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The gas phase hydrodechlorination of chlorobenzene over nickel/silica

✍ Scribed by George Tavoularis; Mark A Keane


Publisher
Wiley (John Wiley & Sons)
Year
1999
Tongue
English
Weight
201 KB
Volume
74
Category
Article
ISSN
0268-2575

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✦ Synopsis


The gas phase hydrodechlorination of chlorobenzene over the temperature range 473 K O T O 573 K has been studied using a 1.5% (w/w) catalyst. Reproducible turnover fre-Ni/SiO 2 quencies are quoted and the eΓΎ ects of varying such process variables as reaction time and temperature, contact time, chlorobenzene and hydrogen partial pressures are presented. The catalyst was 100% selective in promoting hydrodechlorination and the aromatic ring remained intact in every instance. Under reaction conditions far removed from equilibrium conversions, the catalyst exhibited no appreciable short term deactivation while the maintenance of long term activity was also established. Chlorine coverage of the catalyst surface under reaction conditions was probed indirectly by monitoring, via pH changes in an aqueous NaOH trap, HCl desorption after completion of the catalytic step. The hydrogenolysis of bromobenzene, 2-chlorophenol and 3-chlorotoluene under the same reaction conditions were considered for comparative purposes where the turnover frequencies decrease (at 573 K) in the order 2-chlorophenol > 3-chlorotoluene > chlorobenzene > bromobenzene ; reactivity is discussed in terms of thermodynamic limitations and reactant/catalyst interactions. Reaction orders with respect to hydrogen and chlorobenzene partial pressures were obtained at different reaction temperatures and the experimental rate data are adequately represented by an extended power rate expression that approximates the Langmuir-Hinshelwood model for noncompetitive adsorption.


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