An investigation on the reaction mechanism for the partial oxidation of methane to synthesis gas over platinum

Abstract

The partial oxidation of methane to synthesis gas has been investigated by admitting pulses of pure methane, pure oxygen and mixtures of methane and oxygen to platinum sponge at temperatures ranging from 973 to 1073 K. On reduced platinum the decomposition of methane results in the formation of surface carbon and hydrogen. No deposition of carbon occurs during the interaction of methane with a partly oxidised catalyst. Oxygen is present in three different forms under the conditions studied: platinum oxide, dissolved oxygen and chemisorbed oxygen species. Carbon monoxide and hydrogen are produced directly from methane via oxygen present as platinum oxide. Activation of methane involving dissolved oxygen provides a parallel route to carbon dioxide and water. Both platinum oxide and chemisorbed oxygen species are involved in the oxidation of carbon monoxide and hydrogen. In the presence of both methane and dioxygen at a stoichiometric feed ratio the dominant pathways are the direct formation of CO and H₂ followed by their consecutive oxidation. A Mars-van Krevelen redox cycle is postulated for the partial oxidation of methane: the oxidation of methane is accompanied by the reduction of platinum oxide, which is reoxidised by incorporation of dioxygen into the catalyst.