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Kiss, Rothenberg and Dimian 413Preparation of Cs2.5 catalyst [Cs 2.5 H 0.5 PW 12 O 40 ].Cs 2 CO 3 (1.54 g, 10 ml, 0.47 M) aqueous solution were added dropwise toH 3 PW 12 O 40 (5 ml, 10.8 g, 0.75 M aq. sol.). Reaction was performed at roomtemperature and normal pressure while stirring. The white precipitate was filteredand aged in water for 60 hours. After aging, the water was evaporated in an oven at120 o C. White solid glass-like particles of Cs 2.5 H 0.5 PW 12 O 40 (9.0375 g, 2.82 mmol)were obtained.Table 3. Catalyst characterization.Catalyst sampleSurfaceareaPore volumePore diametermax./mean/calc.SulfurcontentCs 2.5 H 0.5 PW 12 O 40 163 m 2 /g 0.135 cm 3 /g 2 / 5.5 / 3 nm N/AZrO 2 /SO 2- 4 / 650°C 118 m 2 /g 0.098 cm 3 /g 4.8 / 7.8 / 7.5 nm 2.3 %TiO 2 /SO 2- 4 / 550°C 129 m 2 /g 0.134 cm 3 /g 4.1 / 4.3 / 4.2 nm 2.1 %SnO 2 /SO 2- 4 / 650°C 100 m 2 /g 0.102 cm 3 /g 3.8 / 4.1 / 4.1 nm 2.6 %Catalyst characterization.Characterization of mixed metal oxides was performed by atomic emissionspectroscopy with inductively coupled plasma atomisation (ICP-AES) on a CEInstruments Sorptomatic 1990. NH 3 -TPD was used for the characterization of acidsite distribution. SZ (0.3 g) was heated up to 600 °C using He (30 ml min –1 ) toremove adsorbed components. Then, the sample was cooled at room temperature andsaturated for 2 h with 100 ml min –1 of 8200 ppm NH 3 in He as carrier gas.Subsequently, the system was flushed with He at a flowrate of 30 ml min –1 for 2 h.The temperature was ramped up to 600 °C at a rate of 10 °C min –1 . A TCD was usedto measure the NH 3 desorption profile. Textural properties were established from theN 2 adsorption isotherm. Surface area was calculated using the BET equation and thepore size was calculated using the BJH method. The results given in Table 3 are ingood agreement with various literature data. Indeed, stronger acid sites lead to highercatalytic activity for esterification.Catalyst leaching. The mixture may segregate leading to possible leaching of sulfategroups. The leaching of catalyst was studied in organic and in aqueous phase. First, asample of fresh SZ catalyst (0.33 g) was stirred with water (50 ml) while measuringthe pH development in time. After 24 h, the acidity was measured by titration withKOH. The suspension was then filtered and treated with a BaCl 2 solution to test forSO 2– 4 ions. In a second experiment, the catalyst was added to an equimolar mixtureof reactants. After 3 h at 140 °C, the catalyst was recovered from the mixture, driedat 120 °C and finally stirred in 50 ml water. The pH was measured and thesuspension titrated with a solution of KOH. SO 2–4 ions in the suspension weredetermined qualitatively with BaCl 2 . In a third experiment, the procedure wasrepeated at 100 °C when the mixture segregates and a separate aqueous phase isformed. From the leaching tests it can be concluded that SZ is not deactivated byleaching of sulfate groups when little water is present in the organic phase but it iseasily deactivated in water or aqueous phase. There are several methods to preventaqueous phase formation and leaching of acid sites: 1) use an excess of one reactant,
414“Green” Catalysts for Biodiesel2) work at low conversions, and 3) increasing the temperature exceeding the boilingpoint of water to preserve the catalyst activity and drive reaction to completion.Selectivity and side reactions. Typically, the alcohol-to-acid ratio inside an RD unitmay vary over several orders of magnitude. Especially for stages with an excess ofalcohol, the use of a SAC may lead to side reactions. Selectivity was assessed bytesting the formation of side products in a suspension of SZ in pure alcohol underreflux for 24 h. No ethers or dehydration products were detected by GC analysis.AcknowledgementsWe thank M.C. Mittelmejer-Hazeleger and J. Beckers for technical support, and theDutch Technology Foundation STW (NWO/CW Project Nr. 700.54.653) andcompanies Cognis, Oleon, Sulzer, Uniquema, Engelhard for financial support.Acknowledgment is made to the Donors of The American Chemical SocietyPetroleum Research Fund, for the partial support of this activity.References1. F. Maa and M. A. Hanna, Bioresource Technol., 70, 1 (1999).2. B. Buczek and L. Czepirski, Inform, 15, 186 (2004).3. A. Demirbas, Energy Exploration & Exploitation, 21, 475 (2003).4. W. Körbitz, Renewable Energy, 16, 1078 (1999).5. M. A. Harmer, W. E. Farneth and Q. Sun, Adv. Mater., 10, 1255 (1998).6. J. H. Clark, Acc. Chem. Res., 35, 791 (2002).7. K. Wilson, D. J. Adams, G. Rothenberg and J. H. Clark, J. Mol. Catal. A:Chem., 159, 309 (2000).8. F. Omota, A. C. Dimian and A. Bliek, Chem. Eng. Sci., 58, 3175 & 3159 (2003).9. T. Okuhara, Chem. Rev., 102, 3641 (2002).10. M. A. Harmer and V. Sun, Appl. Catal. A: Gen., 221, 45 (2001).11. S. Ardizzone, C. L. Bianchi, V. Ragaini and B. Vercelli, Catal. Lett., 62, 59(1999).12. H. Matsuda and T. Okuhara, Catal. Lett., 56, 241 (1998).13. M. A. Harmer, Q. Sun, A. J. Vega, W. E. Farneth, A. Heidekum and W. F.Hoelderich, Green Chem., 2, 7 (2000).14. G. D. Yadav and J. J. Nair, Micropor. Mesopor. Mater., 33, 1 (1999).15. M. A. Ecormier, K. Wilson and A. F. Lee, J. Catal., 215, 57 (2003).16. Y. Kamiya, S. Sakata, Y. Yoshinaga, R. Ohnishi and T. Okuhara, Catal. Lett.,94, 45 (2004).17. R. Koster, B. van der Linden, E. Poels and A. Bliek, J. Catal., 204, 333 (2001).18. H. G. Schoenmakers and B. Bessling, Chem. Eng. Prog., 42, 145 (2003).19. R. Taylor and R. Krishna, Chem. Eng. Sci., 55, 5183 (2000).20. H. Subawalla and J. R. Fair, Ind. Eng. Chem. Res., 38, 3696 (1999).21. A. A. Kiss, A. C. Dimian, G. Rothenberg, Adv. Synth. Catal., 348, 75 (2006).
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Catalysis ofOrganic Reactions
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62. Catalysis of Organic Reactions,
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108. Metal Oxides: Chemistry and Ap
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CRC PressTaylor & Francis Group6000
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xiii14. The Transformation of Light
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xviien Catalisis y Petroquimica (UN
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xix56. Transition Metal Removal fro
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xxiiiChronology of Organic Reaction
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To Zsuzsanna and Tim
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Jones et al. 31. On the Use of Immo
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Jones et al. 5three-phase tests in
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Jones et al. 7In the HKR of rac-epi
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Jones et al. 9term performance char
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Jones et al. 115. A. S. Gruber, D.
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Moses et al. 132. Supported Re Cata
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Moses et al. 15perrhenate, followed
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Moses et al. 17SnCOSnMe 4≡SiOReO
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Moses et al. 19(AlOSi) of the cube.
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Moses et al. 212.510 3 k obs / s -1
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Wang et al. 233. Catalytic Hydrogen
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Wang et al. 25The rate expressions
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32Halophosphite LigandsIn 1970, Pru
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34Halophosphite LigandsThe ligands,
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36Halophosphite LigandsTable 2 Temp
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38Halophosphite Ligands3. P. W. N.
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40Monolithic Bioreactorstrength for
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42Monolithic BioreactorMenten equat
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Gőbölös et al. 456. Highly Selec
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Gőbölös et al. 47was practically
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Gőbölös et al. 49noteworthy that
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Gőbölös et al. 51Figure 2 NMR sp
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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68Synthesis of MIBKwe examined the
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70Synthesis of MIBK1412Conversion (
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72Synthesis of MIBK4,4’-dimethyl
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74Synthesis of MIBKobtained for MIB
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Ardizzi et al. 7710. The Control of
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Ardizzi et al. 79type acidity at th
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Ardizzi et al. 81procedure describe
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84Phenol Benzoylationconsecutive Fr
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86Phenol BenzoylationThis does not
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92Oxidation with Microchannel Immob
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100 Propylene Partial OxidationThe
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102 Propylene Partial OxidationSiO
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104 Propylene Partial Oxidation0.01
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106 Propylene Partial Oxidation0.02
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108 Propylene Partial OxidationRefe
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110Oxidation of n-Pentanemethacryli
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112Oxidation of n-PentaneFReqox1ox2
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114Oxidation of n-Pentanethe presen
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116Oxidation of n-PentaneIn the mec
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118Oxidation of n-PentaneReferences
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120TEMPO Oxidation of Alcoholsthe u
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122TEMPO Oxidation of AlcoholsThe r
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124TEMPO Oxidation of Alcoholsany d
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126TEMPO Oxidation of Alcoholsconce
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128TEMPO Oxidation of AlcoholsMNT :
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130TEMPO Oxidation of Alcoholsuptak
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132Aminoalcohols to Aminocarboxylic
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142Bromine-Free TEMPO-Based Catalys
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148CO OxidationP25 TiO 2 , respecti
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150CO Oxidation0.02(a)21802110(b)21
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152CO Oxidationcarboxylate species
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Yamauchi 15519. 2006 Murray Raney A
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Yamauchi 157transformation is schem
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Yamauchi 159The X-ray diffraction p
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Yamauchi 161was -0.0009, -0.0032 an
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Yamauchi 163shown in Fig. 12. It wa
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168Nitrobenzene Hydrogenationfurthe
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170Nitrobenzene Hydrogenationhydrog
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176Nitrobenzene Hydrogenation10. G.
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178 Hydrogenation of Dehydrolinaloo
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188Modeling Mass Transfer Hydrogena
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198 Fructose HydrogenationHOHCCH 2O
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200 Fructose HydrogenationTable 1.
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202 Fructose Hydrogenationmmol form
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206 Fructose Hydrogenationcleave th
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208 Fructose Hydrogenationfulfills
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Kuusisto, Mikkola and Salmi 237100A
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242 1-Phenyl-1-Propyneof cis-β-met
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244 1-Phenyl-1-Propynealkene. When
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Cao, White, Wang and Frye 28933. Se
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294Chiral Ferrocene Ligandsnew Twin
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296Chiral Ferrocene LigandsTable 1.
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298Chiral Ferrocene Ligandsprevents
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300Chiral Ferrocene LigandsConclusi
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302Chiral Ferrocene Ligandsextracte
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304 Catalyst Library DesignIn gas p
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306 Catalyst Library Designd−(b 0
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310 Catalyst Library DesignD in com
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314 Catalyst Library Design27. S. H
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318 Dendrimer TemplatesThe differen
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322 Dendrimer TemplatesThe 100 cm -
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328Rearrangement of 3,4-Epoxy-1-But
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3382,5-Dimethyl-2,4-Hexadieneharves
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348Heteropoly AcidsSOOO O+ +OS1 2 3
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350Heteropoly AcidsTable 3. Acylati
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352Heteropoly AcidsSiO 2 is the bes
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Page 443 and 444: 416 Production of BiodieselTable 1.
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Page 488: Riermeier et al. 461References1. I.
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464 Chiral 2-Amino-1-Phenylethanolp
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466 Chiral 2-Amino-1-PhenylethanolI
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468 Chiral 2-Amino-1-Phenylethanola
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470 t-Butanol DehydrationResults an
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472 t-Butanol Dehydrationcomprises
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482 Reductive AlkylationSince the p
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504 Electroreductive Catalytic Ullm
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Catalysis of Organic Reactions 507A
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Catalysis of Organic Reactions 509K
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Catalysis of Organic Reactions 511T
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514 Keyword Indexcarboncarbon dioxi
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516 Keyword Indexethanolamine 16 13
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518 Keyword IndexNi, activated 25 2
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520 Keyword Indexsuccinimido ketone
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