A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts

Catalytic partial oxidation of methane has been reviewed with an emphasis on the reaction mechanisms over transition metal catalysts. The thermodynamics and aspects related to heat and mass transport is also evaluated, and an extensive table on research contributions to methane partial oxidation over transition metal catalysts in the literature is provided. Presented are both theoretical and experimental evidence pointing to inherent differences in the reaction mechanism over transition metals. These differences are related to methane dissociation, binding site preferences, the stability of OH surface species, surface residence times of active species and contributions from lattice oxygen atoms and support species. Methane dissociation requires a reduced metal surface, but at elevated temperatures oxides of active species may be reduced by direct interaction with methane or from the reaction with H, H2, C or CO. The comparison of elementary reaction steps on Pt and Rh illustrates that a key factor to produce hydrogen as a primary product is a high activation energy barrier to the formation of OH. Another essential property for the formation of H2 and CO as primary products is a low surface coverage of intermediates, such that the probability of O–H, OH–H and CO–O interactions are reduced. The local concentrations of reactants and products change rapidly through the catalyst bed. This influences the reaction mechanisms, but the product composition is typically close to equilibrated at the bed exit temperature.