Partial oxidation of methane to synthesis gas over Rh/alpha-Al2O3 at high temperatures

Abstract

The partial oxidation of methane to synthesis gas has been studied in a continuous flow reactor using a Rh/a-Al2O3 catalyst under conditions as close as possible to those industrially relevant: pressures up to 800 kPa and temperatures higher than 1274 K in order to avoid the formation of carbon and to obtain high equilibrium selectivities to CO and H2. Intrinsic kinetic data were obtained when the feed was diluted with helium. Gas-phase reactions were found to occur at 500 kPa when the feed was not diluted. A reaction network has been derived from experimental results in which oxygen conversions range from 0 to 1. CO2, C2H6 and H2O are the primary products. C2H4 is formed by oxidative dehydrogenation of C2H6. CO and H2 are formed by reforming of CH4 by CO2 and H2O; an additional direct route to CO and H2 at low oxygen conversions cannot be excluded. The catalyst appears to be present in two states, the transition being at an oxygen conversion of 0.4 under the conditions used. The support probably enhances oxidation reactions by reverse spillover of oxygen or hydroxyl species onto rhodium. The support as such behaves similarly to the catalyst at low oxygen conversions, but shows no reforming activity.