Hydrogenolysis and related reactions of hydrocarbons (C3 to C5) on silica-supported Rh-Pt bimetallic catalysts

Abstract

The reactions with hydrogen of propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2, 2-dimethylpropane and cyclopentane have been studied in a static reactor using a series of highly dispersed rhodium-platinum catalysts supported on high-area silica. The main reaction over all catalysts was hydrogenolysis involving the breaking of a single carbon-carbon bond. Most of the compounds reacted at similar rates over platinum with activation energies in the range 132-144 kJ mol-1. With rhodium, rates varied with hydrocarbon structure by factors of more than 102. The selectivities for the formation of the various products showed that the relative rates of breaking different carbon-carbon bonds over rhodium were S-S > P-S > S-T > P-T > P-Q (P = primary, Q = quaternary, S = secondary and T = tertiary). At temperatures above 455 K, there was evidence of a change of rate-determining step over rhodium with the overall reaction becoming controlled by the rate of desorption of methane. Probable mechanisms over platinum and rhodium are discussed. Rhodium was more active than platinum by factors of about 200 for branched hydrocarbons and of 103 or more for straight-chain compounds. Patterns of activity with metal composition are interpreted in terms of active sites consisting of ensembles of about six metal atoms. But an alternative description of the active site as a single metal atom with properties influenced by a number of nearest neighbours cannot be excluded.