovira i Virgili University, Campus Sescelades, Tarragona, 43007 Spain.
*Corresponding author. Tel: +43 1 250773816, Fax : +43 1 250773890, e-mail: kfoettinger@imc.tuwien.ac.at
Background Chlorinated organic compounds like trichloroethene (TCE) are widely distributed pollutants due to their extensive usage e.g. for metal
degreasing or textile cleaning and lead to contamination of soil and groundwater. Catalytic hydrodechlorination is an interesting approach for removal of such
substances because to it has not only the benefit of destroying the chlorided compound but also of producing valuable products. Control of selectivity is a key
point. Ethene is the desired product, which is more useful than the total hydrogenation product ethane. As catalysts supported noble metals (Pd, Pt) are frequently
used, better selectivities to ethene can be obtained by adding a second metal, such as Cu or Ag. Unsolved problems concern mainly the catalyst stability and
ethylene selectivity.
Results Pt and Pd supported on Cu-hydrotalcites catalysts were synthesized by co-precipitation at three different Mg/Cu molar ratios. The samples were
characterised by XRD, TGA, TPR, FTIR spectroscopy of CO adsorpton and hydrogen chemisorption. Catalytic tests for the hydrodechlorination reaction of
trichloroethylene (TCE) were carried out in a continuous flow fixed-bed reactor at 373-573 K, atmospheric pressure and stoichiometric amounts of hydrogen.
Excellent selectivities to ethene were obtained at 573 K compared to Pd and Pt catalysts supported on -alumina, which produce mainly ethane. Due to the large
amount and high dispersion of Cu in the hydrotalcite materials the TCE is expected to stick mainly to the Cu, which is responsible for cleavage of the C-Cl bond.
Cu is then regenerated by spillover of hydrogen from the noble metal. Such a mechanism was proposed for bimetallic Pd-Ag catalysts supported on alumina in
[1]. However, Cu requires rather high temperatures for significant reactivity compared to Pd and Pt, therefore the catalytic behaviour in the low temperature
range can be mainly attributed to reaction on the noble metal, leading to similar results than on alumina and thus to mainly ethane formation. Differences in
catalytic properties were mainly observed at 573 K.
Another important effect of using hydrotalcites is the higher stability against coke formation due to the basicity of these materials, on the more acidic alumina
significant activity loss was observed.
Hardly any influence of the Mg:Cu ratio was found due to the large excess of Cu and the necessity of sufficient hydrogen activated on the noble metal for
removal of Cl from the chlorinated Cu.
Justification for acceptance This work is clearly dealing with environmental catalysis. Tri- and tetrachlorothene are widely used in industry and belong to the
most wide-spread pollutants contaminating soil and ground water. The process that is the topic of this work can be applied for cleaning contaminated soil (via
flushing the contaminants out), but can also be carried out in liquid phase using the same catalysts for cleaning waste water. In addition valuable products are
produced compared to simple destruction of these compounds via incineration.
References
[1] B. Heinrichs, J.-P. Schoebrechts, J.P. Pirard, J. Catal. 200 (2001) 309.

442 Degradation of clofibric acid in aqueous medium by heterogeneous catalytic oxidation
L. Fialho a , A. Fernandes a A. Dordio, A. Carvalho a , D. Teixeira b , A. Candeias a , C.T. Costa a , A.P. Pinto b , J.E. Castanheiro a *
a CQE, Departamento de Química, Universidade de Évora, 7000-671 Évora, Portugal
b ICAM, Universidade de Évora, Portugal
Corresponding author. Tel.: +351 266745311; fax.: +351 266744971; E-mail address: jefc@uevora.pt
Background
Many drugs are not completely removed during the wastewater treatment and as a result pharmaceuticals have been found in a wide range of environmental
samples including surface water, groundwater and drinking water. Clofibric acid (CA) is the bioactive metabolite of drugs such as clofibrate and
etofyllineclofibrate, widely used as blood lipid regulators [1]. Advanced oxidation processes (AOP) have been used for the degradation of different organic
pollutants (e.g. pharmaceuticals compounds). These processes are characterized by the formation of OH radicals, which ensure high reactivity and low selectivity
[2]. In this work, we report the heterogeneous catalytic oxidation of clofibric acid with H 2 O 2 over transitions metal complex dispersed in the polymeric matrix.
Results
The transition metal complexes (V(acac), VO(acac) and Co(acac)) were dispersed in the PDMS matrix according the Neys et al [3]. In order to determine the
amount of metal in the polymeric matrix, ICP analysis was carried out. The composite catalysts were also characterized by UV-Vis spectroscopy. It was observed
that the UV-Vis spectrum of the catalyst shows the characteristics bands of transition metal complexes, suggesting the acac complex structure is kept intact during
immobilization. The catalytic reactions were carried out in a batch reactor at ambient temperature under magnetic stirrer. The experiments were carried out using
aqueous solutions containing 10 mg L -1 of CA, 1g of catalyst and 1 mL of hydrogen peroxide.
Justification for acceptance
There is great interest in the environmental relevance of pharmaceutical drugs and their metabolites as emerging pollutants in waters because conventional water
treatment systems are not efficient in their removal. In this work the removal of clofibric acid from aqueous solutions was investigated by the application of
heterogeneous advanced oxidation processes.
References
[1] I. Sirés, C. Arias, P. L. Cabot, F. Centellas, J. A. Garrido, R. M. Rodríguez, E. Brillas, Chemosphere 66 (2007) 1660.
[2] R. Molinari, F. Pirillo, V. Loddo, L. Palmisano, Cat. Today 118 (2006) 205.
[3] P.E.F. Neys, I: F.J. Vankelecom, M. L’abbé, R.F. Parton, E. Cenlemans, W. Dehaen, G.L’abbé, P.A. Jacobs, J.Mol. Cat. A 134 (1998) 209.
444 TiO 2 -ZrO 2 based catalysts for chlorinated organics combustion.
S. Albonetti, R. Bonelli*, J. Epoupa Mengou, F. Trifirò
Dipartimento di Chimica industriale e dei Materiali, Alma Mater Studiorum Università di Bologna, Viale Risorgimento 4, 40136 Bologna, Italy - INSTM, Research Unit of
Bologna, Italy.
*Corresponding author. Tel: 0039-051-2093677, Fax: 0039-051-2093680, e-mail: rosa.bonelli@unibo.it
Background
Chlorinated organics molecules are important class of air pollutants, emitted from industrial process and urban incinerators. Catalytic combustion is one of the
most promising technologies for their destruction, due to its definitive character and save of energy. VOCs and Cl-VOCs can be, in fact, oxidised over catalyst at
temperatures much lower than those used for the thermal oxidation. In the case of stationary sources, the most important applications consist in VOC abatement
and DeNOx process [1]. Commercial catalysts for the latter are based on V 2 O 5 /WO 3 mixed oxides supported on a high surface area TiO 2 (anatase).
In a previous work [2] we demonstrated that isolated and well dispersed vanadium sites resulted beneficial for o-dichlorobenzene (o-DCB) conversion.
Nevertheless, the presence of high amount of tungsten and/or vanadium on the support was proven to lead to the formation of partial oxidation products.
Results
In this work, we have investigated the effect of additives such as La 2 O 3 , WO 3 , SiO 2 , Fe 2 O 3 and P 2 O 5 on the activity of V 2 O 5 -ZrO 2 -TiO 2 catalysts on the course of
the total decomposition of o-DCB. A series of catalysts prepared by incipient wetness impregnation of vanadium on doped TiO 2 -ZrO 2 supports were
characterized by XRD, TEM, H 2 -TPR, Raman spectroscopy and surface area measurements. All studied catalysts were active in the decomposition of o-DCB,
but the kind of additive present on the support was demonstrated to be important in controlling the vanadium dispersion on the support and, thus, the material
activity. While La 2 O 3 and P 2 O 5 have a negative impact, WO 3 , and Fe 2 O 3 have a positive influence on catalyst performances. This beneficial effect seems to reside
in the absence of mutual spreading between VOx and these two oxides, preventing the coverage of VOx by the secondary phase and promoting the links between
vanadium and TiO 2 based support. On the contrary La 2 O 3 and P 2 O 5 species tend to react and spread on vanadium sites, leading to a decrease of the number of
active sites at the surface of the catalyst.
Justification for acceptance
These results are interesting because the identification of new formulations with high catalytic activity, able to increase the oxidation potential of classical SCR
catalysts, is an important goal for efficiency improvement in chlorinated pollutants destruction and for commercial applications.
References
[1] P. Forzatti, Appl. Catal. A 222 (2001) 221.
[2] S. Albonetti, S. Blasioli, A. Bruno, J. Epoupa Mengou, F. Trifirò, Appl. Catal. B 64 (2006) 1.

449 Parametric study on the durability of CoO x /TiO 2 catalysts for low-temperature CO oxidation
Ki-Hwan Kim a , Moon Hyeon Kim a,* , Dong Woo Kim a , Sung-Won Ham b
a Department of Environmental Engineering, Daegu University, 15 Naeri, Jillyang, Gyeongsan 712-714, Korea
b Department of Display and Chemical Engineering, Kyungil University, 33 Buho, Hayang, Gyeongsan 712-701, Korea
*Corresponding author. Tel: (+82-53) 850-6693, Fax: (+82-53) 850-6699, E-mail: moonkim@daegu.ac.kr
Background
We have recently studied CO oxidation at 100 o C over CoO x /TiO 2 catalysts that were prepared using TiO 2 pellets with binders and exhibited the highest steadystate
activity when calcined at 450 o C [1]. However, much longer activity maintenance in the oxidation reaction has been indicated for a 5 wt% CoO x catalyst,
dispersed on pure TiO 2 , after calcination at 350 o C [2]. Therefore, we are of particular interest to the durability of this pure TiO 2 -based system in the lowtemperature
CO oxidation reaction.
Results
A 85-% initial activity was obtained for the oxidation of CO at 100 o C over a 1 wt% CoO x catalyst, and it decreased rapidly with time and became zero since a
continuous operation of 7 h. Samples with 8 and 12 wt% CoO x also gave a short residence in a period of total oxidation. It is clear that the durability of this
supported catalyst in the oxidation reaction was determined by its CoO x content. Surprisingly, repeated calcinations and measurements on a single sample having
5 wt% CoO x altered the duration in the oxidation reaction. On-stream durability of 5 wt% CoO x /TiO 2 for the oxidation depended significantly on other reaction
parameters, such as temperature, O 2 and CO concentrations and so forth, as well. Only peaks for Co 3 O 4 nanocrystallites were observed for all the calcined
samples upon XRD measurements, which was very consistent with results acquired by Raman spectroscopy. XPS measurements for fresh samples gave a
surface CoO x phase which consists of Co 3 O 4 , irrespective to CoO x loading, but Co 2p binding energies in used samples varied with duration impairment. These
characterization results were a good vehicle to understand the dependence of the durability on the parameters selected.
Justification for acceptance
Homogeneous charge compression ignition (HCCI) engines give CO and hydrocarbons emissions with high concentrations greater than 1% [3]. The durability of
CoO x /TiO 2 catalysts to control them for road applications has been extensively examined as a function of reaction parameters.
References
[1] W.H. Yang, M.H. Kim, S.W. Ham, Catal. Today 123 (2007) 94.
[2] K.H. Kim, M.H. Kim, in Proceedings of 2 nd Internal Conference on Environmental Sciences (ICES’07), Ulaanbaator, Mongolia, 28 June – 2 July, 2007, p.
106.
[3] A. Bhave, M. Kraft, F. Mauss, A. Oakley, H. Zhao, SAE Technical Paper 2005-01-0161.
452 Effect of acidity in the catalytic destruction of 1,2-dichlorobenzene over V 2 O 5 /TiO 2 based catalysts.
S. Albonetti a,* , S. Blasioli a , R. Bonelli a , J. Epoupa Mengou a , S. Scirè b , F. Trifirò a
a Dipartimento di Chimica industriale e dei Materiali, Alma Mater Studiorum Università di Bologna Viale Risorgimento 4, 40136 Bologna, Italy - INSTM, Research Unit of
Bologna, Italy.
b Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, 95125 Catania (Italy).
*Corresponding author. Tel: 0039-051-2093681, Fax: 0039-051-2093680, e-mail: stefania.albonetti@unibo.it
Background
During our studies on the activity of V 2 O 5 /TiO 2 -based catalysts for the destruction of chlorine-containing organic compounds, we have investigated the
oxidation of 1,2-dichlorobenzene (o-DCB) over supported vanadium catalysts [1]. Our research, for the first time, spotlighted the formation of 3,4-dichlorofuran-
2,5-dione (dichloromaleic anhydride, DCMA) as a by-product during catalytic oxidation with some of the tested systems. Since the formation of this molecule
could be strongly affected by the acidity of the catalysts, the present work was mainly aimed at investigating the effect of this parameter on catalytic
performances.
Results
Catalytic activity data proven that the o-dichlorobenzene conversion on all V 2 O 5 /TiO 2 -based systems resembles the trend of Brønsted acidity indicated that these
sites are beneficial for o-DCB conversion. Nevertheless, these materials lead, in some case, to the formation of partially oxidized compounds, and the presence of
a high number of Brønsted acid sites significantly increases the formation of these molecules. On the contrary, Lewis acid sites, acting as absorbing sites,
promote the further oxidation of intermediates to CO and CO 2 , without any by-products desorption. These effects were confirmed by the study of dichloromaleic
anhydride decomposition on materials with different acidity. On the basis of these data a reaction mechanisms for the oxidation of o-dichlorobenzene over
vanadium supported catalysts in presence of different acid sites was proposed. Furthermore, the presence of water in the feed-stream was proven to decrease o-
DCB conversion but also to play a positive role on process selectivity, increasing COx production. Plausible reasons for this effect are the reduction of the
number of Brønsted acid sites in presence of water and the hydrolysis of anhydride that favours its decomposition.
Justification for acceptance
This work proves that the decomposition of chlorinated organics on V 2 O 5 /TiO 2 can lead to even more toxic chlorined by-products and that the formation of these
molecules is strongly connected with the Brønsted acidity of the catalysts. The detection of dichloromaleic anhydride in our reaction conditions can be utilized to
figure out the key aspects of catalyst design for the destruction of chlorinated waste on vanadia supported systems.
References
[1] S. Albonetti, J. Epoupa Mengou, F. Trifirò, Catal. Today 119 (2007) 295.

453 Total oxidation of toluene over cluster-derived gold/iron catalysts.
S. Albonetti a, *, R. Bonelli a , L. Folli Ruani a , C. Femoni b , C. Tiozzo b , S. Zacchini b , F. Trifirò a
a Dipartimento di Chimica industriale e dei Materiali, Viale Risorgimento 4, 40136 Bologna, Italy
b Dipartimento di Chimica Fisica ed Inorganica, Viale Risorgimento 4, 40136 Bologna, Italy
*Corresponding author. Tel: 0039-051-2093681, Fax: 0039-051-2093680, e-mail: stalbone@fci.unibo.it
Background
It has been recently reported that gold/iron catalysts revealed high activity in the catalytic oxidation of different molecules. Since the catalytic behavior of multicomponent
supported catalysts is strongly affected by the size of the metal particles and by their reciprocal interactions, the method of synthesis is a crucial point
to obtain systems with good performances. The use of bimetallic clusters with preformed bonds between metals of different properties is, thus, a promising
method for the preparation of highly dispersed catalysts. Among these, metal carbonyl clusters are quite attractive, since the fact that they can be prepared with
several different sizes and composition and, moreover, they are decomposed under very mild conditions.
Results
Little has been reported so far in the literature regarding supported bimetallic catalysts containing gold, thus, in this work, gold/iron bimetallic carbonyl cluster
salts were utilized as precursors to synthesis TiO 2 -supported catalysts and their catalytic activity and stability in the complete oxidation of toluene were
investigated [1]. A series of Au/FeOx/TiO 2 catalysts with different content of gold and iron were prepared by impregnation of the bimetallic carbonyl cluster salts
[NEt 4 ] 4 [Au 4 Fe 4 (CO) 16 ] and [NEt 4 ][AuFe 4 (CO) 16 ] on TiO 2 . The novel preparation method resulted in small gold nanoparticles already after air exposure at
ambient temperature and, depending on the gas atmosphere utilized during thermal treatments, highly dispersed metallic gold can be formed at 673 K. All the
iron/gold cluster-derived catalysts exhibited an excellent stability under catalytic conditions in toluene total oxidation and the catalytic activity was demonstrated
strongly dependent on the cluster loading and on the Au/Fe ratio. Moreover, no formation of partial oxidation products was revealed for any of the tested
materials and CO 2 was the only formed product.
Justification for acceptance
The use of carbonyl clusters to synthesize bimetallic catalysts is a promising way to obtain innovative systems with highly dispersed active phase where
synergistic effects are maximized. In this work on Au/FeOx/TiO 2 , with the goal of optimizing the method of synthesis and verify the activity and stability of
these materials in well known fields, we start testing these catalysts for toluene decomposition. Nevertheless, obtained information can be utilized also for other
oxidation reactions.
References
[1] S. Albonetti, R. Bonelli, J. Epoupa Mengou, C. Femoni, C. Tiezzo, S. Zacchini, F. Trifirò “Gold/Iron carbonyl clusters as precursors for TiO 2 supported
catalysts” Catal. Today doi 10.1016/j.cattod.2007.11.003.
458 Platinum catalysts on activated carbon support for water denitrification.
States of oxygen surface groups and textural properties after impregnation and reduction steps.
P. Gheek 1,2 , G. Finqueneisel 1* , T. Zimny 1 , J. Trawczyski 2
1 Wrocaw University of Technology, Department of Coal and Petroleum , Gdaska 7/9,
50-344 Wrocaw, Poland
2 LCA/LCME - Université Paul Verlaine Metz, Rue Victor Demange, F 57500 Saint Avold, France
* corresponding author. Tel: (33)+3 87 93 91 00, e-mail: gisele.finqueneisel@univ-metz.fr
Background
The continuous increase in the use of carbonaceous materials as catalyst supports makes necessary a deep knowledge of the preparation variables determining the
properties and performance of the final catalysts. Carbon-supported platinum is widely used in a great variety of reactions (hydrogenation, hydrogenolysis…). In
water denitrification, highly dispersed platinum is required and is related to support characteristics. It is well known but not yet completely understood that
surface chemistry and/or the porosity of catalyst carrier plays an important role during the preparation (impregnation and reduction steps) but also influence the
activity and selectivity of the final catalyst.
Results
In this study, commercial granular activated carbon (AC) obtained by activation of coconut shell in steam at 1123K, differing in the degree of burn-off were used
as catalyst carriers. The effect of surface functional groups on the metal dispersion and properties of carbon-supported platinum catalysts for hydrogenation of
nitrates has been investigated. 1 wt% of Pt was deposited over prepared carbon carriers and the obtained catalysts were characterized by H 2 -adsorption to
determine dispersion, temperature-programmed reduction (H 2 -TPR) and TPD experiments. The temperature of reduction set was 573K. The surface functional
groups were characterized after all preparation steps of the catalyst (support, impregnation and reduction) by acid-base titrations, temperature-programmed
desorption (TPD) of the decomposition products (CO and CO 2 ) and water vapor adsorption. During the impregnation step, the interaction between the precursor
(H 2 PtCl 6 ) and the carbon surface causes the formation of oxygen surface groups and the reduction of the platinum but the textural properties are not significantly
modify. However, after a reduction treatment to obtain a metallic platinum phase, the main part of less stable oxygen complexes is decomposed.
Catalytic activity has been tested in the hydrogenation of nitrites in water. In typical experiments initial concentration of nitrite was fixed. The evolution of nitrite
and ammonium ions concentration was monitored by ion chromatography (ICD). The relation between properties of carrier surface properties and both activity
and selectivity of Pt catalysts supported on this material in the nitrites reduction was determined.
Justification for acceptance
This research work is supported by CNRS, in the frame of the Groupement de Recherche International "Catalysis for Environment : Clean and sustainable
Energy and Fuels".

475 Oxidation of benzyl alcohol in aqueous medium by ZrO 2 catalyst at mild conditions
Mohammad Sadiq*, Mohammad Ilyas
National Centre of Excellence in Physical Chemistry
University of Peshawar, Peshawar 25120, Pakistan
* e-mail: mohammad_sadiq26@yahoo.com Phone: 92-91-9216766, Fax: 92-91-9216671
Background
Catalytic oxidation of benzyl alcohol in aqueous medium by ZrO 2 is a significant and cheaper method for industrial synthesis of benzoic acid and for
cleaning of benzyl alcohol from industrial wastewater as well. The Oxidation of benzyl alcohol in aqueous medium under atmospheric pressure by molecular
oxygen/ air over ZrO 2 catalyst has been investigated. Major oxidation products of benzyl alcohol detected with GC and UV spectrophotometer were
benzaldehyde and benzoic acid. Optimal conditions were setup for better catalytic activity of ZrO 2 .
Results
XRD patterns show that the dominant phase is monoclinic. Monoclinic phase is responsible for alcohol oxidation activity. SEM images of ZrO 2 before reaction
and after reaction have no structural change pointing to the fact that the catalyst maintains its stability. EDX give the proof of chlorine absence in the zirconia
matrix. BET surface area of catalyst was found to be 62 m 2 /g. The study of different parameters like agitation and activation energy ~ 87.15 KJ/mole supports the
absence of mass transfer resistance. The Kinetic study supports the Longmuir- Hinshelwood mechanism.
Conclusion
Monoclinic ZrO 2 is to be proved a better catalyst for oxidation of benzyl alcohol in aqueous medium at very mild conditions. The higher activity
performance of ZrO 2 for the total oxidation of benzyl alcohol in aqueous solution attributed here to a high temperature of calcinations and to a remarkable
monoclinic phase of zirconia. It can be used with out any base addition to achieve good results. The catalyst is free of any promotion or additive and can be
separated from reaction mixture by simple filtration. This gives us reasons to conclude that catalyst can be reused several times.
References
1. M. Ilyas, M. Sadiq, Chem.Eng. Technol 30(2007) 1391
2. M. Ilyas, M. Sadiq, I. Khan, Chin J Catal 28 (2007), 413-416
3. St. Christoskova and M. Stoyanova , Water Res 3096 (2000), pp. 1–5
476 Sulfur organic compounds oxidation by hydrogen peroxide in the presence
of transition metal peroxo complexes and crown ethers
A.V.Anisimov*, A.V.Tarakanova, M.Kh.Baishev, V.A.Certkov
Department of Chemistry, Moscow State University, Moscow, 119991, Russia
*Corresponding author. Tel.7-495-9391227, e-mail: anis@petrol.chem.msu.ru
Background
Thiols, sulfides, and benzothiophene derivatives oxidation is very important route for purification of hydrocarbon raw materials and oil fractions from sulfur
compounds. Among the different catalysts proposed for this process transition metal peroxo complexes are the most frequently studied. There are many
difficulties to carry out benzothiophene derivatives oxidation in the presence of homogeneous and heterogeneous catalysts.
Results
In the present work, we dedicated particular attention to niobium and vanadium peroxo complexes with N- and O-containing ligands which are able with high
activity to catalyze oxidation of organic sulfides and benzothiophenes by hydrogen peroxide in bi-phase system. The concept of this system is a combination of
phase transfer and metal complex catalysis. In this case sulfide and oxidation products are dissolved in organic phase and catalyst is presented in water phase.
Alkylaryl sulfides in the presence of vanadium peroxo complexes can be oxidized mainly to corresponding sulfoxides, and in the presence of niobium peroxo
complexes sulfides and benzothiophenes can be oxidized to corresponding sulfones with almost quantitative yield in mild conditions. Oxidation of sulfides and
benzothiophenes by hydrogen peroxide in the presence of crown ethers without any metal catalysts has been studied as well. This oxidation system gives
possibility to carry out oxidation of dibenzothiophenes which have very low activity in motor fuels desulfurization processes to corresponding sulfone.
Transition metal peroxo complexes and crown ether were applied for diesel fuel oxidative desulfurization with high effectivity.
Justification
Niobium and vanadium peroxo complexes and crown ethers can be applied for containing in oil fractions sulfur organic compounds oxidation by hydrogen
peroxide. Crown ethers can be used without additional metal compounds.
References.
[1] A.V.Anisimov, A.V.Tarakanova, E.V.Fedorova, A.Z.Lesnugin, L.A.Aslanov. Catalysis Today 78 (2003) 369.
This work was supported by Russian Foundation of Basic Research (grant N 03-06-33267).

477 Selective Methanation of CO over Supported Noble Metal Catalysts
P. Panagiotopoulou, D.I. Kondarides, X.E. Verykios *
Department of Chemical Engineering, University of Patras. Greece
* Corresponding author. Tel/Fax: +30 2610 991527, e-mail: verykios@chemeng.upatras.gr
Background
The methanation reaction has been widely used in the past as a method for the removal of carbon oxides from inlet streams in hydrogen or ammonia plants.
Currently, the selective methanation of CO has become attractive as a potentially effective means of reduction of CO content of hydrogen-rich reformate gases to
extremely low levels, as required in fuel cell applications. In such applications, the undesirable methanation of CO 2 , which is also present in the effluent of the
reformer or WGS units, is often unavoidable. Consequently, it is important to develop selective CO methanation catalysts characterized by high activity at
sufficiently low temperatures, able to retard both the CO 2 methanation and the reverse WGS reactions.
Results
The catalytic performance of supported noble metal catalysts for the title reaction has been investigated with respect to the structural and morphological
properties of the dispersed metallic phase (Pt, Pd, Rh, Ru), as well as with respect to the nature of the support (Al 2 O 3 , CeO 2 , TiO 2 ,YSZ, SiO 2 ). Catalytic
performance has been examined in the temperature range of 150-450 C using a feed stream consisting of 1%CO, 50%H 2 , 15%CO 2 and 0-30%H 2 O (balance He).
It has been found that, the catalytic performance depends strongly on the noble metal-support combination employed, with Ru and Rh catalysts being generally
much more active, compared to Pt and Pd catalysts of the same metal content. Increasing metal loading results in a significant shift of the CO conversion curve
toward lower temperatures, where the undesired reverse WGS reaction becomes less significant. Results of kinetic measurements show that CO/CO 2
hydrogenation reactions are structure sensitive. In particular, for Ru/TiO 2 and Ru/Al 2 O 3 catalysts, TOFs of CO and CO 2 increase with increasing Ru crystallite
size, which is accompanied by an increase of selectivity to methane. The nature of the metal oxide support affects significantly the catalytic performance. In
particular, the turnover frequency of CO is 1-2 orders of magnitude higher when Ru is supported on TiO 2 , compared to YSZ or SiO 2 , whereas CeO 2 - and Al 2 O 3 -
supported catalysts exhibit intermediate performance. Optimal results were obtained over the 5%Ru/TiO 2 catalyst, which is able to completely and selectively
convert CO at temperatures around 230 o C. Addition of water vapour in the feed does not affect CO hydrogenation but shifts the CO 2 conversion curve toward
higher temperatures, thereby further improving the performance of this catalyst for the title reaction. Long-term stability tests conducted under realistic reaction
conditions show that the 5%Ru/TiO 2 catalyst is very stable and, therefore, is a promising candidate for use in the selective methanation of CO for fuel cell
applications.
Justification for acceptance
The preferential oxidation of CO (PROX) has been studied for the reduction of CO levels by many investigators. However, this approach requires the
addition of O 2 in the hydrogen-rich gas streams, which may give rise to various problems, related to reduced hydrogen yield, dilution, safety and restrictions in
the operating parameters. Thus, CO methanation has been proposed as an alternative purification step.
480 Investigation of total oxidation of toluene over Al 2 O 3 -supported composite metal oxide catalysts
Saleh M. Saqer, Dimitris I. Kondarides, Xenophon E.Verykios *
Department of Chemical Engineering, University of Patras, Greece
*Corresponding author. Tel/Fax: +302610991527, e-mail: salehsaqer@chemeng.upatras.gr
Background
Volatile organic compounds (VOCs) present at low concentrations in industrial waste streams are considered as significant air pollutants due to their toxic
and malodorous nature, as well as their contribution to the formation of photochemical smog. Catalytic combustion over supported noble metal catalysts provides
an effective method for the elimination of VOCs in exhaust gases and this technology seems to be able to satisfy strict emission standards. Efforts in this field are
currently directed toward the development of cheaper, noble metal-free catalytic materials characterized by high activity at low temperatures and long-term
stability under reaction conditions.
Results
The catalytic oxidation of toluene has been investigated over single and composite metal oxide catalysts supported on -Al 2 O 3 . Catalysts were synthesized with
the impregnation method and were characterized with respect to their specific surface area (BET method), crystalline mode and mean crystallite size (XRD
technique), as well as with respect to their reducibility (temperature programmed reduction with H 2 or CO). The effects of the nature, loading and composition of
catalytic materials on their performance for VOC combustion has been investigated in the temperature range of 100-500 o C, using a feed composition consisting
of 0.1% toluene in air. Optimal results were obtained over Al 2 O 3 -supported CuO, CeO 2 , MnO 2 catalysts and their mixtures. For certain metal oxide combinations,
e.g., 10%CuO-60%MnO 2 , 20%CuO-70%CeO 2 and 30%MnO 2 -50%CeO 2 , activity was found to be comparable to that of supported noble metal catalysts.
Measurements of reaction rates under differential reaction conditions showed that specific activity of these materials was up to one order of magnitude higher,
compared to that of the corresponding single metal oxides, implying that a synergistic effect is operable. Results of XRD experiments did not show formation of
new phases, but mixed oxide catalysts were found to exhibit a higher reducibility compared to catalysts consisting of the corresponding single metal oxides.
Justification for acceptance
Results of the present study show that the catalytic performance of certain Al 2 O 3 -supported composite metal oxide catalysts is comparable to that of conventional
supported noble metal catalysts. These materials could provide the basis for the development of cost-effective catalysts for combustion of VOCs present in waste
gas streams.

484 Commercial Application of Catalytic Combustion Treatment Technology for Waste Gases
from Wastewater Treatment System in Petrochemical Enterprises
Chen Yuxiang, Liu Zhongsheng, Wang Xin, Wang Xuehai
Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, China, 113001
Corresponding author. Tel: +86 0413 6389529, Fax : +86 0413 6428097, e-mail: chenyuxiang @fripp.com.cn
Background
The pollutants discharged from oil separator, floatation tanks, etc mainly contain volatile organic compounds with concentrations varied from several thousands
to tens thousands mg/m 3 , and minor amounts of sulfides and ammonia, etc, which are high concentration, badly smell and toxicity, and very harmful to the
human health. Some enterprises had been complained by employee and resident for air pollution from wastewater treatment system in petrochemical enterprises,
which greatly damaged enterprise image.
Results
To dispose the exhaust gases as mentioned above, Fushun Research Institute of Petroleum and Petrochemicals (FRIPP) developed the process “desulfurization
and total hydrocarbon concentration counterpoise - catalytic combustion” and matching WSH-1 catalytic combustion catalysts. This technology has been applied
in six petrochemical enterprises, in which five belong to SINOPEC and one belongs to CNPC. All these units now run well. The first used WSH-1 catalytic
combustion catalysts have been using for nearly two years with good activity. After purified, the removal of non-methane total hydrocarbon (NTHC) was greater
than 95%, and the removal of benzene, toluene, xylene was greater than 99%, and benzene, toluene, xylene, and NTHC of the effluent gases met national
emission standard of “Integrated emission standard of atmosphere pollutant” (GB16297-1996) benzene 12 mg/m 3 toluene 40 mg/m 3 xylene 70
mg/m 3 NTHC 120 mg/m 3 . The commercial unit had the advantage of up-to-date auto-control system, simple operation and low energy consumption. The
technology is being promoted in petrochemical systems.
Justification for acceptance
The technology offers a new method for treating waste gases from wastewater treatment system in petrochemical enterprises, which is beneficial for
reducing diseases arising by these waste gases, improving surrounding atmosphere quality, and gaining good society and environment benefit.
References
[1] Skoglundh M, LÊwendahl L O, Ottersted J E. Appl Catal 77( 1991) 9
[2] Kim H S, Kim T W, Koh H L, Lee S H, Min B R. Appl Catal A 280( 2005) 125
486 Optimal hydrocarbon selection for selective N 2 O reduction over FeZSM-5
Miguel A.G. Hevia a and Javier Pérez Ramírez a,b, *
a Institute of Chemical Research of Catalonia, Avinguda Països Catalans 16, 43007 Tarragona, Spain.
b Catalan Institution for Research and Advanced Studies, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
*Corresponding author. Tel: +34 977 920236, Fax : +34 977 920224, e-mail: jperez@iciq.es
Background
Reducing agents are required to accomplish the abatement of N 2 O at relatively low temperatures (

POSTER
ABSTRACTS
Renewables

107 Catalytic conversion of cellulose over carbon supported tungsten carbide catalysts
Na Ji a , Mingyuan Zheng a , Aiqin Wang a , Xiaodong Wang a , Tao Zhang a, *, Jingguang G. Chen b, *
a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, CAS, Dalian 116023, China
b Department of Chemical Engineering, CCST, University of Delaware, Newark, DE 19716, USA
*Corresponding author. Tel: +86 411 84379015 a , 302 831 0642 b , Fax: +86 411 84691570 a , 302 831 2085 b , e-mail: taozhang@dicp.ac.cn, jgchen@udel.edu
Background
Cellulose is the most abundant renewable resource and the conversion of cellulose into high valued chemicals or fuels is therefore of significant importance.
Previously, Pt-group metals were found to be active for the conversion of cellulose [1-2] . In the present work, we for the first time reported that carbonsupported
tungstencarbidescouldactasefficientcatalystsfortheconversionofcellulose.
Results
The catalysts with W loading of 30 wt% were prepared by incipient wetness impregnation followed by carbothermal hydrogen reduction at 1073 K. The
conversion reaction of cellulose (Merck, microcrystalline) was carried out in a stainless-steel autoclave (100 ml) typically at 463 K and 5 MPa H 2 at RT for 24
hours. For each reaction, 0.5 g cellulose, 0.15 g catalyst and 50 ml water were put into the reactor, and stirred at a rate of 1000 r/min. After the reaction, the
reactant mixtures were centrifuged, and the filtered solution was analyzed by HPLC. The results showed that the W 2 C/MWCNTs-COOH (carboxylfunctionalized
multi-walled carbon nanotubes) catalyst had the best catalytic activity with a hexitol yield of 21%, which was comparable to the precious metal
catalyst Pt/Al 2 O 3 of 30% yield. The W 2 C/AC (activated carbon) catalyst was less efficient with a yield of 13%, followed by W 2 C/CB (carbon black) and
W 2 C/ACF (activated carbon fiber) with a yield of 7% and 4%, respectively. Characterization results showed that the W 2 C phase was the possible active phase.
Justification for acceptance
This research was about the catalysis in a sustainable fine chemical industry from renewable resources. It was found for the first time that with inexpensive
tungsten carbides as the catalyst, the cellulose could be converted into high valuable hexitols under relatively mild conditions.
References
[1] A. Fukuoka, P. L. Dhepe, Angew. Chem. Int. Ed. 45 (2006) 5161–5163.
[2] Ning Yan, Yuan Kou et al. J. AM. CHEM. SOC. 128 (2006) 8714-8715
198 Effect of carbon-nanotube support on Ru-Mn-based Fischer-Tropsch catalysts
for hydrocarbon productions from biomass-derived synthesis gas
K. Murata , *, K. Okabe, I. Takahara, M. Inaba andL. Yanyong
National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8565, Japan
*Corresponding author. Tel. and Fax.:+81-29-861-4776, E-mail: kazu-murata@aist.go.jp
Background
The BTL (biomass to liquid) process is one of the most promising ways to utilize biomass in remote and/or local areas to form sulfur-free transportation fuels [1].
A direct liquid hydrocarbon (C5-C20) production by the FT synthesis is one of the key technologies required for the small-scale BTL process. In this context, Rubased
catalysts will be one of candidates [2], because of their excellent catalytic activities as well as a small-scale catalyst requirement. In fact, we have already
reported that Ru-Mn/-Al 2 O 3 was effective under slurry-phase FT conditions [3]. In this paper, effects of carbon-nanotube support on the control of hydrocarbon
selectivity were investigated.
Results
The Ru-Mn/C catalyst was prepared by impregnating RuCl 3 and Mn(NO 3 ) 2 .6H 2 O with carbon-nanotube (tube), graphite and activated carbons, followed by
dryness at 373K and calcination at 573K for 5 hours. The ruthenium loading was 5wt%. After hydrogenation of catalyst (0.5g), the catalyst and 20 cm 3 of
hexadecane were introduced into an autoclave (100 cm 3 ) under an inert atmosphere, and 30cm 3 /min of synthesis gas (2MPa, H 2 /CO/N 2 = 60/30/10(vol.%)) was
bubbled into the slurry and reaction was carried out at 533K for 33 hours. During reaction, the gas phase was analyzed by online FID and TCD-GCs, in which
inorganic gases and C1-C4 hydrocarbons were determined. After reaction, the contents of C5+ hydrocarbons in the slurry were determined separately by another
FID GC and chain growth probability () was estimated. In each carbon support, the CO conversion was by 5-9% lower than that of -Al 2 O 3 support previously
reported, but the C5+ selectivity was comparable. CH 4 selectivity was 5.7-11.5%, higher than that of -Al 2 O 3 . Ru/carbon catalyst was found to be improved by
Mn addition and the activity became comparable to that of -Al 2 O 3 support. FID-GC analysis of liquid hydrocarbons after reaction showed the hydrocarbon
distributions obeying Anderson-Schulz-Flory equation. The values in tube and graphite were 0.82-0.83, a bit lower than those of activated carbons. For
Ru/Tube catalyst, the catalytic activity depended on Ru and Mn concentration. The CO conversion increased with the increase in Ru concentration, while C5+
selectivity decreased. In these cases, Ru particle sizes increased from 10 nm to 30 nm. The CO conversion increased with Mn concentration up to 5wt% and
thereafter slightly decreased, whereas C5+ selectivity decreased and then slightly increased at above 5wt% Mn concentration. Over Ru-Mn/tube catalyst, the
conversion at 533K was by 10% higher than that at 493K, while C5+ selectivity was 5% lower. The CO conversion at 533K remained constant after 33 hours.
From these investigations, Ru-Mn/tube system was found to be a promising candidate for FT catalyst for middle distillate production. So, further study is now in
progress to improve catalyst performances and to elucidate the Mn effect.
References
[1]. H. W. Lueke, Erdoel, Erdgas, Kohle, 121 (2005) 3.
[2]. T. Yoshinari, F. Suganuma, T. Sera, J. Jap. Pet. Inst., 32 (1989) 248.
[3]. M. Nurunnabi, K. Murata, K. Okabe, M. Inaba, I. Takahara, Catal. Commun. 8 (2007) 1531

200 Nanocomposite heterogeneous catalysts for biodiesel production
L. Sherry* and J.A. Sullivan
UCD School of Chemistry and Chemical Biology, Belfield, Dublin 4, Ireland,
Corresponding Author. Tel:+353 1 7162135, Fax: +353 1 716 2127, e-mail: linda.sherry@ucd.ie
Background
Biodiesel is an alternative fuel which, in the ideal case, can be considered to be a CO 2 -neutral fuel [1]. Production of this renewable fuel (which consists of fatty
acid methyl esters (FAME)) requires the transesterification of vegetable/animal fats with an alcohol using either an acidic or basic catalyst. Although NaOH (aq)
solutions have proven to be active catalysts, there are several problems with the homogeneous alkaline catalysed approach[2] which could be mitigated by the use
of a solid catalyst. Therefore, we plan to synthesize and characterise a number of solid materials which will contain well defined, separated and characterised
acidic and basic sites, and analyse their activities in the production of FAME.
Results
Mesoporous support materials such as MCM-41 and SBA-15 have been synthesised and characterised using XRD, TEM, BET surface area measurements and
FTIR. The surface of these materials has subsequently been modified to allow chemical tethering of acidic and basic species onto the support. The synthesised
solid acids and bases have been characterised using TEM, FTIR, XRD, SEM-EDAX and TPD of adsorbed probe molecules (NH 3 and CO 2 ). The catalysts were
then analysed for their activity in promoting model esterification and transesterification reactions with analysis of the products by 1 H NMR. Finally, attempts
have also been made to design and synthesise a hybrid material, which contains well separated and characterised acidic and basic sites.
Justification for acceptance
Significant amounts of the anthropogenic CO 2 added to the atmosphere are due to automotive applications. Running such applications on a more carbon-neutral
basis would obviously have an impact on these emissions, making the implementation of sustainable automotive fuels an urgent environmental issue. Given
synthesis from both waste and specifically cultured fats and oils, biodiesel is a perfect example of such a fuel and within the past year the number of articles in
the environmental catalysis literature involved in the heterogeneous production of biodiesel has dramatically increased e.g. [3, 4].
References
[1] A.A. Kiss, A.C. Dimian, G. Rothenberg, Adv. Synth. Catal. 348 (2006) 75.
[2] M. Di Serio, M. Cozzolino, M. Giordano, R. Tesser, P. Patrono, E. Santacesaria, Ind. Eng.Chem. Res. 46 (2007), 6379.
[3] J.L. Shumaker, C. Crofcheck, S.A. Tackett, E. Santillan-Jimenez, T. Morgan, Y. Ji, M.Crocker, T.J.Toops, App. Catal, B In Press,
doi:10.1016/j.apcatb.2008.01.010.
[4] M.L. Granados, M.D.Z. Poves, D.M. Alonso, R. Mariscal, F.C. Galisteo, R.Moreno-Tost, J. Santamaría, J.L.G. Fierro, App. Catal, B 73 (2007) 317.
223 Methanolysis of frying oil catalyzed by papaya lipase for biodiesel fuel synthesis
P. Porntippa a, * , P. Jakkrite b
a Department of Chemistry, Faculty of Science and Technology, Uttaradit Rajabhat University, Thailand
b Department of Public Health, Faculty of Science and Technology, Uttaradit Rajabhat University, Thailand
* Corresponding author. Tel: +66 55 411096 ext 1308, Fax : +66 55 411096 ext 1312, e-mail: pimung@hotmail.com
Background
Biodiesel comprises long-chain fatty acid methyl ester. The property of biodiesel is better than petroleum fuel [1]. Biodiesel can be synthesized by methanolysis
of triglycerides which are catalyzed by chemical catalysis or biocatalyst. Acid- or alkali-catalyzed methanolysis has some disadvantages. Lipase-catalyzed
methanolysis have become more attractive because enzymatic catalysis has overcome the drawbacks of chemical catalysis. In the present, the cost of plant oil is
high so the production of biodiesel from frying oil is worthier than vegetable oil. This research indicated that papaya lipase would be a useful in inexpensieve
biocatalyst for biodiesel production from frying oil.
Results
The fatty acid composition of frying oil were determined by acid-catalyzed methanolysis. Papaya lipase obtained by incision of unripe fruit from several sources
of papaya trees was used as a biocatalyst. Improvement activity of lipase was investigated by immersion lipase in isopropanol at various time. Methanolysis
reaction was studied using substrate mixture composed of frying oil 1 mmol and dried methanol 3 mmol. The reaction was started by adding 1 g of lipase and
performed at 37 o C with shaking at 200 rpm for 24 hours. The products formed from the reaction were analyzed by GC-MS.
Frying oil composed of 0.60% lauric acid, 1.23% myristic acid, 47.22% palmitic acid, 0.38% palmitoleic acid, 5.84% stearic acid, 43.00% oleic acid, 1.24%
linoleic acid and 0.49% eicosanoic acid. The precipitate of papaya latex showed hydrolysis activity of frying oil at 30.2 4.4 unit/gram of fresh latex. The
activity of enzyme was improved through immersing enzyme with isopropanol for 3 hours, 6 hours and 24 hours. Lipase immersed with isopropanol catalyzed
hydrolysis of frying oil better than those from native of 31 folds, 24 folds and 18 folds for immersion 3 hours, 6 hours and 24 hours, respectively. Papaya latex
lipase immersed with isopropanol for 3 hours could catalyzed methanolysis of frying oil which produced methyl ester 70%. This can be explained that immersed
papaya lipase was surrounded by isopropanol which can act as an intermediate solvent for better solubility of frying oil and methanol. An addition of 1% (w/w)
of water to the enzyme slightly increased the yield of methyl ester after 24 hours of reaction time since this added water make the enzyme had optimum water
activity (0.208). When the reaction was carried out at various mmol ratio of frying oil and dried methanol, the highest content of methyl ester (80%) was obtained
from the methanolysis using a 1 : 2 mmol ratio of frying oil : dried methanol. This may be explained that increasing of methanol led to lesser dissolution of
triglyceride in frying oil and then the entering of triglyceride into active site of enzyme would decrease.
Justification for acceptance
This research investigate the synthesis of alternative clean energy (biodiesel) using biocatalyst from plant which leading to decreasing the greenhouse effect and
global warming.
References
[1] S.J. Clark, L. Wangner, M.D. Schrock, P.G. Piennaar, J. Am. Oil Chem. Soc. 51 (1984) 1632.

234 Catalytic conversion of glycerol to value-added products
A. Bienholz, P. Claus*
Technische Universität Darmstadt, Petersenstr. 20, D-64285 Darmstadt, Germany.
*Tel: +49 6151 165369, Fax: + 49 6151 4788, e-mail: claus@ct.chemie.tu-darmstadt.de
Background
Due to the lack of fossile raw materials in the future the industrial society has to develop technologies and processes to utilize more effectively renewable
biomass resources which are available to produce chemicals and energy. One of these processes will be the hydrogenolysis of glycerol, the byproduct of the
production of biodiesel from vegetable oils, to value-added products like propylene glycol. Propylene glycol plays a significant role in industry because of its
wide range of practical applications. It is found in such diverse products as antifreeze/coolants, heat transfer fluids, cosmetics, pharmaceuticals, polyesters and
polyurethanes.
Results
Hydrogenolysis of glycerol to propylene glycol was performed in a stainless steel reactor pressurized with hydrogen to the necessary pressure and heated to the
reaction temperature. The samples were taken at desired time intervals and analysed with a Hewlett-Packard 6890 gas chromatograph equipped with a DB-WAX
GC column and a flame ionization detector. The effects of temperature, hydrogen pressure and choice of catalyst were evaluated. While platinum catalysts
showed low reactivities, a high conversion was reached when using ruthenium based catalysts. Ruthenium catalysts showed low selectivities towards propylene
glycol due to competitive hydrogenolysis of C-C and C-O bonds leading to excessive degradation of glycerol to form lower alcohols or gases. On the other hand,
copper based catalysts exhibited compared to ruthenium catalysts lower reactivity but higher selectivity towards propanediols with little selectivity towards
ethylene glycol and other degradation byproducts. Dasari et al [1] proposed a two-step mechanism for the hydrogenolysis of glycerol consisting of a dehydration
of glycerol to hydroxyacetone which further reacts with hydrogen to form propylene glycol. Therefore bifunctional catalysts with acid sides were used to promote
the dehydration of glycerol.
Justification for acceptance
There are only a few literature reports about the conversion of glycerol to propylene glycol with heterogenous catalysts. But these processes suffer from several
drawbacks like low selectivities towards the desired products, high hydrogen pressures and temperatures, diluted glycerol solutions and catalyst deactivation.
Therefore further investigation to optimize the catalysts and process parameters has to be done.
[1] M. Dasari, P. Kiatsimkul, W. Sutterlin, G. Suppes, Applied Catalysis A: General 281 (2005) 225-231.
252 Production of Ethers of Glycerol: Side-Product of Biodiesel Production
N. Ozbay a , N. Oktar a *, G. Dogu a , T. Dogu b
a Chemical Engineering Department, Gazi University, Maltepe, Ankara, Turkey
b Chemical Engineering Department, METU, Ankara, Turkey
*Corresponding author. Tel:+90 312 2317400/2556, Fax :+90 312 2308434, e-mail:nurayoktar@gazi.edu.tr
Background
As a by-product of triglycerides’ transesterification with methanol for the biodiesel (a mixture of methyl esters) production, 1 mol of glycerol is produced for
every 3 mols of methyl esters. Further growth of biodiesel market would result in a major glycerol surplus problem [1]. Glycerol can’t be added to fuel directly,
because at high temperatures it polymerizes - and thereby clogs the engine - and it is partly oxidized to toxic acrolein [2]. One alternative is to etherify glycerol
with either alcohols or alkenes and to produce oxygenated compounds having good burning characteristics [3].
Results
The aim of the present study is to etherify glycerol by tert-butyl alcohol (TBA) to produce high quality motor vehicle fuels and fuel additives. The liquid phase
etherification reaction of TBA with glycerol was investigated in a continuous flow reactor using commercial strong acidic ion-exchange resin catalysts namely,
Amberlyst-15 and Amberlyst-16. Effects of feed composition, catalyst amount and reaction temperature on the product distribution were investigated. TBA to
glycerol ratio was changed in the range between 4:1 and 6:1.The samples of reactants and reaction products were analysed by gas chromatography. Analyses
were carried out using HP Innowax column. Product distributions indicated the formation of mono-ethers, di-ethers and tri-ether. Significant increase in
conversion was observed with an increase in temperature, space time and TBA to glycerol ratio in the feed. No significant change was observed in the selectivity
of mono-, di- and tri- ethers with increasing temperature and space time. Selectivity of mono-ethers were about 0.77, 0.79 and 0.79, selectivity of di-ethers were
about 0.26, 0.20 and 0.20, for a feed stream containing TBA to glycerol ratio of 5:1 for space times of 6, 12 and 18 s g/cm 3 respectively. The results obtained with
Amberlyst-15 were compared with the experimental results obtained using another strong acidic ion-exchange resin, Amberlyst-16.
Justification for acceptance
Production of large quantities of glycerol as a by-product of biodiesel production has a strong potential of creating a major environmental problem. In this study,
it was shown that oxygenated compounds having good burning characteristics can be produced by the etherification reaction of glycerol with TBA over acidic
resin catalysts.
References
[1] R.S. Karinen, A.O.I. Krause, App. Catal. A-Gen 306 (2006) 128.
[2] M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, C.D. Pina, Angew. Chem. Int. Ed 46 (2007) 2.
[3] K. Klepacova´, D. Mravec, M. Bajus, App. Catal. A-Gen 294 (2005) 141.

270 Natural alumosilicates and synthetic zeolites as the catalysts for energy generation
from biomass via low-temperature catalytic pyrolysis
Yu. Kosivtsov a , V. Alfyorov a , A. Sidorov a ,*, M. Sulman a , V. Matveeva a , E. Sulman a , O. Misnikov b , A. Afanasjev b , N. Kumar c and D. Murzin c
a Dept. Biotechnology and Chemistry, Tver TechnicalUniversity, Tver, Russia
b Tver State University, Tver, Russia
c Åbo Akademi University, Turku, Finland
*Corresponding author. Tel/Fax: +74822449317, e-mail: sulman@online.tver.ru
Background
Biomass is an important source of energy in the world. Pyrolysis and gasification are most widely used to intensify the valorization the low-grade raw materials
[1-3]. The use and selection of a suitable catalyst permits to operate at lower temperatures and can provide selectivity towards the desired products, avoiding any
post-process upgrading, thus enhancing the benefit of the process and turning it economically feasible. The aim of the investigations is to study the lowtemperature
pyrolysis of peat (partially renewable bioresource) in the presence of catalytic systems on the basis of natural alumosilicate materials and synthetic
zeolites.
Results
Caoline, bentonite and cambrian clays and clay mergel were used as natural alumosilicates. Synthetic zeolites (H-Beta-25 and H-Mord) were purchased from
"Zeolyst International" (USA)).
Catalytic action of alumosilicate materials was elucidated through their influence on the total amount of the gaseous mixture produced during pyrolysis of peat,
on the concentration of hydrocarbons (methane, ethane, ethylene, propane) in gaseous mixtures and on the heat of combustion of combustible gases. The
influence of the temperature was investigated in the range of 410 – 600°.
Preliminary experiments showed that the addition of 2 % of synthetic zeolites and of 30% of natural alumosilicates to peat was optimal. In the presence of
catalysts the amount of hydrocarbons in gaseous mixture noticeably increased. The increase of the heat of combustion of gaseous mixture was due to the
increased content of alkanes and alkenes obtained when alumosilicate materials were used. The average value of the specific heat of combustion was higher
approximately by twofold in comparison with the data obtained for non catalytic process. It was demonstrated that the highest heat of combustion (23.88 MJ/m 3 )
was reached for bentonite clay at 460°C.
Significant distinction in percentage of optimal amount of alumosilicate component of reaction mixture between natural and synthetic alumosilicates was likely
due to the different structures of these substances. Moreover, natural alumosilicates when present in significant amounts in the reaction mixture, besides having a
catalytic function also acted also heat-carriers, considerably increasing the heat conductivity of the mixture, thus promoting more uniform heating.
Justification for acceptance
As a result of the performed work, it was established that the application of synthetic and natural alumosilicates allowed decreasing the temperature of peat
pyrolysis from 700°C (average temperature of non catalytic pyrolysis) to 460°C. Bentonite clay revealed the highest catalytic activity in peat pyrolysis at 30%
weight concentration.
References
[1] A. Demirbas, Energy Sources 26 (2004) 715.
[2] P. Lv, J. Chang, T. Wang, C. Wu, , Energy and Fuels 18 (2004) 1865.
[3] J. Adam, M. Blazso, E. Meszaros, M. Stöcker, M.H. Nilsen, A. Bouzga, J.E. Hustad, M. Grønli, G. Øye, Fuel 84 (2005) 1494.
289 Bio-fuel synthesis in transesterification of castor oil using heteropolyacid-based solid catalysts
A. Ziba*, T. Kasza, L. Matachowski, A. Pacua, A. Bielaski, E. Serwicka-Bahranowska, A. Drelinkiewicz
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, 30-239 Kraków, Niezapominajek 8, Poland
*Corresponding author. Tel: + 48 12 6395205, Fax : = 48 12 4251923, e-mail: nczieba@cyf-kr.edu.pl
Background
Biodiesel fuel (fatty acid methyl esters) is a renewable alternative fuel produced via transesterification of triglycerides found in vegetable oils with methanol,
catalysed by homogeneous bases and acids. Environmental and economical reasons justify the interest in replacing homogeneous catalysts by the solid ones. Acid
catalysts able to catalyze transesterification using cheaper waste oils are the perspective ones.
Results
This paper reports the comparative study for testing the activity of solid heteropolyacid-based catalysts (HPA) in the transesterification of castor oil to methyl
esters (FAME) with methanol (1 : 29 molar ratio) at 60 0 C under atmospheric pressure using GC and HPLC analyses. Catalytic performance of three series of
catalysts, ZrO 2 -supported H 4 SiW 12 O 40 (9 – 37 wt % HPA) two kinds of montmorillonites-supported H 3 PW 12 O 40 (12 – 51 wt % HPA) and acidic cesium salts
Cs 2.5 H 0.5 PW 12 O 40 and Cs 2 HPW 12 O 40 was compared. Both Cs-salts were prepared by various methods (HPA reacted with CsCl or Cs 2 CO 3 ) giving 2 samples of
different structural properties, acidity, specific surface area and porosity. Morphological and structural properties of catalysts were characterized by BET, XRD
and SEM techniques, acidic properties by FTIR and gas flow-through microcalorimetry methods. For both, ZrO 2 and montmorillonite supported HPA-catalysts
the optimum HPA loading (12-14 wt %) was established. Below this loading they acted as purely heterogeneous catalysts, without leaching the HPA during the
catalytic tests. Higher loading giving the crystalline forms of HPA in both supports resulted in partial leaching of HPA during the transesterification test and
finally “mixed” system operating as homo and heterogenous one. All the Cs-salts of H 3 PW 12 O 4 showed superior catalytic performance compared to those of solid
HPA-supported catalysts. Activity of differently prepared Cs 2 HPW 12 O 40 catalysts quite well correlated to the size of colloidal catalysts particles formed in contact
with methanol under the catalytic test whereas there was no clear correlation to the specific surface area and acidity of Cs-salts.
Justification for acceptance
Biodiesel (fatty acid methyl esters FAME) is a new energy resources non-toxic and biodegradable alternative fuel compared to petroleum diesel. Conventional
technology of FAME synthesis using homogeneous alkaline catalysts (Na, K hydroxide) has several drawbacks like hydrolysis, soap formation and difficult
FAME separation. Therefore studies are undertaken to find heterogeneous catalysts and in particular acid ones seem to be promising catalysts.
Acknowledgement A. Ziba acknowledges a Ph.D. grant of the Polish Academy of Sciences

309 Activity and durability of solid acid catalysts for the esterification of free fatty acids with methanol in vegetable oils.
Frederic C. Meunier 1 ,*Jun Ni 2 , David Rooney 2 ,
1 Laboratoire Catalyse et Spectrochimie, ENSICaen-University of Caen - CNRS, Caen, France.
2School of Chemistry & Chemical Engineering, Queen’s University Belfast, UK.
*Corresponding author. E-mail: frederic.meunier@ensicaen.fr
Background
The transesterification of the triglycerides contained in vegetable oil with methanol to yield fatty acid methyl ester (FAME) is homogeneously catalysed by
NaOH and KOH bases. Free fatty acids (FFA) are a poison to the catalyst, and also lead to soap formation. The FFA content is low ( 0.25 m 2 /g were prepared by impregnation and
catalytic activation using a catalyst support starting powder of a BET surface of at least > 20 m 2 /g, that can be tailor-made by applying the exo-templating
procedure followed by doping with a sufficiently high loading of NiO. In case of a MgO-NiO catalytic layer, a complete conversion of the tar model compound
naphthalene was achieved at 800°C in the absence of H 2 S applying a face velocity of 90 m/h. Using MgO-Al 2 O 3 -NiO as catalytic layer with a higher monolithic
BET surface of 0.91 m 2 /g, an increase of the naphthalene conversion from 49% to 66% was achieved in the presence of 100 ppmV H 2 S. After scale up of the
catalytic activation procedure to filter elements of commercial size, comparable naphthalene conversions of 97% in the absence and 58% in the presence of H 2 S
were found. The measured differential pressure of 54.9 mbar under operating conditions is acceptable. A comparison of the corresponding WHSV value with that
of the catalytically most active catalyst in previous work [1] indicates that a further optimization of the catalytic performance is technically feasible to provide a
comparably active tar reforming catalytic filter element prototype exhibiting complete naphthalene conversion at 800°C in the presence of 100 ppmV H 2 S.
Justification for acceptance
Catalytic activation of silicon carbide filter elements based on impregnation techniques is presented as new and simplified manufacturing method compared to a
previously described fixed bed catalyst integration method [1] to prepare comparably active tar reforming catalytic filter elements.
References
[1] M. Nacken, L. Ma, K. Engelen, S. Heidenreich, G. V. Baron, Ind. Eng. Chem. Res. 46 (2007) 1945.

370
A novel catalyst support for Fischer-Tropsch synthesis Performance of Cobalt-Loaded Powdered Diamond Catalysis
Toshimitsu Suzuki,* Tetsushi Kitano, Atsuo Nishizawa, Takanori Miyake
Department of Chemical Engineering, Kansai University, Suita Osaka 564-8680 Japan
*Corresponding author. Tel +81 6 63680865, Fax +81 6 63888869, e-mail tsuzuki@ipcku.kansai-u.ac.jp
BackGround
In view of the effective utilization of natural gas and production of ultra clean fuel, Fischer-Tropsch (FT) synthesis has again attracted a large number of
researchers. In the 1980’s one step production of gasoline from synthesis gas has been focused. However, currently 2-step processes are mainly developed;
namely synthesis of long chain alkanes, followed by hydro-cracking of them to kerosene and gas oil fractions. Objective of this paper is to understand the effect
of support material of Co-loaded FT catalyst, of which support has no pore structures, such as spherical silica and fine powdered diamond.
Results
Fine powdered diamond was found to behave as an effective support material of several catalytic reactions 1) . This paper deals with application of Co-loaded fine
powdered diamond catalyst for the FT synthesis. Cobalt salts were loaded on pre-oxidized commercial powdered diamond (

405 Transesterification of triglycerides on heterogeneous polymer supported Lewis acid catalysts
N.V. Kramareva*, O.P. Tkachenko, L.M. Kustov
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991Moscow, Leninsky prospect 47, Russian Federation
*Corresponding author. Tel: +7 495 1376617, Fax : +7 495 1372935, e-mail: nkramareva@mail.ru
Background
Biodiesel (fatty acid methyl esters) has become very attractive, because of its environmental benefits and the fact that it is produced from renewable sources.
Recently traditional acid and alkaline catalysts are being replaced by Lewis acid catalysts because of a number benefits provided by Lewis acids (for instance,
homogeneous alkaline catalysts in the transesterification of such types of fats and oils cannot directly be used due to the presence of large amounts of free fatty
acids, and acid catalysts produce hazardous wastes). We prepared and tested as catalysts a range of polymer supported Lewis acid based catalysts with different
metals.
Results
Polymer-based complexes with metals (Zn, Co, Ca, Ni, Sn, and Pb) prepared by different techniques (coprecipitation, adsorption) were tested as catalysts in
transesterification of triglycerides (tributyrin was used as a model oil component). Chitosan, polyaniline, polyethylene glycol were used as carriers for catalysts.
The structure and stability of the complexes were investigated by EXAFS, XPS, IR, and SEM. Catalytic testing revealed a good performance of all the catalysts
for the reaction of transesterification, with Pb -chitosan complexes demonstrating the best catalytic activity, Ni, Sn-complexes demonstrate the activity
comparable with the most active metal. Tributyrin conversion reached 95% for Pb-containing catalysts, and 80% for the Ni-sample, with the selectivity 98%. Sn,
Pb, Ni, Zn, Ca-containing complexes were successfully applied to transesterification of sunflower-seed oil. EXAFS results testify about the catalyst stability
during the catalysis. However, the reaction rate could be increased, for instance, by immobilization of the polymer complex on the surface of macroporous SiO 2 .
In this case, the activity of catalyst increased by a factor of five.
Justification for acceptance
Series of new heterogenized polymer complexes based on Lewis acid metals were prepared and characterized by EXAFS, XPS, IR, and SEM. It was
demonstrated that these complexes are effective and stable catalysts for transesterification of triglycerides (the most active complexes were Pb, Ni, and Sncontaining
complexes).
424 The hydrogenation of vegetable oil: Low trans formation.
S.Mc Ardle 2 , J.J.Leahy 1,2 and T.Curtin 1,2 *.
1 Materials and Surface Science Institute,
2 Chemical and Environmental Science Department, University of Limerick, Ireland.
*Corresponding author. Tel: +353 61 202981, Fax: +353 61 202568, e-mail: teresa.curtin@ul.ie
Background
Hydrogenation of vegetable oil is a major processing step in the fats and oils industry. The process is a complex series of parallel reactions occurring in a batch
reactor system using a nickel catalyst. There are several disadvantages associated with the process. Large quantities of wastes are generated due to catalyst
deactivation and difficulties are encountered with catalyst removal following hydrogenation. In addition, during the process unwanted trans fatty acids are
produced. In recent years, major concerns have been raised because it is clear that consumption of trans fatty acids contribute to coronary heart disease.
Therefore, recently there has been a big drive in efforts to overcome these problems.
Results
This work reports on the hydrogenation of sunflower oil over novel supported catalysts. Sunflower oil was hydrogenated in a batch reactor using solid catalysts
under a variety of conditions (temperature, H 2 pressure etc..). The changes in the iodine value, fatty acid composition and trans fatty acid content during the
hydrogenation process were investigated. The work focuses on bimetallic NiPt catalysts supported on large pore silica supports. An innovative approach was
taken in preparing the catalysts using a surface redox reaction (Srr) technique. The catalyst proved to be highly active for the hydrogenation process and more
importantly resulted in a significant reduction in the trans content of the oil. The trans fatty acid content was reduced from 30% (using the conventional Ni
based catalysts) down to 5% trans content using the bimetallic catalyst. This important result was achieved using a combination of reaction conditions and novel
catalyst. Geometric and electronic effects due to the two supported metals were used to explain the reduced trans formation. A range of techniques were used to
characterise the catalysts, including dispersion measurements and transmission electron spectroscopy (both dark field and bright field imaging).
Justification for acceptance
The process presented is a significant improvement in terms of current industrial state of the art. The current catalyst, which is composed of 22wt% Ni, can be
replaced by a supported catalyst containing less that 1wt% Ni and less than 2wt% Pt. This facilitates the possibility of supporting this catalyst onto a membrane
type reactor that can offer the possibility of designing a continuous hydrogenation process.

427 Investigation of hydrotreating of vegetable oil-gas oil mixtures
J. Hancsók*, M. Krár, T. Kasza, Cs. Tóth
Pannon University, Dept. of Hydrocarbon and Coal Processing, Hungary, H-8201 Veszprém, P.O. Box 158.
*Corresponding author. Phone: +36 88 624870, Fax. +36 88 624520, e-mail: hancsokj@almos.uni-pannon.hu
Background
In the recent years research, development and use of biofuels has emerged into focus caused by saving crude oil reserves and environmental protection reasons.
Biodiesel (vegetable oil fatty acid methyl ester) suitable for the operation of Diesel engines has many disadvantages during its application: low heat- and
oxidation stability (low storage stability) caused by the double bonds in its molecular structure, ability for hydrolysis (danger of corrosion) caused by the ester
bonds, not adequate viscosity and cold filter plugging point etc. Thus it is necessary to find novel conversion processes that are capable to produce fuels and its
blendstocks from vegetable oils with better quality compared to biodiesel. One of the possible solutions is the catalytic conversion of vegetable oils mixed in
straight run gas oil. The paper shows the main results of the experiments of the above mentioned catalytic conversion.
Results
Quality improvement possibilities of a straight run gas oil and 5, 8, 12% rapeseed oil containing straight run gas oil was investigated on NiMo,P/Al 2 O 3 catalyst.
Experiments were carried out in a reactor system with 100 cm 3 effective volume and the reactor was operated without back-mixing. The effect of process
parameters (T: 330-380 °C; p: 40-60 bar; LHSV: 1.0-4.0 h -1 ; H 2 /hydrocarbon: 400-800 cm 3 H 2 gas/ cm 3 liquid feed) on the liquid product yield and its quality
properties (viscosity, sulphur- and nitrogen content, aromatic content, acid number etc.) was investigated. Based on our results we established that quality
properties of the products improved significantly compared to that of the feedstock. Under expediently selected process parameters (T: 350-360 °C; p: 50-60 bar;
LHSV: 1.5-3.0 h -1 ; H 2 / liquid feed volume ratio: 600 cm 3 /m 3 ) sulphur- and nitrogen content of the liquid product fractions above 200 °C boiling point (diesel
fuels) were lower than 10 mg/kg and their cetane number was significantly higher (53-55) than the limit (min. 51) of the standard (EN 590:2004). The above
mentioned is the result of the high paraffin content of the products, mainly formed during the catalytic conversion of vegetable oil. Based on the analytical tests
of the products we established that paraffins are formed – apart from the saturation of double bonds – by hydrodeoxygenation (H 2 O formation) and in lower
amount by decarboxylation and decarbonylation.
Justification of acceptance
Disadvantageous properties and high cost-price of biodiesel fuels result the need for producing better quality and higher value products from vegetable oils. In
the refineries one of the possible solutions is the catalytic conversion of the mixture of vegetable oil and gas oil to high cetane number, environmental friendly
diesel fuel.
433 Enzymatic transesterification of used frying oils
M. Krár*, S. Kovács, J. Hancsók
Pannon University, Dept. of Hydrocarbon and Coal Processing, Hungary, H-8201 Veszprém, P.O. Box 158.
*Corresponding author. Phone: +36 88 624870, Fax. +36 88 624520, e-mail: krarm@almos.uni-pannon.hu
Background
Environmental, human biological and economical reasons forced the research of converting used frying oils (dangerous waste) to less harmful but much higher
value products. A possible way is the conversion of used frying oils to fuels and their application in Diesel engines either in themselves or as blendstocks for
diesel fuels. Alkali catalyzed conversion to biodiesel was studied in detail but there are only a few results published about enzymatic transesterifcation. Used
frying oils are available throughout the world, independently of geographical location, climatic or relief conditions. Their characteristics, however, can
significantly differ and their fatty acid composition is determined by the vegetable oil from which the waste frying oil formed. The effect of these conditions on
the enzyme-catalyzed transesterification should therefore be studied in order to see the interactions.
Results
In the research work waste frying oils were first properly pre-treated then transesterified in the presence of Novozym 435 enzyme catalyst under different process
conditions. Characteristics of the used frying oil methyl esters were evaluated according to the requirements of EN 14214 standard. Our experimental results
indicated that enzyme-catalyzed transeterification is suitable for the conversion of used frying oils. We have found proper combination of process conditions
(pressure: atmospheric, temperature: 50°C; methanol to triglyceride molar ratio: 4:1; reaction time: 16 hours) resulting in high (>90%) yield of monoesters.
Monoester content of the product mixtures highly depended on the conditions of used frying oil pre-treatment while product qualities were influenced by the fatty
acid composition of the expediently refined frying oil. We clearly established that the best results through the enzymatic transesterification were obtained with
used frying oils containing the highest amount (>88%) of oleic acid.
Justification for acceptance
Price of vegetable oils (rapeseed oil, sunflower oil) applied as feedstock for biodiesel production has nearly doubled in the last year, resulting in the rise of the
cost-price of biodiesel. Thus, the investigation of using cheaper feedstock (e.g.: used frying oil) has become more important.

443 Esterification of glycerol with acetic acid over heteropolyacids encaged in USY zeolite
P. Ferreira a , I.M. Fonseca b , A.M. Ramos b , J. Vital b , J.E. Castanheiro a *
a CQE, Departamento de Química, Universidade de Évora, 7000-671 Évora, Portugal
b REQUIMTE/CQFB, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
Corresponding author. Tel.: +351 266745311; fax.: +351 266744971; E-mail address: jefc@uevora.pt
Background
Glycerol is one of the renewable resources and it is obtained as a by-product in hydrolysis of fat, soap-manufacturing process and production of biodiesel. The esterification of
glycerol with acetic acid can be a good alternative for the glycerol transformation. The mono, di and triacetyl esters have great industrial applications. The triacetylated
derivative has applications going from cosmetics to fuel additive [1], while the mono and diacetylated esters have applications in cryogenics and as raw material for production
of biodegradable polyesters. Heteropolyacids with Keggin-type structure (HPA) have higher Brönsted acidity than the conventional solids acids. The heteropolyacid supported
on solids have many advantages over homogenous catalysts, such as their easy separation from liquid products [2]. In this work, we studied the esterification of glycerol with
acetic acid catalysed by heteropolyacids encaged in USY zeolite.
Results
The preparation of the encaged heteropolyacid catalyst by the synthesis of dodecamolibdophosphoric acid (HPMo) in the supercages of Y-type zeolite, it was performed
according to the procedure of S. Mukai et al [3]. The FTIR spectrum of samples exhibits the bands at 954~975 cm -1 , 869-880 cm -1 and 785~810 cm -1 assignable to the bending
vibrations Mo-O (terminal oxygen), Mo-O-Mo (corner-sharing oxygen) and Mo-O-Mo (edge-sharing oxygen) is an indication that HPMo encapsulation was succeeded. The
catalytic experiments were carried out in a stirred batch reactor at 120ºC. The main product of the esterification of glycerol with acetic acid over HPMo encaged in USY zeolite
was the monoacetin being also diacetin and triacetin. It is observed that the catalytic activity increases with the amount of HPA.
Justification for acceptance
The growing production of biodiesel by transesterification of oil with methanol or ethanol is responsible for the surplus production of glycerine. The production of acetylated
glycerol derivatives has great industrial applications. However, there are few examples of the esterification of glycerol with acetic acid over heterogeneous catalysts.
References
[1] H. Nabeshima, K. Ito, JP patent 276787 (1995).
[2] I. Kozhevnikov, Chemical Reviews 98 (1998) 171.
[3] S. Mukai, T. Masuda, I. Ogino, K. Hanhimoto, Appl. Catal. A 165 (1997) 219.
457 Selective oxidation of glycerol to dihydroxyacetone using bimetallic platinum catalysts
A. Brandner, S. Demirel, K. Lehnert and P. Claus*
Darmstadt University of Technology, Ernst-Berl-Institute/Chemical Technology II, D-64287 Darmstadt, Germany
Corresponding author. Tel: +49 6151 16 4733 Fax: +49 6151 16 4788, e-mail: claus@ct.chemie.tu-darmstadt.de
Background
The growing production of biodiesel as a renewable source based fuel leads to an increased amount of raw glycerol. This is an ideal biosustainable feedstock for
a new generation of processes leading to products like dihydroxyacetone that can be obtained by oxidation of the secondary hydroxyl function of glycerol.
Especially dihydroxyacetone, which is already produced from glycerol and in use as fine chemical, is the desired product during these experiments due to its high
but differentiated functionality. It might serve as intermediate for further chemicals if higher production capacities can be achieved by heterogeneous instead of
enzymatic catalyzed oxidation processes.
Results
Semi-batch experiments were performed in a glass reactor at atmospheric pressure and under pH control as described elsewhere [1]. Continuous experiments
were conducted in a trickle bed reactor. All reaction products were quantitatively analyzed by HPLC (Agilent 1100, Aminex HPX-87H).
All bimetallic catalysts with platinum were prepared by coimpregnating the support with a solution containing appropriate amounts of hexachloroplatinic acid
and metal chlorides as precursors for the corresponding second metal followed by a reduction with formaldehyde [2].
The presented results show a strong influence of the second metal as promoter for dihydroxyacetone selectivity. While several platinum catalysts exhibit
maximum selectivities to glyceric acid as main product from about 50 %, the addition of Group 14 and Group 15 elements as promotors change the selectivity
behaviour dramatically to the benefit of the target product dihydroxyacetone. Beside reactions conditions (pH, temperature, stirring speed, glycerol concentration,
molar glycerol to platinum ratio) many different catalysts (various platinum and bismuth contents, different support materials, preparation and pre-treatment
conditions) were tested and characterized.
Justification for acceptance
Therefore the aim of this work was to investigate the influence of the second metal in bimetallic Platinum catalysts in terms of selectivity towards the target
molecule dihydroxyacetone by various characterization methods. Reaction conditions and catalyst properties were successfully tuned to maximize
dihydroxyacetone yield.
References
[1] S. Demirel, K. Lehnert, M. Lucas, P. Claus, Appl. Catal. B: Env. 70 (2007) 637.
[2] M. Besson, R. Garcia, P. Gallezot, App. Catal. A: Gen. 127 (1995) 165.

POSTER
ABSTRACTS
General Topics

114 Characterization and photocatalytic activity of highly active mesoporous TiO 2
prepared in weak acid solutions by assistance of the hydrothermal treatment
Taicheng An a* , Jikai Liu a, b , Guiying Li a , Xiangying Zeng a , Guoying Sheng a , Jiamo Fu a
a
State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou 510640, China; b Graduate School of Chinese Academy of Sciences, Beijing 100049, China
*Corresponding author. Tel: +86-20-85291501; Fax: +86-20-85290706, e-mail: antc99@gig.ac.cn
Background: Mesoporous TiO 2 (M-TiO 2 ) is a excellent material used in fields of catalysis[1], separation technology[2] , sensors[3], and solar cells[4] due to
the uniform particle size, well-defined porosity as well as large specific surface area[5]. Considerable attentions were also received in the last few decades
because of its outstanding photocatalytic activity for the complete destruction and elimination of organic contaminants in the environment[6] . A great deal of
innovative strategies are being employed to successfully synthesize highly active mesoporous TiO 2 photocatalysts for environmental catalysis applications[6].
Results: We aim to the synthesise of large-pore M-TiO 2 with large surface area and narrow pore size distributions by using different the template direction
reagent, for example amphiphilic triblock copolymer (Pluronic P123) and poly ethylene glycol (PEG) and with assistance of a hydrothermal treatment for the
improvement of the photocatalytic degradation of endocrine disrupting chemicals. These preparations can be achieved in weak acid aqueous solutions rather than
HCl and HNO 3 in this work, and the results found the hydrolysis reaction of titanium sources has been controlled by using a low concentration acetic acid acting
as both hydrolytic retardants and acid catalysts because of the strong chelating effect and acidity of acetic acid. The hydrothermal treatment was employed as an
efficient method to shorten the preparation time and to control the phase composition and the morphology of resulted photocatalysts. The obtained M-TiO 2
exhibit uniform mesoporous structures with different mean pore sizes of up to 9.0 nm and 13.3 nm for P123 and PEG templates, respectively. Both prepared M-
TiO 2 possesses much better photocatalytic activity than Degassa P25 photocatalyst for the degradation of dimethyl phthalate and tribromophenol, respectively.
Moreover, the crystal phase and the pore structures as well as the photocatalytic activity of the obtained M-TiO 2 are all tunable by changing the synthetic
conditions, such as the concentration of acetic acid, the calcinations temperature, hydrothermal treatment time and molecular weight of PEG.
Justification for acceptance: In the present work, large-pore M-TiO 2 with narrow pore size distributions have been prepared for the purposes of less
experimental pollution, time saving, improved structural qualities and enhanced photocatalytic activity using a hydrothermal-assistant sol-gel method at low
concentrated organic weak acids (acetic acid) used as hydrolytic retardants.
References
[1] V. Parvulescu, C. Anastasescu, C. Constantin and B. L. Su, Catalysis Today 2003, 78, 477-485.
[2] M. Raimondo, G. Perez, M. Sinibaldi, A. D. Stefanis and A. A. G. Tomlinson, Chemical Communications 1997, 1343-1344.
[3] M. R. Mohammadi, D. J. Fray and M. C. Cordero-Cabrera, Sensors and Actuators B-Chemical 2007, 124, 74-83.
[4] K. Ishibashi, R. Yamaguchi, Y. Kimura and M. Niwano, Journal of the Electrochemical Society 2008, 155, K10-K14.
[5] Y. Chen and D. D. Dionysiou, Applied Catalysis A-General 2007, 317, 129-137.
[6] M. R. Hoffmann, S. T. Martin, W. Choi and D. W. Bahnemann, Chemical Reviews 1995, 95, 69-96.
161 Zeolite-encapsulated sensitizers for the photocatalytic decomposition of sulfur containing chemical warfare agents
B. Cojocaru a , V. I. Parvulescu a *, E. Preda b , G. Iepure b , V. Somoghi b , E. Carbonell c , M. Alvaro c , H. García c
a University of Bucharest, Department of Chemical Technology and Catalysis, Bucharest 030016, Romania
b N.B.C. Defence and Ecology Scientific Research Center, Sos. Oltenitei 225, Bucharest 041309, Romania
c Departamento de Química e Instituto de Tecnología Química CSIC-UPV, E-46022 Valencia, Spain
*Corresponding author. Tel. +4021 4100241, Fax. +4021 4100241, e-mail: v_parvulescu@yahoo.com
Background
Sulfur-containing compounds are by-products of industrial processes and pollutants of waste and natural waters or compounds like yperite are dangerous
chemical weapons. Efficient photocatalytic decomposition of these molecules is a process that can find application in emergency situations or for the controlled
destruction of chemical warfare stockpiles. As an alternative to inorganic semiconductors, metallophthalocyanines (MPcs) have been used to devise
photocatalytic systems [1]. Encapsulated TP + can be also used as organic photocatalyst for the degradation of a wide range of pesticides in water [2].
Results
A series of heterogeneous photocatalysts consisting on a metal phthalocyanine or 2,4,6-triphenylpyrylium as photoactive component encapsulated inside the
cavities of zeolite Y or the mesoporous channels of MCM-41 or supported on silica or titania-silica were tested for the photocatalytic decomposition of yperite.
The catalysts were prepared using the ship-in-a-bottle method or by adsorption of the commercial complex on the surface of the support [1]. The MCM-41 and
TiO 2 -SiO 2 supports were prepared by sol-gel method. The catalysts were characterized spectroscopically by UV-Vis and IR. Other characterizations using
adsorption isotherms, XRD, XPS, and TEM were made as well. They confirmed the encapsulation of the investigated photosensitizers. Spectroscopic
investigations also indicated the existence of host-guest interactions, their intensity depending on both the photosensitizer and host nature. Hence, the
coordination sphere of the metal ion in the apical positions was modified depending on the size of the cavity and the presence of framework oxygen donors able
to coordinate with the central metal atom of the complex. On the other side, the order of the complex band position TiO 2 -SiO 2 (674.8 nm)> NaY (640.6 nm)~
MCM-41 (640.7 nm) > SiO 2 (635.2 nm) indicated changes in the polarity of the support.
Two types of photoreactors: an open reactor naturally aerated and a closed quartz tube with a constant air flow, using UV or visible ambient light, were used for
testing the catalysts. These tests demonstrated that iron and manganese phthalocyanine and 2,4,6-triphenylpyrylium embedded in NaY or titania-silica can be
suitable photocatalysts for the degradation of yperite using UV and Vis irradiation with a decontamination degree of 100% in 2 hours. FePc is more active than
MnPc using ambient light, while the reverse was found using UV light. These results correlated very well with the catalysts characterization data. With respect to
the photoreactor, the data obtained showed that a tubular photoreactor with a constant air flow is more efficient than an open photoreactor. Combining the
analytical results (GC-MS analysis) with the temporal evolution a reaction mechanism has been proposed. This includes two branches, one going to complete
mineralization of yperite, the other ending at the level of sulfone.
References
[1] O.L. Kaliya, E.A. Lukyanets, G.N. Vorozhtsov, J. Porphyr. Phthaloc. 3 (1999) 592.
[2] M. Alvaro, E. Carbonell, H. Garcia, Appl. Catal. B: Environmental 51 (2004) 195.
[3] A. Sanjuan, G. Aguirre, M.Alvaro, H. Garcia, Appl. Catal. B: Environmental 15 (1998) 247.

166 Synthesis and Application of NaTaO 3 Photocatalysts for Water-Splitting to Produce Hydrogen
Ien-Whei Chen * , Chih-Hao Tan, Guo-Cheng Peng
Department of Chemical Engineering, Tatung University
Taipei 104, Taiwan, Republic of China
Corresponding author. Tel: +886-225925252-2561-128, e-mail: iwchen@ttu.edu.tw
Background
It is important to develop a renewable energy system to substitute for fossil fuel. The production of hydrogen via photocatalytic water-splitting reaction is one of
the ideal solutions to meet the energy and environmental issues. Kudo et al. [1-2] reported that the tantalates phtocatalysts possess conduction bonds consisting of
Ta5d orbitals at more negative position than titanates (Ti3d) and niobates (Nb4d) and which should be advantageous to reduce water into hydrogen under
ultraviolet irradiation. The main purpose of this study is to investigate the differences of tantalates photocatalysts synthesized via the common solid state reaction
method (SSRM) [3] and molten salt method (MSM) [4], respectively, and their application for water-splitting reaction in hydrogen production.
Results
NaTaO 3 :La photocatalysts for water-splitting reaction to produce hydrogen in this research were prepared with the precursor of Ta 2 O 3 , Na 2 CO 3 and La 2 O 3 by
using of solid state reaction method (SSRM) and the molten salt method (MSM), respectively. NiO loaded NaTaO 3 :La photocatalysts were also prepared for
water-splitting reaction to produce hydrogen. The characteristics of prepared photocatalysts were investigated by means of X-Ray Diffraction (XRD), UV-Vis
Spectrometer, Scanning Electronic Microscopy (SEM), and Brunauer-Emmett-Teller Surface Measurement (BET). From XRD results the structure and
composition of photocatalysts prepared by SSRM or MSM were shown to be identical. The UV-Vis results showed that the absorption band-edge
NiO/NaTaO3:La(2%) was found to be the greatest value of wavelength among the photocatalysts prepared by SSRM or MSM. Form SEM results the surface
structure of photocatalysts prepared by SSRM or MSM were also shown to be identical. Water-splitting reactions of pure water or 10% methanol aqueous
solution on prepared photocatalysts were carried out in a batch reactor with the irradiation of 450W high pressure mercury light. The composition of gas products
were analyzed using gas chromatography (GC). It could be found that the photocatalytic activity of NiO/NaTaO 3 :La prepared by MSM, which has the advantages
of short preparation time and low calcination temperature, was found to be higher than that of the photocatalysts prepared by SSRM. The highest production rate
of hydrogen was obtained to be 30.2mmole/10hr, i.e. 74ml/hr with NiO/NaTiO 3 :La(2%) photocatalyst and 10% methanol aqueous solution.
Justification for acceptance
Hydrogen production from photocatalytic water-splitting using solar energy is a potentially clean and renewable fuel. Also, the combustion of hydrogen only
produces water. Therefore the study of photocatalysts for water-splitting reaction absolutely meets the research in the context of the ICEC.
References
[1] H. Kato, A. Kudo, Catal. Today 78 (2003) 561.
[2] H. Kato, K. Asakura, A. Kudo, J. AM. CHEM. SOC. 125 (2003) 3082.
[3] H. Kato, A. Kudo, Catal. Lett. 58 (1999) 153.
[4] A.V. Gorokhovsky, J. I. Escalante-Garcia, T. Sanchez-Monjaras, C. A.Gutierrez-Chacarria, J. Euro. Cera. Soc. 24 (2004) 3541.
192 Photodecomposition of H 2 S to Produce H 2 over Cd x Zn 1-x S Composite Photocatalysts
Xuefeng Bai a Dan Wu b
a
Heilongjiang Instituye of Pertochemistry, Harbin,Heilongjiang 150040,P.R.China
b
School of Chemical Engineering, Dalian University of Technology, Dalian,Liaoning 116012,P.R.China
*Corresponding author. Tel: +86 451 82623663, Fax: +86 451 82623693, e-mail: bxuefeng@163.net
Background
H 2 S is the by-product from oil refinery, natural gas processing, and other chemical production. It can corrode the equipment and pollute the environment
seriously. The photocatalytic decomposition of H 2 S to produce H 2 over semiconductor photocatalysts is to convert solar energy to storable chemical energy in the
form of H 2 , and the reaction condition is relatively mild. So it will be a commercial way to produce H 2 and break a new path for the H 2 utilization as a kind of
fuel [1~4] .
Results
The composite photocatalysts Cd x Zn 1-x S (x=0.1~0.9) are prepared by coprecipitation and are applied in the H 2 production from the H 2 S saturated alkaline
solution. It was known from XRD patterns of Cd x Zn 1-x S photocatalysts that the prepared photocatalysts are composite structure in the form of solid solution, and
neither pure ZnS nor pure CdS phase exist. The structure of Cd x Zn 1-x S photocatalysts is hexagonal as same as CdS with the Greenockite structure. The diffraction
peaks of the photocatalysts shift to higher angle with the decrease of x value in Cd x Zn 1-x S. It is considered that the radii of Zn 2+ ion is smaller than that of Cd 2+
ion, and the Zn 2+ ion incorporated into the CdS lattice. It was shown from UV-Vis spectroscopy of Cd x Zn 1-x S photocatalysts that the absorption edges of
photocatalysts shift to red, and the band gap energy decrease with the increase in Cd x Zn 1-x S, which extend the light absorption scope. And the band gap energy
shows successive change with x value. So the band structure could be controlled in Cd x Zn 1-x S photocatlysts through adjusting the ratio of Cd/Zn in preparation.
The experimental results showed the H 2 evolution rate over Cd x Zn 1-x S photocatalysts from the H 2 S saturated alkaline solution reached the highest value
(7.61mmol/hg) at x=0.7 and the activity of Cd x Zn 1-x S photocatalysts are higher than the pure CdS or ZnS.
Justification for acceptance
The work was supported by the National High-Technology Project (863) of China (2007AA03z337) & Heilongjiang Science Fund for
Distinguished Young Scholars of China (JC200615).
References
[1] R.F.Service.,Science, 309:( 2005)1811
[2] J.Zaman, A.Chakma,Fuel Processing Technolog , 41( 1995)159
[3] S.V.Tambwekar, M.Subrahmanyam, Int.J.Hydrogen Energy, 22(1997):959
[4] N.Serpone, E.Borgarello, M.Grätzel. J.Chem.Soc.,Chem.Commun., 30:(1984)342

197 Investigation of photocatalytic degradation of p-chlorophenol exploiting zinc oxide
Umar Ibrahim Gaya a , Abdul Halim Abdullah a,b* , Zhulkarnain Zainal a and Mohd Zobir Hussein a,b
a Department of Chemistry, Universiti Putra Malaysia,
43400 Serdang, Selangor D.E., Malaysia
b Advanced Materials and Nanotechnology Laboratory, Advanced Institute of Technology, Universiti Putra Malaysia,43400 Serdang, Selangor D.E., Malaysia
* Corresponding author.: Tel:+60389466777; Fax:603-89435380,
E-mail: halim@science.upm.edu.my
Abstract
In this report the photocatalytic degradation of p-chlorophenol in oxygen-saturated aqueous suspension of ZnO in an immersion photoreactor is described. The
factors affecting the photocatalytic reactivity of p-chlorophenol including the amounts of substrate and ZnO were studied. Experimental data on p-chlorophenol
degradation agreed remarkably with the pseudo zero order model with the rate constant K = 0.25min -1 . Solution acidity was found to have significant influence
on photodegradation rate of p-chlorophenol. The transformation of p-chlorophenol was qualitatively monitored by high performance liquid chromatography.
Background
Attention has been given to p-chlorophenol given the double fact that it is severely phytotoxic and zootoxic [1]. Previously, a high number of researches
utilised mostly UV or UV/TiO 2 to eliminate this important pollutant. The present study aimed at investigating the promise of ZnO to mediate p-chlorophenol
photodestruction.
Results
A series of photocatalytic experiments were carried out using synthetic p-chlorophenol solution in presence of ZnO at 25 o C. The optimum p-
chlorophenol concentration and photocatalyst mass were determined from various analytical results to be 50mg/l and 2g respectively. The photodecomposition of
p-chlorophenol followed the pseudo zero-order kinetic model. The photodegradation of p-chlorophenol was favoured by alkaline pH. The adjustment of pH to
extremely low or high values resulted in drastic decrease in degradation rate. The diminution in p-chlorophenol concentration and the evolution of photoproducts
during the progress of the reactions was demonstrated by changes in chromatographic peak size. Attempt is made to characterise these products of degradation.
Justification
p-chlorophenol has direct to environment. Striking results will be presented during the conference. By-products and reaction mechanism for the ZnO
photoprocess shall be reported.
References
[1] K.R. Krijgsheld, A. van der Gen, Chemosphere Vol. 15 No.7 (1986) 825-860.
207 Reaction Studies of a Combined Plasma Catalyst Reactor
D.T Lundie a , J.A. Rees b , D.L Seymour b , , T.D. Whitmore b
a Catalysis Division, b Plasma and Surface Analysis Division
Hiden Analytical Ltd, 420 Europa Boulevard, Warrington, WA5 7UN, UK
Tel: +44 (0)1925 445 225 Email: Info@hiden.co.uk
Background
The combination of plasmas and catalysis under moderate temperatures is an emerging area [1]. The techniques are commonly combined in one of
two ways. The first is the introduction of a catalyst in the plasma discharge (in plasma catalysis, IPC), the second by placing the catalyst after the
discharge zone (post plasma catalysis, PPC). The introduction of a plasma to a catalytic system may have several effects such as a change in the
distribution or type of reactive species available for reaction or a change of catalyst properties such as an increase in dispersion or a change in
catalyst structure.
Results
A microreactor has been constructed that allows the study of catalysis using traditional temperature programmed techniques. However, the reactor
also allows a dielectric barrier discharge (DBD) to be generated over the whole length of the catalyst region (IPC). The DBD produces a cool
atmospheric plasma and is an established technique for generating surface modifications and as a source of ions and radicals for reaction processes.
A number of test reactions have been studied to show differences in reaction product distributions and activation temperatures when compared with
the catalyst alone. Reaction product distributions were measured using a conventional capillary inlet mass spectrometer. A molecular beam inlet
mass spectrometer (MBMS) was also used to sample the reactive gas species generated inside the plasma/catalyst system. Combining these two
techniques gives a unique insight into plasma catalysis process.
Justification for Acceptance
The combination of a plasma and catalyst shows potential for altering reaction conditions to produce more efficient processes. The combination of
techniques described above gives insight into the processes involved. Uniquely, the use of MBMS for analysing reactive gases in situ provides
information not available using conventional inlet systems.
References
[1] J.Van Durme, J. Dewulf, C. Leys, H. Van Langenhove, Appl. Catal. B Environ. 78 (2008) 324-333.

208 Photocatalytic Mineralization of Organic Acids in Aqueous Medium using Nano-crystalline Titania
Prepared by Sol-Gel Technique
V. G. Gandhi a , M. K. Mishra a , M. S. Rao a , A. Kumar b , K. R. Krishnamurthy b , P. A. Joshi a *, D. O. Shah c
a Department of Chemical Engineering, Faculty of Technology,
Dharmsinh Desai University, Nadiad- 387 001, Gujarat, India
b R&D Division, Reliance Industries Limited, Baroda, India
c Center for Surface Science and Technology, University of Florida, USA
*Corresponding author. Tel: +91268 2520502 131, Fax – +91268 252050, Email: zvg23_7@yahoo.com
Background
The carboxylic acids are one group of organic pollutants, released by the pharma, paint, dyes and fine chemical industries. The Photocatalytic
degradation of organic compounds in aqueous solution has attracted more attention in recent years to remove organic pollutants, present in water effluents.
Titania has been found as a better Photocatalytic material for decomposition of organic compounds in aqueous medium [1, 2]. In order to improve the catalytic
activity of the catalysts, the synthesis of nano-crystalline catalyst has been found worth promising in catalysis.
Result
Nano-crystalline titania sample was synthesized by sol-gel technique using titanium tetra isopropoxide as precursor (in methanol), hydrolyzing with
aqueous ammonia at the pH of 9 – 10. The nano-crystalline titania samples were characterized by X-ray diffraction study, FT-IR study, TGA-DTA, SEM and
surface area analysis. The samples, after calcination at different temperatures from 300 – 500 °C, were applied for the removal of carboxylic acids by
photocatalytic oxidation in liquid phase batch reactor in aqueous medium. The samples showed good catalytic activity for the photodegradation reactions giving
more than 50% degradation of organic acids. However, the activity was observed to be dependent on calcination temperature, therefore, the crystalline phase
composition of the titania, catalyst dose and the nature of organic acid. The anatase phase shows higher activity for degradation of organic acids.
Justification for acceptance
The chemical industries using esterification, acylation type reactions for the synthesis of fine chemicals, pharma intermediates, paints, dyes, etc.
generate water effluents containing significant amount of organic acids. These organic acids have harmful effect on biosystem. In order to remove the organic
acids from waste water, the photocatalytic oxidation process using nano-crystalline titania has been found one of the best methods. The present work is related to
the environmental catalysis, which is the theme of the 5 th International Conference on environmental Catalysis.
References
[1] T. Wakanabe, A. Kitamura, E. Kojima, C. Nakayama, K. Hashimoto, A. Fuijishima, in: D.E. Olis, H. Al-Ekabi (Eds.), Photocatalytic Purification and
Treatment of Water and Air, Elsevier, Amsterdam, 1993, p. 747.
[2] M.A. Fox, M.T. Dulay, Chemical Reviews 93 (1993) 341.
216 TiO 2 /vc-SBA-15: Preparation, characterization and photocatalytic reduction of CO 2
Shu-Hua Chien,* Yi-Jhen Feng, Chin-Jung Lin, Wen-Yueh Yu and Kuo-Pin Yu
Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwa.
*Corresponding author. Tel.: +886 2 2789 8528; Fax: +886 2 2783 1237. e-mail: chiensh@gate.sinica.edu.tw
Background
Recently the global warming caused by the greenhouse gases has drawn much attention both from industry and academia around the world. Highly
dispersed titania (TiO 2 ) on mesoporous molecular sieves (e.g. MCM-41 and SBA-15) have been demonstrated promising activities for the photocatalytic
reduction of carbon dioxide to methanol [1]. In this study, we present that SBA-15 with vertical nanochannels (vc-SBA-15) is a better support for TiO 2
photocatalysts as compared with conventional SBA-15. In photocatalytic reduction of CO 2 in NaHCO 3(aq) under UV irradiation, TiO 2 /vc-SBA-15 photocatalyst
shows 7.7 times higher methanol yield than TiO 2 /SBA-15.
Results
vc-SBA-15 was prepared in a ternary surfactants system (C 16 TMAB, SDS and P123) using sodium silicate solution as Si source under weakly acidic
condition by modifying Chen’s method [2]. Conventional SBA-15 was synthesized by hydrothermal method with P123 alone as template for comparison. The
grafting of TiO 2 -layer followed the same procedure by using TBOT as Ti source as described previously [3]. HRTEM image show that vc-SBA-15 has short and
face-up nanochannels, which is extremely different from SBA-15 of longer parallel channels. The XRD patterns of vc-SBA and SBA-15 both exhibit a
characteristic (100) peak, indicating that they are of highly ordered hexagonal structure. After grafting with TiO 2 -layer, there is no significant change in the
structure and morphology. The photocatalytic activities were evaluated by photocatalytic reduction of CO 2 in NaHCO 3(aq) under UV irradiation. As a result of
the short and face-up nanochannels that permits the higher accessibility for the reactants, the methanol yield of TiO 2 /vc-SBA-15 (19.9 mole/g-cat/hr) is much
higher than that of TiO 2 /SBA-15 (2.6 mole/g-cat/hr).
Justification for acceptance
These results demonstrats that the TiO 2 -modified verticle-channeled SBA-15 prepared in this study is a potential photocatalyst for application in the CO 2
removal and CH 3 OH production. This study is related to the session topics of 5th ICEC - catalysis for sustainable energy conversion, to include aspects of global
warming and CO 2 removal/recycle.
Reference
[1] J. Hwang, J. Chang, S. Park, K. Ikeue, M. Anpo, Topics. Catal. 35 (2005) 311.
[2] B. C. Chen, H. P. Lin, M. C. Chao, C. Y. Mou, C. Y. Tang, Adv. Mater. 16 (2004) 1657.
[3] S. H. Chien, G. C. Huang, M. C. Kuo, Stud. Surf. Sci. Catal. 154 (2004) 2876.

245 Kinetic Studies for Photocatalytic Degradation of Methyl Orange on Transition Metal Modified TiO 2
C.-G. Wu*; S.-H. Hong; I-L. Sung
Department of Chemistry, National Central University, Chung-Li, Taiwan 32054, ROC
Corresponding author: Tel 886-3-4227151, Fax:886-3-4227664, e-mail: t610002@cc.ncu.edu.tw
Background:
TiO 2 is a well-known, high band-gap semiconducting catalyst for photo degrading of organic wastes. Transition metal has been added to enhance the catalytic
activity by reducing the band-gap energy and avoiding the recombination of electron and hole. The kinetic study of the catalytic degradation of methyl orange
showed that the reaction order of bare TiO 2 and Ag modified TiO 2 .is 0.6 and 1.2 respectively. The results indicated that the photocatalytic reaction mechanisms
of transition metal modified TiO 2 and bare TiO 2 are not the same.
Results:
The kinetics of photodegradation of methyl orange catalyzed with Ag-TiO 2 was explored. It was found that the reaction order of Ag-TiO 2
was different from that of pure TiO 2 . This suggested that Ag in Ag-TiO 2 also get involve in the photodegradation of methyl orange. It was known
that doping with suitable transition metal ions allows extending the light absorption of large band-gap semiconductors, such as TiO 2 to the visible region.
Furthermore, the transition metals or metal oxides (especial metals belonging to group VIII) can act as an electron trapper, and therefore, avoiding the
recombination of the electron-hole pairs of TiO 2 based catalysts, enhancing the activity. The kinetic data reveal that the function of transition metal in TiO 2
based catalyst is not only the two effects mentioned above. Transition metals or metal oxides may also absorb the substrate, such as methyl orange and they may
transfer the electron/or hole more efficiently compared to TiO 2 .
Justification for acceptance:
Heterogeneous photocatalysis has been a viable treatment technology for handling industrial effluents and contaminated drinking water. Semiconducting
photocatalyst, TiO 2 is a well-know low cost, radiation stable, non-toxic, high band-gap semiconducting photo catalyst. How to further improve the performance
of TiO 2 catalyst is very important. This study may provide a clue to this issue.
References:
[1]. Chun-Guey Wu, Chia-Cheng Chao, Fang-Ting Kuo, Catal. Today 97/2-3 (2004) 103.
[2] S. Zhou, A. K. Ray, Ind. Eng. Chem. Res. 42 (2003) 6020.
[3] L.C. Chen, T.C. Chou, Ind. Eng. Chem. Res. 32 (1993) 1520.
[4] A. L. Linsebigler, G. Lu, J. T. Yates Jr., Chem. Rev. 951995735-758.
254 Photocatalytic activity of (Fe, Eu) doped TiO 2 nanocrystals synthesized by a hydrothermal route
L. Diamandescu a , F. Vasiliu a* , V. Danciu b , D. Tarabasanu-Mihaila a
a National Institute of Materials Physics, P.O. Box MG-7, Bucharest, Romania.
b Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, Cluj-Napoca, Romania.
*Corresponding author. Tel: + 40 21 3690185, Fax: +40 21 3690177, e-mail: fvasiliu@infim.ro.
Background
Titanium dioxide (titania) is a highly efficient photocatalyst, extensively applied for the degradation of organic pollutants. A considerable number of studies
were devoted to the development of efficient titania photocatalysts [1, 2]. Transition metal and rare earth selective doping is a suitable approach to improve the
photocatalytic properties of titanium dioxide. This work aims at studying the photocatalytic degradation of the salicylic acid (standard pollutant) induced by iron
and europium doped TiO 2 photocatalysts, prepared by hydrothermal synthesis [3]. The photocatalytic properties, in correlation with the structural and optical
peculiarities of the hydrothermal samples, are discussed.
Results
Iron and Europium doped TiO 2 nanoparticles were synthesised by a hydrothermal route, at mild temperature and pressure (~ 200 C and ~ 15 at).
Photodecomposition experiments were performed in a flow installation having a quartz tubular cell, supplying vessel, flow pump, magnetic stirrer and six low
pressure Hg lamps ( = 312 nm). Stock solution of 10 mM salicylic acid were prepared and used in all experiments. The suspension was kept 30 min in the dark
before the degradation experiment assisted by TiO 2 photocatalysts. Photodegradation profile was obtained from the concentration of salicylic acid measured with
a Jasco V-530 spectrophotometer (from the decrease in intensity of the electronic absorption band located at 295 nm). The apparent rate constant was calculated
from the slope of the plot ln(C 0 /C) vs time after applying a linear fit.
The photocatalytic activity of the Fe-, Eu- and (Fe, Eu)-doped titania samples was investigated in each case. In the photodegradation reaction catalyzed by
hydrothermally synthesized titania, the constant rate was calculated for the following specimens: TiO 2 (Degussa), undoped, TiO 2 , Fe-doped TiO 2 (TF), Eu-doped
TiO 2 (TE) and (Fe, Eu)-codoped TiO 2 (TFE). The undoped titania gave a value of ten times higher than TiO 2 Degussa, while the codoped Fe/Eu sample gave the
highest activity. For separate doping, the apparent constant rate increase with 25 % (Fe doping) and 43% (Eu doping) as compared to undoped TiO 2 , while for
co-doped sample is nearly three times greater.
The remarkable conversion degree recommends the co-doped specimen TFE, obtained by a simple hydrothermal route at moderate temperature, as a promise
photocatalyst for the degradation of harmful organic compounds in water. The better photocatalytic activities of the hydrothermally doped titania samples can be
attributed to the cationic species present in the doped and codoped titania which avoid possible electron-hole recombination stabilizing the holes in the valence
band and electrons in the conduction band. Moreover, the hydrothermal catalysts have high surface areas (~ 100 m 2 /g) and O-H groups on the surface which
seem to stabilize the electron-hole pairs.
The obtained results were corroborated with the morphostructural data acquired by using BET, XRD, and TEM.
References
[1] R.S. Sonawane, B.B. Kale, M.K. Dongare, Mater. Chem. Phys. 85 (2004) 52.
[2] P. Yang, C. Lu, N. Hua, Y. Du, Mat. Letters 57 (2002) 794.
[3] L. Diamandescu, M. Feder, D. Tarabasanu–Mihaila, F. Vasiliu, Applied Catalysis A: General 325 (2007) 270.

261 Design of hydrophobic zeolite and mesoporous materials by the modification using TEFS
and its application as supports of TiO 2 photocatalyst
Y. Kuwahara, K. Maki, K. Mori, H. Yamashita*
Division of Material and Manufacturing Science, Graduate School of Engineering, Osaka University
2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
*Corresponding author. Tel & Fax: +81-6-6879-7457
e-mail: yamashita@mat.eng.osaka-u.ac.jp
Background
Recently many kinds of applications of photocatalyst system for reduction of global atmospheric pollution or purification of polluted water have been studied.
Especially the combination of TiO 2 photocatalyst and porous materials which is conventionally used as absorbents have been revealed that it has high potential of
photocatalytic degradation, however the photocatalytic property much depends on the hydrophilic-hydrophobic properties of these materials surface deriving
from SiO 2 /Al 2 O 3 ratio and number of surface silanol group 1) 2) . In this study, we attempted to design a high hydrophobic zeolite and mesoporous materials
through surface silylation using TEFS reagent and applied as supports of TiO 2 photocatalyst for the degradation of organics diluted in water.
Results
The surface of Y-zeolite (SiO 2 /Al 2 O 3 : 5, 40, 200) and high mesoporous silica was modified using
triethoxyfluorosilane (TEFS) which is able to eliminate surface hydroxyl groups by fluorination and the
ratio of TEFS was changed to 0, 10, 40 mol%. The prepared samples were characterized by various
spectroscopy analysis. The prepared zeolites were applied as the supports of TiO 2 photocatalysts. The
local structure of titanium oxide species was investigated by XAFS and the influences of the
modification for photocatalytic activity were evaluated by the degradation of 2-propanol diluted in
water under UV-light irradiation.
From the results of some spectroscopy analysis, the ability of water adsorption of Y-zeolite and HMS
after the surface modification dramatically decreased while the both microporous structure and the
surface area had been maintained. These materials prepared by this modification seem to be very stable
even after the process of calcinations over 773 K in order to immobilize the TEFS reagent or to
incorporate TiO 2 particles on them. After the loading TiO 2 photocatalysts on these modified materials,
it was affirmed from the results of XAFS measurement that the crystallinity of TiO 2 nano particles in
the porous structure was increased. Furthermore results of practical photocatalytic degradation
indicated that the TiO 2 photocatalytic activities were highly enhanced on all modified materials
regardless of SiO 2 /Al 2 O 3 ration as shown in Fig.1. It is thought that both the hydrophobicity of supports
and the crystallinity of TiO 2 particles led the high absorption and photocatalytic degradation of organics.
References
[1] H. Yamashita, K. Mori, Chem. Lett., 36 (2007) 348.
[2] H. Yamashita, S. Kawasaki, S. Yuan, Catal. Today, 126 (2007) 375.
Photocatalytic activity / mmol·h -1·TiO2 g -1
2.5
2.0
1.5
1.0
0.5
0.0
SiO2/Al2O3
=5
TiO2/Y
TiO2/TEFS 10%-Y
TiO2/TEFS 40%-Y
SiO2/Al2O3
=40
SiO2/Al2O3
=200
P-25
Fig.1 Photocatalytic activity for degradation of 2-propanol diluted
in water on 10 wt% TiO 2 photocatalyst loaded on the original Y-
zeolites, surface modified Y-zeolites (TEFS : 10, 40 %) and TiO 2
powder (P-25).
279 Metallic monoliths and microreactors coated with carbon nanofiber layer as catalyst support
E.García-Bordejé a , V. Martinez-Hansen b , C. Royo b , E. Romeo b and A. Monzon b
a Instituto de Carboquimica (C.S.I.C.), Miguel Luesma Castán 4, 50015 Zaragoza, Spain
b Dep. of Chemical and Environmental Engineering. University of Zaragoza. 5000 Zaragoza. Spain.
*Corresponding author. Tel:+ 34 976733977; Fax: +34 976733318, e-mail: jegarcia@icb.csic.es
Background
Metallic monoliths and microreactors, which are both structured reactors with parellel channels, have some favourable properties for process intensification such
as low pressure drop, enhanced mass and heat transport enabling isothermal operation, improving selectivity and security [1]. To increase the surface area of
monolith and microreactor usually the channels are coated by a catalyst support material. In this work, we study the coating with carbon nanofibers (CNF) and
carbon nanotubes (CNT) on monoliths and microreactors. CNF and CNT hold many promises as catalyst support [2]. CNF form aggregates with high surface
areas, high mesopore volumes and low tortuosity, which are favourable for liquid phase applications of environmental interest.
Results
To have a CNF-based structured catalytic reactor with good activity and durability, first requirement is the preparation a catalytic coating with good properties
such as good adhesion to substrate, open porosity (mesoporosity) to enhance the diffusion of reactants, uniform thickness of CNF layer, good mechanical
strength and control over the microstructure of CNFs. In this work, we have grown a CNF layer over monoliths and microreactors via catalytic chemical vapor
deposition (CCVD). The CNF coating properties have been optimised by studying different variables such as pretreatment of microreactor substrate, CNF yield,
reaction temperature and addition of H 2 . The characterization of CNF layer includes adhesion tests, SEM-EDX, XRD, Raman spectoscopy, TEM, Temperature
programmed oxidation and N 2 adsorption. The deposition of Pt catalyst and the testing in the reduction of nitrates in water is underway. In a more general
perspective, monoliths aim at reducing pressure drop, energy use and hence operation costs, while microreactors aim at increasing mass and heat transport,
selectivity and reducing by product generation.
Justification for acceptance
CNF and CNT are relatively new catalyst support. Metallic monoliths and microreactors are structured reactors that hold many promises for process
intensification. The combination of both has good prospect as catalyst support for several environmental applications such as cleaning of pollutants in water, H 2
production, e.g. by NH 3 decomposition and intensification of chemical processes by increasing selectivity and reducing by product generation, hence developing
more sustainable and greener processes.
References
[1] G. Kolb, V. Hessel, Chemical Engineering Journal, 98 (2004) 1.
[2] P. Serp, M. Corrias, P. Kalck, Applied Catalysis A-General, 253 (2003) 337.

294 Different strategies to improve photocatalytic activity of titania-based systems
A. Marinas*, M.A. Aramendía, J.C. Colmenares, J. Hidalgo, S. López-Fernández, J.M. Marinas and F.J. Urbano
Organic Chemistry Department, University of Cordoba, Campus de Rabanales, Marie Curie Building, E-14014, Cordoba (Spain)
*Corresponding author. Tel: +34 957 218638, Fax: +34 957 212066, e-mail: alberto.marinas@uco.es
Background
Photocatalysis is usually set as a clear example of Green Chemistry Technology. The most generally-used photocatalyst is titania. Nevertheless, it presents two
main drawbacks: i) the relatively high electron-hole recombination rate which is detrimental to photoactivity and ii) low adsorption (ca. 5%) of solar light energy.
The present piece of research is aimed at exploring some strategies to improve photocatalytic activity of titania. All systems were tested for gas-phase selective
photooxidation of 2-propanol to acetone [1].
Results
Several titanium oxides were synthesized by the sol-gel technique starting from titanium tetraisopropoxide (TTIP) or tetrachloride and by diverse aging methods
(magnetic stirring, sonication, reflux and microwave radiation). Screening of such different synthetic conditions led us to choose titanium isopropoxide as the
titanium precursor and sonication as the method of choice for aging the gel since its ensured obtaining 100% anatase particles with a relatively high surface area.
The method was then applied to the synthesis of different metal-doped systems, in a 1% atomic metal/Ti ratio. The most active system, platinum-doped one, was
submitted to different oxidative and reductive thermal treatments. Interestingly, heating at 850ºC either in synthetic air flow or in static air resulted in better
catalytic performance than Degussa P25, despite the fact that our catalysts consisted in very low surface area rutile specimens. XPS analyses showed that thermal
treatment at 850ºC resulted in electron transfer from titania to Pt 0 particles through the so-called strong metal-support interaction (SMSI) effect. Improvement in
photocatalytic activity is explained in terms of avoidance of electron-hole recombination through the electron transfer from titania to platinum particles. The last
approach to be commented is the synthesis of titania on zeolitic structures (USY and ZSM-5) with a view to obtain highly dispersed low-sized titania particles
which exhibit the so-called quantum-size effect thus resulting in an improvement in photocatalytic activity.
References
[1] J.C. Colmenares, M.A. Aramendia, A. Marinas, J.M. Marinas and F.J. Urbano, Appl. Catal. A 306 (2006) 120.
295 Selective photooxidation of 2-propanol to acetone on different titania and vanadia-based ZSM-5 systems
M.A. Aramendía, J.C. Colmenares, S. López-Fernández, A. Marinas*, J.M. Marinas and F.J. Urbano
Organic Chemistry Department, University of Cordoba, Campus de Rabanales, Marie Curie Building, E-14014, Cordoba (Spain)
*Corresponding author. Tel: +34 957 218638, Fax: +34 957 212066, e-mail: alberto.marinas@uco.es
Background
Photocatalysis is one of the most promising disciplines in the context of Green Chemistry. Its main application, at least as far as the number of the publications
on the topic is concerned, is degradation of pollutants present in waters through complete mineralization. Nevertheless, in non-aqueous media there is the
possibility of selectively photooxidizing a chemical, which is very attractive. In the present piece of research different titania and vanadia-based systems were
synthesized and tested for gas-phase selective photooxidation of 2-propanol to acetone [1].
Results
The use of zeolites in photocatalysis presents some advantages such as the high surface area, transparency to UV-vis radiation above 240nm or the possibility to
modulate both the micropolarity of the zeolite inner surface and the size of the channels. In the present communication, vanadia and titania were synthesized on
ZSM-5 zeolites (Si/Al=63 and 17) through the sol-gel process. The nominal content in TiO 2 or V 2 O 5 was of 2 mmol/g of catalyst. Resulting systems had high
photocatalytic activity for gas-phase photocatalytic oxidation of 2-propanol which could not be simply ascribed to the high surface area. Instead, the decrease in
the crystalline size of TiO 2 (anatase) and V 2 O 5 thus exhibiting the so-called quantum size effect (as determined by XRD and UV-Vis spectroscopies,
respectively) could account for that. Subsequent deposition of platinum (Pt/Ti atomic ratio below 0.2%) on the most active systems resulted in a sharp increase in
molar conversion, low deactivation with time on-stream and significant increase in selectivity to acetone which was over 80%, at ca. 75% conversion, after 5
hours.
Justification for acceptance
As stated above, photocatalysis is one of the most promising areas in the context of Green Chemistry and to our mind selective photooxidations are to be more
intensively developed in the next few years. Moreover, gas-phase selective photooxidation of 2-propanol is quite a simply, reliable test reaction for rapid
screening of photocatalysts.
References
[1] J.C. Colmenares, M.A. Aramendia, A. Marinas, J.M. Marinas and F.J. Urbano, Appl. Catal. A 306 (2006) 120.

296 Novel nanohybrid basic material L-leucine/Mg-Al layered double hydroxide
R. A. Miranda a , A. M. Segarra a , F. Medina a and J. E. Sueiras a
a Department of Chemical Engineering, Universitat Rovira i Virgili, Tarragona,Av. Països Catalans, 26,, 43007, Spain.
*Corresponding author. Tel: +34977558556, Fax : +34977559621, e-mail: anamaria.segarra@urv.cat
Background Layered double hydroxides (LDHs) are known as hydrotalcite-like compounds and they are anionic two-dimensional layered clays with general
formula [M 2+ 1-x M 3+ x(OH) 2 ][A - x/n·yH 2 O] (M 2+ =Mg 2+ , M 3+ =Al 3+ and A - =OH - , CO 3 2- , NO 3- ). LDHs have been used as inorganic anion-exchangers and base
catalysts in the chemical industry. 1 Especially, the synthesis of organic-inorganic nanohybrid materials, as amino acid/LDH, by intercalation has received
extensive research in recent years. 2-4 However, in the few examples of amino acid/LDH as an asymmetric catalyst, lower selectivity than the homogeneous
counterpart were obtained due to difficult access to the chiral active centers. 4 Recently, our group has developed a new hydrotalcite type by rehydration of the
mixed oxides under ultrasounds, LDH RUS(t) , which contains stronger and more accessible - OH interlayer anion as active basic sites. 5 Then, we have investigated
the immobilization behavior of amino acids in the LDH RUS(t) through only the replacement of the - OH anions at the edge-interlayer sites.
Results In this study, the immobilization of L-leucine as a guest amino acid onto the Mg-Al-layered double hydroxide LDH RUS(t) has been investigated by the
reconstruction method under ultrasounds for 60 and 120 min. using Mg-Al oxide precursor at 298 K and the subsequent addition of the L-leucine water solution.
The mixture was stirred for short time. The uptake amounts of L-leucine were determined by TOC measurements and showed 0.20-0.03 mmol of L-leucine
grafted per 1.0 mmol of LDH RUS(t) . The new organic-inorganic nanohybrid material was examined by using XDR where no expansion of interlayer distance of the
solid product was observed. The IR spectra of L-leucine/LDH RUS(t) solids showed a new band at 1583 cm -1 corresponding to the (CO) of the carboxylate group, -
COO - , from the L-leucine and no band of the (OH) of the carboxylic group, -COOH. It indicates that L-leucine is immobilized into LDH RUS(t) uniquely on the
edge-interlayer sites, probably, through the substitution of the - OH anions as a result of a simple and quick acid-base reaction. The employed of the L-
leucine/LDH RUS(t) as a novel heterogeneous catalyst for asymmetric catalytic reactions which need basic medium (i.e. Julia-Epoxidation) is a subject for future
work.
Justification for acceptance The fresh L-leucine/LDH RUS(t) organic-inorganic nanohybrid is an environmental innocuous material with basic character and
accessible chiral amino acid compound grafted. These properties give this solid an added value because it can be used as a catalytic/support material in
asymmetric catalytic reactions. Furthermore, it is a low cost chiral catalyst, eco- friendly, simple to prepare and it can be easily recycled and reused.
References
[1] F. Cavani, F.Trifiro, A.Vaccari, Catal. Today 11 (1991) 173.
[2] H. Nakayama, N. Wada and M. Tsuhako, Int. of Pharm. 209 (2004) 469.
[3] S. Aisawa, H. Kudo, T. Hoshi, S.Takahashi, H. Hirahara, Y. Umetsu, E. Narita, J. of Solid State Chem. 177 (2004) 3987.
[4] B. M. Choudary, B. Kavita, N. Sreenivasa Chowdari, B. Sreedhar and M. Lakshmi Katam , J. Catal. Letters 78 (2001) 373.
[5] R. J. Chimentão, S. Abelló, F. Medina, J. E. Sueiras, Y. Cesteros, P. Salagre, J. Catal. 252 (2007) 249.
314 Synthesis and Characterization of N-doped Visible Light Response TiO 2 Nanotubes
Aimin Yu, Baocheng Lv, Guoqing Pan, Yong Pi, Fuxiang Zhang, Yali Yang, Naijia Guan*
Lab of Functional Polymer Materials, Department of Materials Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, PR China
*Corresponding author. Tel. /Fax: +86-22-2350-0341
E-mail: guannj@nankai.edu.cn
Background
TiO 2 nanotubes as photocatalysis have aroused much attention owning to their potential in environmental cleaning and energy regeneration. However, pure TiO 2
nanotubes have almost no visible-light response. Scientists have paid much attention for years to doping TiO 2 with different modifers [1-3] in order to spread their
optical response. Among all of the doped elements, nitrogen, introduced by treating the TiO 2 in NH 3 gas, was found to be more effective and facile method than
others. Here we report a simple route to obtain N-doped TiO 2 nanotube with excellent results of degradation of methylic orange under visible light.
Results
The titanate nanotubes by protonating the surface with HCl as starting materials were synthesized by hydrothermal method. Nitridation of titanate nanotube was
carried out in a tubular quartz reactor by flowing ammonia at 300-600 o C. N atoms could be confirmed by the N 1s binding energy of the XPS spectra and UV-
Vis spectra, which have proved that the O atoms in TiO 2 have been partly substituted by N and therefore lead into a visible light absorption. The representative
TEM images indicated that the structures of nanotube structure could be kept after NH 3 flow treatment at as high temperature as 500 o C. Mesoporous structures
were also observed by the N 2 adsorption-desorption isotherms of the as-synthesized samples. However, the NH 3 flow treatment has caused a shrinkage of
nanotube to some extent and resulted in a decrease of surface area from original 450 m .g -1 to 368 and 200 m .g -1 , treated at 400 and 500 o C respectively. The
average pore diameter also decreased from 13.4 nm to 9.1 nm, parallelly. It was revealed by the XRD patterns that the titanate treated by NH 3 flow have been
turned into anatase TiO 2 , and no obvious peaks assigned to TiN species were observed. The absence of Ti-N bond was also confirmed by the Ti-XPS spectra and
IR spectra. It can be proposed that the incorporation of N from NH 3 to titanate nanotubes caused a H 2 O formation, which promoted the reorganization of titanate,
which finally converted into anatase TiO 2 due to the loss of water at high temperatures. Additionally, the reorganization of inorganic framework caused the
shrinkage of nanotube due to their different space matrix. The detailed formation mechanism is under investigation. The photocatalytic performances of the assynthesized
samples were investigated by degradation of methylic orange under a 125 W super-high-pressure Hg lamps (mail =420 nm). The optimal
conversion of 95% for methylic orange has been achieved under stirring and room temperature (200 ml 20 mg/l methylic orange aqueous solution and 0.1 g
catalyst powder), much higher than 20% on the N-doped P25 TiO 2 catalyst.
Justification for acceptance
This paper introduced a feasible route to obtain N-doping TiO 2 nanotubes with high visible light activity. Characterizations of catalyst have proved that the
simple nitridaton at a suitable temperature caused the incorporation of N atoms and re-arrangement of titanate nanotube to formation of visible-response TiO 2
nanotube. On the as-synthesized samples, superior photocatalytic degradation performance under visible light irradiation was demonstrated with respect to N-
doped P25 TiO 2 .
References
[1] Mor G. K., Shankar K., Paulose M., .Grimes C. A. Nano. Lett. 6 (2006) 215
[2] Wang, C.; Bahnemann, D. W.; Dohrmann, J. K. Chem. Commun. 16 (2000) 1539.
[3] R. Asahi, T. Morikawa, T. Ohwaki, Science 293 (2001) 269.

316 Photocatalytic properties of TiO 2 supported catalyst under sunlight irradiation for air treatment
T. Lewis b , S. Suárez a *, J.A. Coronado a , R. Portela a , P.Avila c , B. Sanchez a
a CIEMAT-PSA Environmental Application of Solar Radiation Unti, Avda. Complutense 22, 28040, Madrid (Spain)
b Instituto de Química – USP, Av. Prof. Lineu Prestes, Butantã São Paulo, Brasil
c Institute for Catalysis and Petrochemistry, C/ Marie Curie 22, Madrid 280
*Corresponding author. Tel: +34 91 346 6177, Fax : +34 91 346 6037 e-mail: silvia.suarez@ciemat.es
Background
Heterogeneous photocatalysis is an efficient technology for the treatment of pollutants in air or water. TiO 2 is the most widespread semiconductor for such
applications. Even if experiments under sun irradiation using a Compound Parabolic Collector (CPC) have been carried out for polluted water treatment [1], no
much information regarding to air treatment can be found in the literature. In a previous article the possibility of using this technology for air purification was
studied using supported TiO 2 [2].
Results
In this work we have deeply analysed the performance of ceramic plates based on TiO 2 under sun irradiation, monitoring experiments from June to October 2007
(Madrid, Spain), analysing the photocatalyst activity in continuous flow under different operating conditions i.e. total gas flow, VOC concentration and water
vapour content. The evolution of the reactants and products was monitored by FTIR with the UV radiation intensity and temperature during all day long, using
trichloroethylene (TCE) as a target molecule. A special attention was devoted to analyse the photocatalyst selectivity to undesirable reaction products.
The reactor used is based on a glass tube centre on the focus of the CPC collector under sun irradiation conditions (latitude 40º27’ N, longitude 3º44’ W) [2]. The
modification of the total flow (1 to 4 L·min -1 ) keeping constant the TCE concentration at 130 ppm, indicated that the photocatalyst was able to treat up to 2.5
L·min -1 with a conversion nearly 100% from 12:00 h to 19:00 h during summer time (UV max intensity 6.5 mW·cm -2 ), using 35 cm 3 of photocatalyst volume.
Moreover, experiments carried out changing the TCE amount and fixing the total flow to 1L·min -1 indicated that 400 ppm were eliminated with conversion
higher than 95% (UV max intensity 4.5 mW·cm 2 ). As expected the mayor reaction products detected in the absence of water vapour were dichloroacetyl chloride
(DCAC), COCl 2 along with CO 2 and CO [2]. But the presence of 5% relative humidity totally suppresses the formation of COCl 2 with a complete TCE removal.
Justification
In summary, the behaviour of TiO 2 ceramic plates under sunlight irradiation using a CPC collector, open a new possibility to treat large gas volumes with high
concentration of pollutant for air treatment in continuous mode.
[1] S. Malato, J. Blanco, A. Vidal, D. Alarcón, M.I. Maldonado, J. Cáceres, W. Gernjak Sol. Energy, 75-4 (2003) 329.
[2] J.M. Coronado, B. Sanchez, R.Portela, , S. Suárez, Journal of Solar Energy Engineering 130 (2008) 1-4.
[3] S. Suárez, J. Coronado, R. Portela, J.C Martín, M. Yates, P. Avila, B. Sanchez. Env. Sci. Tech. 2008 (accepted).
333 in situ spatially resolved near-infrared imaging for heterogeneous catalytic reactions
F. Aiouache a *, M. Nic An tSaoir a , K. Kitagawa b , C. Hardacre a
a CenTACat, School of Chemistry, Queen’s University Belfast, Belfast, BT9 5AG, Northern Ireland
b School of Applied Chemistry, Nagoya University, Chikusa-ku, Furo-cho, Japan
*Corresponding author. Tel: +44 28 90974065, e-mail: f.aiouache@abc.ac.uk
Background
We discuss the application of spatially resolved near-infrared (NIR) imaging to in situ monitoring gas-solid reactions on supported catalysts. NIR beam is less
sensitive to adsorbed and gaseous species as compared to infrared (IR) one. This disadvantage has made NIR spectroscopy be rarely applied to gas-solid catalysis
where both gas and adsorbed species can be probed simultaneously. However, short wave lengths of NIR offer the technique a superior beam penetration in solid
phases and beam scattering. We will show in the following two examples the advantages of NIR imaging, namely, thermography and species-based spatially
resolved spectroscopy for the investigation of methane steam-reforming reaction along with partial oxidation.
Results
High-throughput near-infrared imaging was used to distinguish catalyst activity for low-temperature methane steam-reforming. Geminal hydroxyls of reduced
ceria were depicted during methane reforming at 673 K 1 . The changes in absorbance maps under various water partial pressures showed evidence of formate
intermediate formations without redox exchanges. Higher resolution was observed in absorbance change images than that of thermal images obtained from
catalyst surface self-emissions. The experimental results illustrated higher activity of pure rhodium catalyst than that of bimetallic ones likely due to the high
dispersion of rhodium on the catalyst support. Moreover, the reaction was accelerated when high surface area silica was added. Our filter bandwidths limited our
interest in band-shift distribution of geminal hydroxyl band during the reduction process. Nevertheless, a correlation between the image intensities and surface
densities was not achieved. The low signal to noise ratio and time instability of both illumination source and camera detector necessitated recording of
background images before each test. A qualitative approach based on the ratio of the light intensities was used to distinguish among catalyst sample activities.
The subsequent investigation on the application of NIR imaging technique to heterogeneous reactions was the dynamic flow of gas–solid reactions carried out in
a catalytic fluidized bed reactor for reforming and partial oxidation. In particular, our work has revealed the existence of hot reactive zones for both oxidation
and reforming regions. The combination of NIR imaging with thermography has been used to visualize the spatial distribution of the reactant-to-product
conversion within an operating reactor.
Justification for acceptance
Recent advances in near-infrared tunable lasers, highly sensitive focal planar detectors and chemometrics enable us to foresee a promising future of in situ
spatially resolved NIR imaging for transient heterogeneous reactions under realistic conditions.
References
[1] F. Aiouache, H. Oyama, K. Kitagawa, AIChE J. (2006) 52, 4, 1516

344 Direct synthesis of H 2 O 2 from H 2 and O 2 over Pd-loaded powdered diamond catalyst
Ryosuke Yamane, Na-oki Ikenaga, Takanori Miyake, Toshimitsu Suzuki
Department of Chemical Engineering, Kansai University, Suita, Osaka, 564-8680, Japan
E-mail : va7m605@ipcku.kansai-u.ac.jp
Background
Increasing demand for H 2 O 2 is expected from green chemistry view. Direct synthesis of H 2 O 2 from H 2 and O 2 has attracted much attention as a new process. A
large number of palladium loaded catalysts have been reported to be active in the present proton 1) . In this study, we have developed a new type of palladium
loaded powdered diamond catalyst and proton exchang resin as a proton source for the direct synthesis of H 2 O 2 .
Results
Our group reported several catalytic reactions, using powdered diamond as a support material of catalyst 2) . Here we will extend palladium loaded diamond
catalyst for the direct synthesis of H 2 O 2 . Commercial powdered diamond was pre-treated in air at 450 o C for 5 h, and it is called oxidized diamond (O-Dia). The
catalyst was prepared by impregnating Pd(OAc) 2 to O-Dia, and it was calcinated in air at 450 o C for 5 h (Pd/O-Dia). The reaction was curried out in a 70 ml three
necked flask. After H 2 treatment at 90 o C, ethanol containing HCl (4x10 -4 M) and Amberlyst (50 mg) were added. Then H 2 -O 2 mixed gas (1:9) was introduced
into the flask.
With a 25 mg of Pd/O-Dia (3wt%) catalyst acidified with H 2 SO 4 (0.12 M), 0.58 mmol of H 2 O 2 was obtained after the reaction for 3 h at 10 o C (Entry 1).
Addition of 50 mg of Amberlyst (H + : 0.01 M), in place of H 2 SO 4 , increased the amount of H 2 O 2 from 0.58 to 0.89 mmol with a selectivity to H 2 O 2 of 40.3 %
against consumed H 2 (Entry 2). H 2 O 2 production was increased at a low concentration of proton by using Amberlyst as proton source.
Direct syntheses of H 2 O 2 with several palladium loaded catalysts were compared. Activated carbon and silica loaded Pd catalysts (Entry 3, 4), gave slightly
smaller amounts of H 2 O 2 with a lower H 2 O 2 selectivity as compared to Pd/O-Dia in the presence of Amberlyst. Thus, Pd/O-Dia-Amberlyst is one of interesting
catalyst systems in the H 2 O 2 synthesis.
Justification for acceptance
H 2 O 2 is an environmentally benign oxidizing reagent. This paper involves two new aspects in the direct production of H 2 O 2 from H 2 and O 2 ; namely use of
Table 1 Activities of various catalysts in direct formation of hydrogen peroxide over Pd catalysts
Cation-exchanging
H 2 consumption Product H 2O 2 H 2O 2 selectivity
Entry Catalyst
Solvent
[H + ]
resin
(mmol) (mmol) (%)
410 -4 M HCl
1 Pd(3wt%)/O-Dia
- 0.24 mol . L -1 1.56 0.58 37.2
+ 0.12M H 2SO 4 /Ethanol
2 Pd(3wt%)/O-Dia 2.22 0.89 40.3
Amberlyst 15dry
3 Pd(3wt%)/AC 410 -4 M HCl /Ethanol
0.01mol . L -1 2.38 0.77 32.2
(H + : 4.7 mmol/g)
4 Pd(3wt%)/SiO 2 2.49 0.81 32.6
Catalyst: 50 mg, Solvent: 20 ml, Cation-exchanging resin: 50 mg : Reaction temperature: 10 oC, Reaction time: 3 h
Catalyst pre-treatment: H 2 reduction at 90 o C for 1 h
oxidized diamond as a new support material of Pd and use of a cation exchanging resin as a proton source. Thus after removal of the resin, pure H 2 O 2 solution
could be obtained. From these points, this paper should presented in 5th ICEC.
References
[1] S. Chinta, J. Catal., 225 (2004) 249
[2] Matsumura, et al., J. Mol. Catal. A, 250 (2006) 122
350 CO-TPR-DRIFTS in situ study of CuO/Ce 1-x Tb x O 2- (x = 0, 0.2 and 0.5) catalysts:
Support effects on redox properties and catalysis
Parthasarathi Bera a , Aitor Hornés a , Daniel Gamarra a , Guillermo Munuera b , Arturo Martínez-Arias a,*
a Instituto de Catálisis y Petroleoquímica, CSIC, C/ Marie Curie 2, Campus Cantoblanco, 28049 Madrid, Spain
b Departamento de Química Inorgánica, Universidad de
Sevilla, 41092 Sevilla, Spain
*Corresponding author: Tel: +34 915854940, Fax: + 34 915854760, E-mail: amartinez@icp.csic.es
Background
Catalysts based on combinations between copper and cerium (or related) oxides are most interesting from an economical point of view for processes involving
CO oxidation. In general terms, their catalytic properties appear related to their redox activity. This has been typically analysed by classical TPR technique, as
nicely shown in a recent report by Luo et al.; 1 however, most relevant redox details are apparently detected when including DRIFTS analysis within the TPR
study.
Results
Three CuO/Ce 1-x Tb x O 2- catalysts (x = 0, 0.2 and 0.5), all with 1 wt. % copper, are studied; preparation and characterization details for the examined catalysts are
available elsewhere. 2 HREM shows the presence of more or less round nanocrystals (ca. 5-7 nm size) displaying the fluorite structure of the corresponding
supports. Analysis by XPS is in agreement with copper in the initial samples being in the form of fully oxidized CuO-like entities although somewhat modified
by their interaction with the respective supports in comparison with bulk CuO, in agreement with previous XAFS examination. 1 The CO oxidation activity (as it
occurred under CO-PROX conditions too) 2 decreases with increasing the amount of Tb in the support in spite of the apparently decreasing CuO size (based on
Ar + -sputtering XPS experiments), thus revealing significant support effects. Careful analysis by CO-TPR using the DRIFTS cell as reactor (including isotopic
effects upon changing between 12 CO and 13 CO) indicates that CuO reduction can occur even at subambient temperature, involving at such low temperatures
exclusively interfacial copper sites; it is such redox process (not detectable in classical TPR runs), which basically determines the catalytic properties of the
systems, in agreement with recent findings. 3 Additional in situ-DRIFTS under CO-O 2 mixture uniquely reveals that a reductive preinduction involving Cu +
formation is produced prior to CO oxidation onset. Support effects on differences in onset of such process are related to the specific interfacial redox properties
and also account for the observed catalytic differences.
Justification for acceptance
Combinations between Cu and Ce (or related) oxides are promising for substituting noble metals in processes involving CO oxidation. Deeper knowledge of
their catalytic behaviour is here achieved by combining DRIFTS and CO-TPR. It reveals that interfacial redox changes are most relevant to the catalysis.
References
[1] M.-F. Luo, Y.-P. Song, J.-Q. Lu, X.-Y. Wang, Z.-Y. Pu, J. Phys. Chem. C 111 (2007) 12686.
[2] A. Martínez-Arias, A.B. Hungría, M. Fernández-García, J.C. Conesa, G. Munuera, J. Power Sourc. 151 (2005) 32, and reference 15 therein.
[3] D. Gamarra, C. Belver, M. Fernández-García, A. Martínez-Arias, J. Am. Chem. Soc. 129 (2007) 12064.

357 Effect of TiO 2 particle size on photocatalytic reduction of CO 2
K. Koí a* , L. Obalová a , L. Matjová b , D. Plachá a , Z. Lacný a , J.C.S. Wu
a TechnicalUniversityofOstrava,17.listopadu15,70833Ostrava,CzechRepublic
b
Institute of Chemical Process Fundamentals CAS, Rozvojová 135, Prague, Czech Republic
c NationalTaiwanUniversity, Taipei10617,Taiwan
* Corresponding author. Phone: +420 596991592, e-mai kamila.koci@vsb.cz
Background
The titanium dioxide has been found as the most photoactive, inert, corrosion resistant and inexpensive semiconductor. TiO 2 can be used either pure or doped
with metals or metal oxides. These modifications can enhance its photocatalytic activity. Particle size is an important parameter for photocatalytic efficiency.
This contribution deals with the effect of various particle size of TiO 2 catalyst on CO 2 photocatalytic reduction, since this problem has not been investigated yet.
Results
A series of titanium dioxide catalysts with various particle sizes (6 nm - 40 nm) were prepared by sol-gel method in reverse micelle arrangement and calcinated at
various temperatures for 4 hours in an air stream. The catalysts were characterized by various methods (XRD, BET area and pore size measurements, UV-
VIS) and tested for CO 2 photoreduction. The CO 2 reduction in 0.2 M NaOH increased with decreasing particle size of TiO 2 , subsequent drop of products yield
(methane and methanol) was observed for crystal sizes smaller than 7 nm. It can be concluded that changes of particle size cause changes in structural and
electronic properties of nanometer crystal. The band gap of the TiO 2 nanoparticles is a function of the primary particle size and the high catalytic activity can be
achieved by decreasing band gap. The observed dependence of product yield on the particle size is connected with changes of the dynamics of e - /h +
recombination [1].
Justification for acceptance
The greenhouse gas making the largest contribution from human activities is carbon dioxide (CO 2 ), the global concentration of CO 2 in the atmosphere is
increasing. The reduction of CO 2 by photocatalysts is one of the most promising methods since CO 2 can be reduced to useful compounds by irradiating it with
UV light. However, the efficiency of this method is relatively low and the increasing of yield is necessary.
References
[1] Z. Zhang, C.-C., Wang, R. Zakaria, J. Y. Ying, J. Phys. Chem. B. 102 (1998) 10871.
Acknowledgements
This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic MSM 6198910019.
365 Visible-Light Induced Photocatalytic Activities of N- and Si-codoped Titanias modified with Fe
S. Iwamoto * , H. Ozaki, K. Fujii, and M. Inoue
Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan
*Corresponding author. Tel: +81 75 3832481, Fax: +81 75 3832479, e-mail: iwamoto@scl.kyoto-u.ac.jp
Background
Removal of chemical contaminations in water and air by using photocatalytic materials has attracted great attention. TiO 2 photocatalyst is
most promising for this purpose because of its favorable physical and chemical properties as well as its low cost, chemical stability, and nontoxicity.
TiO 2 exhibits, however, photocatalytic activity only under UV irradiation because of its relatively wide band gap energy, and attempts to obtain
visible-light sensitive photocatalysts have been made in recent years. Previously, we reported that nitrified Si-doped titanias exhibited relatively high
photocatalytic activities under visible-light irradiation [1] and that the Fe addition to the N- and Si-codoped titanias markedly improved the
activities [2]. In this study, the effects of Fe source and thermal treatment on the photocatalytic activity under visible-light irradiation of Femodified
N- and Si-codoped titanias were examined.
Results
Si-doped titanias were synthesized by a glycothermal method and the products were treated in an NH 3 flow at high temperature to obtain N-
and Si-codoped titanias, and Fe loading on them was carried out by an impregnation method using Fe(acac) 3 and Fe(NO 3 ) 3 solutions. After
calcination at high temperatures, the photocatalytic decomposition of acetaldehyde under visible-light irradiation was examined.
To decompose the iron precursors after the impregnation, thermal treatment higher than 300 ºC was required. However, when the samples were
treated at temperatures higher than 400 ºC, the photocatalytic activity decreased gradually. The catalysts prepared by using Fe(acac) 3 showed
slightly higher activities compared to those prepared with Fe(NO 3 ) 3 . UV-vis spectra suggested the dispersion of Fe species was different according
to the Fe sources and the thermal treatment temperature. The catalysts were also characterized by XRD, XPS, XAFS and TPR, and the relationship between
the structure of Fe species and the photocatalytic activity is discussed.
Justification for acceptance
Purification of air and water using photocatalytic materials attract great attention recently. In this paper, we report enhanced visible-light sensitive
photocatalytic activities of Fe-modified N- and Si-codoped titanias. The catalyst components are inexpensive and harmless, indicating that the present catalyst
has a high potential for practical applications. We think, therefore, this presentation will provide significant contribution in the ICEC.
References
[1] H. Ozaki, et al., J. Mater. Sci., 42 (2007) 4007.
[2] H. Ozaki, et al., J. Phys. Chem. C, 111 (2007) 17061.

385 Carbon nanotube-TiO 2 materials for visible-light-driven heterogeneous photocatalysis
C. G. Silva, J. L. Faria*
Laboratório de Catálise e Materiais, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias s/n 4200-465 Porto, Portugal
*Corresponding author. Tel: +351 225 081 465, Fax: +351 225 081 449, e-mail: jlfaria@fe.p.pt
Background
Embedding carbon nanotubes (CNT) in TiO 2 matrices has become an attractive method to produce materials for heterogeneous photocatalysis. A careful control
of CNT electronic, adsorption, mechanical and thermal characteristics [1] can produce biphasic materials with remarkable catalytic properties for use with solar
radiation. In this aspect CNT can compete with activated carbon [2] because of the possibility of specifically control its surface chemistry. This will widespread
the possibility of producing new photocatalysts for solving environmental problems, especially for removing toxic chemicals from waste waters [3]. Here we
report the preparation, characterization and test of multi-walled CNT-TiO 2 composite catalysts in visible-light-driven heterogeneous photocatalysis of solutions
containing phenol like compounds to mimic environmental hazardous aromatics.
Results
XRD analysis of both TiO 2 and CNT-TiO 2 catalysts revealed the sole presence of anatase phase with crystallite dimensions of 8.5 and 9.9 nm, respectively. TEM
images of CNT-TiO 2 composite shows CNT dispersed in a non-agglomerated TiO 2 matrix with a large surface area. Catalysts were tested in the photocatalytic
oxidation of phenol and 4-chlorophenol in aqueous solutions at a discrete range of visible spectral wavelengths ( exc of 366, 436 and 546 nm). HPLC analysis
confirmed the occurrence of substituted poly-hydroxy aromatics and chloroaromatics, suggesting that HO • radicals are the primary oxidizing species involved in
the process. The introduction of CNT into the TiO 2 matrix produced a synergy effect in the photocatalytic degradation with an increase in both reaction rate
constant and total organic carbon removal. This synergy is ascribed to CNT acting as a dispersion media for TiO 2 particles as well as a photosensitizer agent.
Justification for acceptance
The search for novel photocatalysts capable of acting in the visible spectral region is of extreme importance in the field of catalysis for clean air and water. CNT-
TiO 2 composites revealed to be very efficient in the photocatalytic oxidation of phenol and 4-chlorophenol like molecules.
Acknowledgments: The authors gratefully acknowledge FCT and FEDER for financial assistance (fellowship SFRH/BD/16966/2004 and projects POCI/EQU/58252/2004 and
POCTI/1181/2003).
References
[1] P. Serp, M. Corrias, P. Kalck, Appl. Catal. A 253 (2003) 337.
[2] J. Matos, J. Laine, J.-M. Herrmann, J. Catal. 200 (2001) 10.
[3] C.G. Silva, W. Wang , J.L. Faria, J. Photochem. Photobiol. A 181 (2006) 314.
391 Study of the “anatase / electrolyte solution” Interface: Streaming Potential Measurements and Potentiometric Titrations
N. Spanos,*, A. Tsevis and G. Kamarianakis
School of Science and Technology, Hellenic Open University,Patras,GR26223,Greece
*Corresponding author. Tel: +30 2610 367525, Fax: +30 2610 367520, e-mail: nspanos@eap.gr
Background
The study of the electrical double layer (EDL), developed in the titania/electrolyte solution interface, is of paramount importance in photocatalytic processes,
photoelectrochemistry and photovoltaic cells. The characteristic parameters of the EDL, such as surface charge, potential, surface conductivity, and mobility of
the counter ions behind the shear plane, play an important role in the applications mentioned above. These parameters may be determined either in suspensions
by potentiometric titrations and microelectrophoresis, or in closely packed plugs by streaming potential measurements [1]. In the present work a combined study
was undertaken both in suspension and in closely packed particles of anatase.
Results
Anatase was prepared from titanium isopropoxide using the sol-gel method. The resultant solid was characterized by powder XRD and SEM. It was found that
the point of zero charge (pzc) may be determined by the intersection point of the suspension and blank titration curves, obtained at one ionic strength value.
Moreover, it was found that the surface charge may be easily determined at various pHs by subtracting blank titration curve from that of suspension. Concerning
surface conductivity, it was found to increase as pH draws away from pzc=6.3, due to the increased surface charge which causes an increase in the amount of the
counter ions and therefore in the conductivity due to these ions. As regards the mobility of the counter ions behind the shear plane, it was found to decrease as
pH draws away from pzc. This trend should be attributed to the increase of the surface charge, as pH draws away from pzc, which results in stronger electrostatic
interactions between the surface of the solid and the counter ions behind the shear plane, rendering these ions less mobile. Finally, it was found that surface
conductivity plays an important role in the calculation of potential, especially at relatively low ionic strength values. The interrelation of potential with ionic
strength revealed a spurious maximum. This maximum disappears and the absolute value of potential diminishes with increasing ionic strength, in the case of
potential calculated considering the total surface conductivity [2].
Justification for acceptance
The enhancement of the photocatalytic activity of titania or titania supported catalysts by adjusting the EDL parameters, in order to regulate the adsorptivity of
various pollutants in liquid-solid systems, as well as the catalysts preparation with the optimum dispersion of the supported on titania phase, is the aim of this
work.
References
[1] N. Spanos, P.G. Klepetsanis, P.G. Koutsoukos, in Encyclopedia of Surface and Colloid Science (Editor: Dr. Arthur Hubbard) Marcel Dekker Inc., New York,
2002.
[2] R.W. O’ Brien, J. Colloid Interface Sci. 110 (1986) 477.

432 Simplification method for the fast simulation of catalyst models with surface reactions
R. Möller a* , M. Votsmeier b , C. H. Onder a , L. Guzzella a , J. Gieshoff b
a Department of Mechanical and Process Engineering ETH Zurich, 8092 Zurich, Switzerland
b Umicore AG & Co. KG, Rodenbacher Chaussee 4, D-63403 Hanau
* Corresponding author. Tel: +41 44 632 79 28, Fax: +41 44 632 11 39, e-mail: roman.moeller@imrt.mavt.ethz.ch
Background
Parameter optimization of catalyst simulation models is an important class of problems, which is often limited by computing power. A problem of this kind is the
estimation of unknown rate parameters by minimizing the error between measurement data and simulation results. The higher the number of unknown
parameters, the greater becomes the number of simulations requiring to be performed, which can easily reach tens of thousands. To do such optimizations within
a reasonable time, a very fast and robust simulation is essential. In this investigation a model simplification method is discussed that is designed to achieve this
goal. Its application to the case of a three-way catalyst is presented as well.
Results
One-dimensional catalyst models often consist of a set of partial differential equations for the gas species in the channel, the gas species in the washcoat, and the
surface species. The idea investigated here is to reduce the model order by replacing the dynamic equations of all gas species by quasi-stationary approximations.
First, the required formulation of the dynamic equations and the conditions necessary for the validity of the simplification are discussed. The main goal of
improving the simulation speed is only achieved if an explicit analytical solution of the quasi-stationary approximation exists. Therefore it is shown how this can
be calculated in an automated way using a software for symbolic calculations such as Mathematica and the conditions are analyzed when an explicit solution is
guaranteed.
Together with some other model simplifications and a robust integration algorithm this simplification method was then used in a simulation of a three-way
catalyst. The model of the three-way catalyst is based on a 14 forward/backward reaction step surface mechanism. This simulation is capable of simulating the
catalyst during a FTP75 cycle approximately 100 times faster than real-time on a 3GHz PC.
Simulation results of the three-way catalyst model are demonstrated for various tolerance settings and with and without the suggested simplifications. A number
of computation timings are given.
Justification for acceptance
Multi-parameter optimization is usually only feasible if very fast simulation models are available. The simplification method discussed in this presentation can be
applied on a wide range of surface reaction models and is therefore interesting in the context of catalyst modelling.
446 Ba-incorporated mesoporous MCM-41 synthesis and characterization
E. KAYA a , N. OKTAR a* , G. KARAKAS b , K. MURTEZAOGLU a
a Chem. Eng. Dep., Gazi Univ., Maltepe, Ankara, Turkey
b Chem. Eng. Dep., METU, Ankara, Turkey
*Corresponding author. Tel:490 312 231 74 00/2556, e-mail: nurayoktar@gazi.edu.tr
Background
Nitrogen oxides (NOx) are the generic term for a group of highly reactive gases, all of which contain nitrogen and oxygen in varying amounts. Removing of NOx
from exhaust gases is challenging problem which has been extensively studied worldwide in recent years. The NOx emission is a major cause for the formation
of acid rains and for other environmental problems [1, 2]. The aim of this study is to develop the Ba-incorporated, MCM-41 supported adsorbent that has a high
adsorption capacity for trapping of the NOx gases. MCM-41 is a member of mesoporous M41S family, noticed with having high surface areas and narrow poresize
distributions [3].
Results
In this study, comparison of direct hydrothermal synthesis and wet impregnation method were performed for synthesis of Ba-incorporated MCM-41 supported
adsorbents. XRD, nitrogen adsorption-desorption analysis (BET-BJH), TGA-DSC, FTIR and SEM-EDS analysis were used for determining the structural and
physical properties of synthesized materials. XRD patterns showed that crystal structure of MCM-41 was achieved and high surface areas were obtained. For the
synthesis method investigated, besides silicate formation barium oxide and barium nitrate species were observed in the high angle region XRD patterns. XRD
patterns also revealed the differences between synthesis methods. The adsorbents prepared by hydrothermal synthesis were in crystalline phase, however the
adsorbents prepared by wet impregnation method demonstrated an amorphous phase formation. All adsorbents exhibited type IV isotherm except the adsorbents
prepared by wet impregnation method which had demonstrated hysteresis effect. In impregnation method, citric acid was added to impregnation solution in
different amounts. It was observed from the characterization studies that adsorbents prepared by addition of citric acid had higher surface areas and more
homogeneous pore size distribution had been obtained. In the case of citric acid addition higher pore volume was also achieved.
Justification for acceptance
A novel application of mesoporous MCM-41 as a support is in NOx adsorbents. Ba-incorporated MCM-41 is also prepared by a novel technique which involves
Ba incorporation using direct hydrothermal synthesis method. This work is a forerunner for other synthesis and characterization studies of Ba-incorporated
MCM-41.
References;
[1] EPA, Office of Air Quality Planning & Standards, “NOx-How Nitrogen Oxides Affect the Way We Live and Breathe”, http://www.epa.gov/oar/urbanair/nox/index.html,
1998.
[2] Dabrowski, A., “Adsorption - from theory to practice”, Advances in colloid and interface science 93 (1-3): 135-224, 2001.
[3] Taguchi, A., Schüth, F., “Ordered mesoporous materials in catalysis”, Microporous and mesoporous materials, 77: 1-45 (2005).

447 Characterization of Nb 2 O 5 -ZrO 2 mixed oxides synthesized from Nb(V) peroxo precursor as novel solid acids
M. Kantcheva a* , O. Samarskaya a , I. Cayirtepe a , H. Butunoglu a , G. Ivanov b and A. Naydenov b
a Department of Chemistry, Bilkent University, 06800 Bilkent, Ankara, Turkey
b Institute of General and Inorganic Chemistry, BAS, Sofia 1113, Bulgaria
*Corresponding author. Tel: +90 312 290 2451, Fax: +90 312 266 4068, e-mail: margi@fen.bilkent.edu.tr
Background
Supported Nb 2 O 5 catalysts are usually prepared by impregnation using different niobium precursors. Niobium oxalate and its ammonium complexes are
easy to handle and have fairly low prices. In contrast to these precursors, the peroxoniobium(V) compounds have high solubility in water and are suitable for
catalyst preparation. Here, we report the results of structural and surface characterization of Nb 2 O 5 -ZrO 2 system prepared by impregnation of ZrO x (OH) 4-2x with
acidic solutions (pH~0.5 ) containing [Nb 2 (O 2 ) 3 ] 4+ ions. The precursor solutions were taken in concentrations ensuring various ZrO 2 :Nb 2 O 5 mole ratios (Table 1).
Results
Table 1. Nominal Nb loading and phase composition
Sample Nb Mole ratio Crystallographic phases
wt% ZrO 2 :Nb 2 O 5
1NbZ 1 150:1 t-ZrO 2 +m-ZrO 2
5NbZ 5 30:1 t-ZrO 2 +m-ZrO 2
10NbZ 10 15:1 t-ZrO 2
15NbZ 15 10:1 t-ZrO 2 +Zr 6 Nb 2 O 17
19NbZ 19 8:1 t-ZrO 2 +Zr 6 Nb 2 O 17
25NbZ 25 6:1 Zr 6 Nb 2 O 17
30NbZ 30 5:1 Zr 6 Nb 2 O 17
32NbZ 32 4.8:1 t-ZrO 2 +Zr 6 Nb 2 O 17 +Nb 2 O 5
38NbZ 38 4:1 t-ZrO 2 +Zr 6 Nb 2 O 17 +Nb 2 O 5
(t: tetragonal; m: monoclinic)
Absorbance
0.2
30NbZ
25NbZ
19NbZ
10NbZ
5NbZ
ZrO 2
1680 1640 1600 1560 1520
Wavenumber [cm -1 ]
Fig. 1. FT-IR spectra of lutidine
(2.5 mbar) adsorbed at RT after the
evacuation at 423 K for 15 min.
Table 1 shows the crystallographic phases in the samples detected by XRD. The Raman spectra confirm that the materials with Nb loading up to 30 wt %
do not contain crystalline Nb 2 O 5 . The formation of Zr 6 Nb 2 O 17 is favored by the partial solubility of hydrated zirconia in H 2 O 2 solution.
The FT-IR spectra of adsorbed lutidine (Fig. 1) reveal that the amount of Brønsted acid sites reaches maximum for the sample with ZrO 2 :Nb 2 O 5 mole
ratio of 6:1 corresponding to a pure phase of Zr 6 Nb 2 O 17 . This material does not possess Lewis acidity and has sufficient amount of Brønsted acid sites necessary
for the stabilization of dispersed Pd(II) species. The catalytic properties of Zr 6 Nb 2 O 17 promoted with 0.1 wt% of Pd(II) were evaluated in the SCR of NO x with
propene. To the best of our knowledge, there are no reports dealing with the surface acidity of Zr 6 Nb 2 O 17 and the potential of Pd/Zr 6 Nb 2 O 17 as a SO 2 -tolerant
catalyst.
448 Photocatalytic Waste Waters Treatment from Pharmaceutical Industries
E. M. Méndez a *, M. V. Lemus Salazar, J. E. Zaldaña Gómes
a Universidad de El Salvador Facultad Multidisciplinaria de Occidente
* Corresponding autor: Tel: (503) 2484-0951, Fax (503) 2440-0352, e-mail eemendezsv@hotmail.com
Abstract
The degradation of organics pollutants in water by photocatalysis, using semiconductors, such as TiO 2 and ZnO, has attracted extensive attention during recent 20
years [1]. Previous studies have proved that such semiconductors can degrade most kinds of persistent organics pollutants, such as detergents, dyes, pesticides,
aromatics compounds, among others by UV-light irradiation [2-5].
A wide variety of pharmaceutical industries introduce into the waste water systems from various sources chemical compounds persistent to natural degradation
such as phenol and their derivatives. These have been the cause of much concern to societies and regulating authorities around the word [6]. The biodegradation,
which is the major mechanism in the waste-water treatment, is inefficient at the low level of the susbtrate and photochemical oxidation processes such as
ZnO/UV or TiO 2 /UV have therefore been applied for the treatment of these waste waters.
Results
Two production lines from a local pharmaceutical laboratory were considered for the treatment of the waste waters produced. One line produce the
pharmaceutical product namely Syrup Ambroxol which is a formulation based in dextromethorphan like active principle, the other one lines selected produce the
pharmaceutical product Oraldex which is an oral serum based in electrolytes and glucose. The waste water obtained from the two production lines were irradiated
with a xenon arc lamp of 150 W in the presence of colloidal ZnO, in both case were observed a decay of the UV_VIS absorption band of the spectrum as the time
of irradiation lapsed. First-order reaction rates were obtained for the two waste waters studied with rate constants of 0.006 s -1 and 0.004 s -1 for ambroxol and
oraldex formulations respectively. Chemical and microbiologist analysis were carry out for the two waste waters to know the quality of the waters before and
after the treatment. The microbiologist parameters analyzed were total coliforms, thermo tolerant coliforms and E. coli, the physical chemical parameters were
truth color, turbidity, pH, hardness, total iron, manganese, sulfate and zinc, these parameters were compared with the salvadorean norm of drinking quality waters
and all of them completed the salvadoream norm. These results are considered very important because to satisfy the drinking quality water norm it is necessary
that advanced oxidation processes to be efficient and the photocatalytic processeses using ZnO as photocatalyts is one of them.
References
[1] M. R. Hoffmann, S. T. Martin, W. Y. Choi, D. W. Bahnemann, Chem. Rev. 95 (1995)
69.
[2] P. Qu. J. C. Zhao, T. Shen. H. Hidaka. J. Mol. Cat. Part A. Chem. 129 (1998) 257.
[3] A. L. Linsebigler, G. Q. Lu, J. T. Yates Jr. Chem. Rev. 95 (1995) 735.
[4] T. Torimoto, S. Ito, S. Kuwabata, H. Yoneyama, Environ. Sci. Technol. 30 (1996) 1275.
[5] R. M. Dowd, M. P. Anderson, in : proceeding Monitoring of the Second National Oudoor
Action Conference on Aquifer Restoration, Groundwater Geophysical Association, Method,
National Water Well, Dublin, 1988.
[6] Z. Cohen, C. Eiden, M. N. Lober, in: Evaluation of Pesticide in Groundwater, ACS Symp. 1986.

478 Modeling exploration of the relationships between meteorological parameters and homogeneous nucleation
in the continental boundary layer over China
Enagnon A. GBAGUIDI a, b* , Jinnan CHEN a* , Zifa WANG b and Chao GAO b
(a) School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing, China
(b) LAPC/NZC, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing
(*)Corresponding authors: Jinnan Chen, email: jnchen68945980@126.com
Background
Homogeneous nucleation is an important source of sulfate aerosols. Understanding nucleation event is an important issue in understanding aerosols contribution
to atmosphere radiative fluxes and climate change process. The use of coal for industrial activities in China results in important sulfate aerosols loading over the
country which becomes the biggest in sulfur dioxide and sulfate aerosols emissions source in the world. Thus, China is a strong laboratory for homogeneous
nucleation study.
Results
The influence of meteorological parameters (temperature, relative humidity, solar radiation and cloud cover) on homogeneous nucleation process in the Chinese
continental boundary layer in January 2004 is examined using US/EPA Models-3 CMAQ modeling system coupled with the Mesoscale Model MM5. Results
indicate seven event days, 5 th , 6 th , 9 th , 13 th , 20 th , 26 th and 27 th detected in daytime over southern and western China under specific meteorological condition
such as: temperature288K, solar radiation600W/m2, 40 relative humidity52% and 0 cloud fraction 0.25 and weak preexisting particles surface area. The
new particles formation process suggests an ultra dominance of ternary nucleation. This highlights the key role of atmospheric ammonia in homogeneous
nucleation over China. Estimating nucleation parameter values shows the importance of relative humidity, greater than water molecule in the nucleation process.
The nucleated sulfate particles increase sulfate aerosols loading in the Chinese boundary layer and may reinforce sulfate reflexion of solar radiation.
Justification of acceptance
This paper analyzing the homogeneous nucleation over Chinese boundary layer, contributes to provide insights into the physico-chemical processes of sulfur
transformation into sulfate aerosols and thereby its consequence on surface air temperature changes via increasing of direct and indirect radiative effects. This is
important in understanding the potential role sulfate aerosols can play as catalysis in compensating green house effect at regional and global scale in the context
of global warming that is one of important sessions for ICEC.
References
(1) Anttila, H. Vehkamaki, I. Napari and M. Kulmala, (2005), Effect of ammonium bisulfate formation on atmospheric water-sulfuric acid-ammonia nucleation.
Boreal Environment Research 10.
(2) Birmilli, W. and Wiedensohler, A.,(2000), New particle formation in the continental boundary layer: Meteorological and gas phase parameter influence,
Geophys. Res. Let., 27, 3325–3328.
481 A Characterization Study of CeO 2 and Carbon Supported AgCu and FeNi Bimetalics:
Search for Their Potential as Anode Electrodes in DEFC
Background
N.A. Tapan a , * Ö. Yldz a
a Gazi University, Faculty of Engineering and Arthitecture, Chemical Engineering Department,06570,Maltepe, Ankara/TURKEY.
*Corresponding author. Tel: +90 312 2317400/2545, Fax : +90 312 230 8434 e-mail: atapan@gazi.edu.tr
In order to understand the electrochemical activity of non platinum based electrocatalysts towards etanol electrooxidation, an electrochemical study was
performed on carbon and cerium oxide supported FeNi and AgCu bimetalics prepared by wet impregnation, coprecipitation and ion exchange techniques.
Supported bimetallics were compared and analyzed by voltammetric techniques , BET, TPR and direct ethanol fuel cell anode polarization. It is decided that
AgCu/CeO 2 samples reduced under H 2 atmosphere at 400 o C has an application potential as anode electrode in direct ethanol fuel cell.
Results
Cerium oxide based AgCu exhibit changes in electrochemical activity in ethanol containing electrolyte environment and electrical conductivity after reduction in
H 2 atmosphere. AgCu/CeO 2 reduced at 400 o C when mixed with Pt/C has a potential as an anode electrode in direct alcohol fuel cell. Although most of the
reduced cerium oxide based samples show a decrease on the anodic peak currents in ethanol containing electrolyte environment, %50 Cu and %50 Ag /CeO 2
,reduced at 400 o C show an opposite behaviour in cyclic voltammetric studies.
Justification for acceptance
In this systematic study, cheap transition metals Ag, Cu, Fe, Ni were selected[1] and potentials of supported AgCu and FeNi samples as anode electrodes in
direct alcohol fuel cells were investigated with the aid of characterization tools like cyclic voltammetry, electrical conductivity measurements, BET and fuel cell
anodic polarization.
References
[1] U. B.,Demirci, Journal of Power Sources 173 (2007)11.