Hydrogenolysis of some saturated hydrocarbons over a platinum black catalyst

Deuterium exchange reactions of methane, ethane, propane and neopentane, and the hydrogenolysis and isomerization of ethane, propane, n-butane and isobutane on platinum black have been studied in the temperature range 363–743 K. There is a gap of 150 K between the temperature of deuterium exchange and that of hydrogenolysis and isomerization. Only at high hydrogen pressure (about 50 kN m–2) and at low catalytic activity is the hydrogenolysis characterized by selective loss of a terminal methyl group, except for n-butane in which there is an equal chance of any of the C—C bond rupturing. The selectivity for isomerization has a maximum at high hydrogen pressure. These values together with kinetic data suggest that the ability of platinum in an exchange reaction to convert weakly bonded intermediates into strongly bonded ones is much less than that of nickel. The phenomenon of π-olefin and π-allyl bond conversion is applied in part to explain the results obtained. Brief comparison is given between the catalytic properties of platinum and those of nickel for the reactions investigated.