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Hydrogenation of alkenes over cobalt/molybdenum/alumina catalyst

Journal Article · · J. Catal.; (United States)

The hydrogenation of nine C/sub 2/-C/sub 10/ 1-alkenes, cis- and trans-2-butene, and 2,3-dimethyl-2-butene was studied at 300/sup 0/C and various hydrogen-alkene ratios on a commercial 12% MoO/sub 3//43% CoO/alumina hydrotreating catalyst. All alkenes had a maximum raction rate at approx. 0.15 mole fraction alkene in hydrogen, and the magnitude of the maximum rate varied from 0.62 mole/hr kg catalyst for 2,3-dimethyl-2-butene to 46 mole/hr kg catalyst for ethylene. The rates did not depend on the size and number of substituents on the double-bonded carbons, as they do in metal-catalyzed hydrogenation. Cis- and trans-2-butene, 2,3-dimethyl-2-butene, and 2,3-dimethyl-1-butene had comparable reactivities which suggested that in the slow step, they had already changed into an identical intermediate species. The maximum rates were correlated to the Taft (SIGMA)E/sup 0/(s) constants of substituents in the half-hydrogenated state; 3,3-dimethyl-1-butene deviated from the correlation towards higher reactivity, probably caused by steric acceleration. The kinetics could be described with a four-step reaction scheme within the Langmuir-Hinshelwood framework. Of the four steps, i.e., dissociative hydrogen adsorption, alkene adsorption, surface reaction with one hydrogen, and surface reaction of the half-hydrogenated species with a second hydrogen, the last step was rate-determining.

Research Organization:
Inst. Chem. Process Fundam., Czech. Acad. Sci.
OSTI ID:
6318569
Journal Information:
J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 64:1; ISSN JCTLA
Country of Publication:
United States
Language:
English