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  • enantioselective  (3)
  • Industrial Chemistry and Chemical Engineering  (2)
  • 1995-1999  (5)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 41 (1996), S. 199-202 
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; cinchonidine ; Pd/alumina ; methylpentenoic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A chiral alkanoic acid was prepared with up to 52% excess of the (S) enantiomer by hydrogenating anα,β-unsaturated carboxylic acid with a cinchonidine-Pd/Al2O3 catalyst system. Favourable conditions are: high surface hydrogen concentration (⩾ 60 bar hydrogen pressure, low catalyst concentration and apolar solvents), near ambient temperature and a cinchonidine/reactantmolar ratio of at least 0.4 mol%. It is proposed that high hydrogen solubility and the presence of 2-methyl-2-pentenoic acid reactant as dimers are advantageous for enantiodifferentiation.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; ketopantolactone ; cinchonidine ; catalyst pretreatment ; adsorbate‐induced restructuring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of reductive and oxidative heat treatment on the enantioselectivity of chirally modified Pt/alumina has been reinvestigated, using the hydrogenation of ketopantolactone as a test reaction. Enhancement in ee by 39–49% has been observed after treatment in hydrogen at 250–600°C, as compared to untreated or preoxidized catalysts. The changes in ee after reductive and oxidative treatments are reversible, and always the final treatment is decisive. A HRTEM study indicates that adsorbate‐induced restructuring of Pt crystallites during hydrogen treatment at elevated temperature can play a role in the selectivity improvement, but the changes are superimposed by the strong structure‐directing effect of the alumina support. The possible contribution of other effects (complete reduction of Pt n+ surface species, removal of impurities, or change of Pt particle size) could be excluded.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 59 (1999), S. 95-97 
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; isomerization ; cinchonidine ; Pd/alumina ; alkenoic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The enantioselective hydrogenation of 2-ethyl-propenoic acid over Pd/alumina modified with cinchonidine has been studied. The reaction, carried out in a batch reactor at 1 bar hydrogen pressure and room temperature, revealed that the isomerization of the C=C double bond is a competing side reaction. Double-bond migration and the subsequent hydrogenation of the two isomer alkenoic acids lowered the enantioselectivity drastically due to the formation of opposite enantiomers.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two vanadia/titania catalysts, containing 1 and 8 wt% vanadia on anatase, have been investigated for the selective oxidation of o-xylene to phthalic anhydride. In a comparative study, activity and selectivity in o-xylene oxidation were measured using an integral reactor and a reactor with external product recirculation, with the objective of studying the influence of backmixing in the latter on the reaction behaviour. Adsorbed surface species were investigated by means of in-situ diffuse reflectance FT-IR spectroscopy, using an environmental chamber which corresponds to an integral reactor. No difference in activity and selectivity in o-xylene oxidation was observed between the two catalysts. FT-IR studies showed adsorbed o-xylene, benzoate and a high concentration of phthalic anhydride on the surface of both catalysts. o-Xylene oxidation follows a sequential reaction path, with o-tolualdehyde as the first intermediate and phthalide, phthalic anhydride and maleic anhydride as sequential products. No evidence was found for a direct oxidation-path of o-xylene to phthalic anhydride. Total oxidation products CO and CO2 are formed by direct oxidation of the o-xylene and by oxidation of the reaction products. Due to greatly reduced concentration and temperature gradients, the recycle reactor proved to be highly suitable for studying the extremely exothermic oxidation of o-xylene.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 19 (1996), S. 89-95 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behavior of a Pt-Rh/CeO2-Al2O3 three-way catalyst (TWC) under pulsed flow operation conditions (intermittent mode), such as occur in a newly developed hybrid drive system, has been studied experimentally in a laboratory apparatus with simulated exhaust gas. The parallel hybrid system is based on the combination of an Otto-cycle engine with an electric motor and a flywheel providing a short-term energy storage. This configuration permits intermittent charging of the flywheel by the combustion engine which runs only during about 10% of the driving time. Each exhaust gas pulse (duration typically ca. 3 s) is proceeded by an air pulse, which results from the filling of the engine cylinders with air at start up and shut off. Experimental studies indicated that the air pulses have a negative impact on the performance of the catalytic converter, reducing the inherent benefits resulting from the intermittent operation mode of the combustion engine.Forced asymmetric λ-cycling during exhaust pulse was found to be most beneficial for improving catalyst performance. A simple reduced kinetic model derived from a Langmuir-Hinshelwood model for CO oxidation, which was extended by introducing CO and O2 equivalents to mimic the complex exhaust gas, was used to describe the dynamic behavior of the TWC. The model proved to be useful for finding the optimal λ-cycling conditions. Experiments with the real Otto-cycle engine exhaust proved that the reduced kinetic model is suitable for use in a closed loop λ-control.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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