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Liu, Cant and Smith 139an exact fit at the maximum but at the expense of worse fit at the extremes. Only asmall fraction of the apparent increase in rate at high conversion can be explained interms of an increase in the ratio of catalyst weight to liquid volume as liquid samplesare removed for analysis. Most of the discrepancy must arise from another cause.One possibility is that the difference in rate constant between DEA and HEG arises,at least in part, because they compete for catalyst surface with HEG beingdisfavoured when its mole fraction is low, perhaps because it lacks the second OH asan attachment point to the surface. In this case the reduced concentration of DEA athigh conversion would permit greater access by HEG leading to a faster end stagereaction.Table 4. Estimated values for k 1 and k 2 for the reaction of diethanolamineCu catalyst Cu-Cr catalystk 1 , L g -1 h -1 0.009 0.013k 2 , L g -1 h -1 0.004 0.009ConclusionsThe oxidative dehydrogenation of alcohols over skeletal copper catalysts exhibits awide range of rates. Inductive effects can account for some of the differences butother factors, possibly related to binding between nitrogen atoms and the surface, arealso present. Diethanolamine reacts sequentially with 2-hydroxyethylglycine as anintermediate. Changes in mole fraction, measured by 1 H NMR, during much of thereaction can be modeled according to sequential first order kinetics but the finalstages of reaction are faster than predicted.Experimental SectionUnpromoted and chromia-promoted skeletal copper catalysts were prepared asdescribed in detail previously (10, 11, 14, 15) by leaching a CuAl 2 alloy, sieved to106-211µm, in a large excess (500 mL) of 6.1 M NaOH, either alone or containingNa 2 CrO 4 (0.004 M), for 24 hours at 5°C.Each batch of catalyst was characterised as to BET surface area, Al content,Cr 2 O 3 content, and tested in the modified autoclave described earlier (10). Thiscomprised a 300 mL stainless steel autoclave (Parr Inst. Co., series 4560) modifiedwith a side valve connected to an independently heated stainless steel cylinder(150 mL). Each sample of catalyst (~9 g) was first pretreated in the autoclave in ~9.7M NaOH at 200°C for 6 hours. After cooling it was washed with distilled water anda second quantity of NaOH solution (identical to the above) added. The autoclavewas flushed with N 2 and pressurised to ~2 bar at room temperature. The temperaturewas brought to near the desired reaction temperature (160°C, ~6 bar) on a linearramp over a period of 45 minutes with the stirrer operating at 80 rpm. 60-70mL ofalcohol was preheated in the reservoir to a matching temperature and then introducedusing N 2 at >10 bar as a driving gas. The alcohols tested were obtained fromcommercial sources with minimum stated purities of at least 95% (97% or more inmost cases).
140Aminoalcohols to Aminocarboxylic Acid SaltsThe reaction was followed continuously by measurement of H 2 vented, throughan electronic pressure controller (Rosemount Inst, model 5866) set at 9 bar, using awet gas meter. Liquid samples, of 0.5 mL each, preceded by 0.5 mL to flush the line,were removed for NMR analysis at times corresponding to a spread of conversionsfrom 10 to 90% as estimated from the cumulative hydrogen evolution. Spectra wererecorded on 0.1 mL samples accurately diluted with 0.5 mL of D 2 O containing0.05% DSS (2,2-dimethyl-2-silapentane-5-sulfonate, sodium salt) as an internalstandard using a Bruker DPX-300 spectrometer operating at 300 MHz for protons.AcknowledgementsThis work was supported by grants from the Australian Research Council. Theauthors are grateful to Drs. B. Messerle and J. Hook for advice concerning the NMRstudies and to Dr. P. Stiles for assistance with some aspects of the modelling.References1. T. Goto, H. Yokoyama and H. Nishibayashi, U.S. Pat. 4,782,183, to NipponShokubai Kagaku Kogyo Company Limited (1988).2. Y. Yang, Z. Duan, W. Liu, G. Li and X. Xiong, Huaxue Fanying Gongcheng YuGongyi, 17, 210 (2001).3. Z.-Y. Cai, Z.-G. Lu and C.-W. Bai, Jingxi Huagong, 20, 187 (2003).4. X. Zeng, G. Yang and W. Liao, Nongyao, 41, 19 (2002).5. H.-P. Ye, Z.-K. Duan, Y.-Q. Yang, J. Wu and J. Yu, Gongye Cuihia, 12, 48(2004).6. T. S. Franczyk, US Pat. 5,367,112 , to Monsanto Company (1994).7. J. R. Ebner and T. S. Franczyk, U.S. Pat. 5,627,125, to Monsanto Company(1997).8. T. S. Franczyk, Y. Kadono, N. Miyagawa, S. Takasaki and H. Wakayama, USPat. 5,739,390, to Monsanto Company (1998).9. D. A. Morgenstern, H. C. Berk, W. L. Moench and J. C. Peterson, US Pat.6,376,708, to Monsanto Technology LLC (2002).10. D. Liu, N. W. Cant, A. J. Smith and M. S. Wainwright, Appl. Catal. A, in press.11. D. Liu, N. W. Cant, L. Ma and M. S. Wainwright, Chemical Industries (CRCPress), 104, (Catal. Org. React.) 27-36 (2005).12. N. W. Cant, S. P. Tonner, D. L. Trimm and M. S. Wainwright, J. Catal., 91, 197(1985).13. P. W. Atkins, Physical Chemistry, 4th edition, Oxford University Press, Oxford,1990, p. 798-799.14. L. Ma and M. S. Wainwright, Appl. Catal. A: General, 187, 89 (1999).15. L. Ma and M. S. Wainwright, Chemical Industries (Dekker), 89, (Catal. Org.React.) 225-245 (2003).
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Catalysis ofOrganic Reactions
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14. Catalyst Manufacture: Laborator
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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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Wang et al. 27Schiff’s base forma
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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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Gőbölös et al. 53internal TMS in
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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Mantilla, Tzompantzi, Torres and G
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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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Page 147 and 148: 120TEMPO Oxidation of Alcoholsthe u
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Page 151 and 152: 124TEMPO Oxidation of Alcoholsany d
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Page 155 and 156: 128TEMPO Oxidation of AlcoholsMNT :
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Page 179 and 180: 152CO Oxidationcarboxylate species
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Page 203 and 204: 176Nitrobenzene Hydrogenation10. G.
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190Modeling 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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204 Fructose Hydrogenationthe subst
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206 Fructose Hydrogenationcleave th
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208 Fructose Hydrogenationfulfills
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210 Fructose Hydrogenationis not th
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Disselkamp et al. 21324. Cavitating
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Disselkamp et al. 215column. In a p
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Disselkamp et al. 217selectivity es
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Disselkamp et al. 219hydrogenated (
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Disselkamp et al. 221A somewhat mor
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Disselkamp et al. 223Scheme 4.cis-2
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Disselkamp et al. 225conventional c
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Ostgard et al. 22725. The Treatment
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Ostgard et al. 231metal atoms. Thes
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Ostgard et al. 233In conclusion, th
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Kuusisto, Mikkola and Salmi 23526.
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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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Musolino, Apa, Donato and Pietropao
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Gőbölös and Margitfalvi 25329. R
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Gőbölös and Margitfalvi 255maxim
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Rothenberg et al. 26130. How to Fin
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Rothenberg et al. 265pre-define the
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Rothenberg et al. 267Table 1. Parti
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Rothenberg et al. 269Experimental S
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Angueira and White 27131. Novel Chl
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Angueira and White 273optimizedgeom
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Angueira and White 275F igure 4 - c
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Angueira and White 277Table 1. 27 A
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Angueira and White 279obtained from
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Robitaille, Clément, Chapuzet and
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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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308 Catalyst Library DesignBasic Pr
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310 Catalyst Library DesignD in com
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312 Catalyst Library DesignCatalyst
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314 Catalyst Library Design27. S. H
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316 Dendrimer TemplatesWe are devel
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318 Dendrimer TemplatesThe differen
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320 Dendrimer TemplatesWe encounter
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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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Diez, Di Cosimo and Apesteguia 3554
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Diez, Di Cosimo and Apesteguia 357T
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378 Polyurethane from Natural OilMe
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380 Polyurethane from Natural Oilco
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382 Polyurethane from Natural Oilfr
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384 Polyurethane from Natural OilTh
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386 Carbonylation of Chloropinacolo
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396 Recycling Homogeneous Catalysts
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406“Green” Catalysts for Biodie
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416 Production of BiodieselTable 1.
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418 Production of Biodieselto a mas
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420 Production of BiodieselEthyl st
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422 Production of Biodiesel10080Sel
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424 Production of Biodieselproduct
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Marincean et al. 431neutralize all
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Kocal 43748. Developing Sustainable
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Kocal 439description of the four st
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Kocal 441metallurgy in parts of the
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Kocal 443that capital investment co
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448Propylene Oxidation to POSupercr
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450Propylene Oxidation to POTable 1
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452Propylene Oxidation to PO
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Riermeier et al. 45550. catASium ®
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Riermeier et al. 457It is interesti
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Riermeier et al. 459Reaction of the
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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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Pohlmann et al 47553. Leaching Resi
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Pohlmann et al 477this study. In th
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Pohlmann et al 479Experimental Sect
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482 Reductive AlkylationSince the p
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484 Reductive AlkylationTable 2. Re
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Wolf, Seebald and Tacke 48755. Acce
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Wolf, Seebald and Tacke 489100Norma
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Wolf, Seebald and Tacke 4911,88Figu
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Woods et al. 49356. Transition Meta
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Woods et al. 495Effect of oxidation
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Woods et al. 499removed the samples
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502 Electroreductive Catalytic Ullm
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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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