The reaction between methane and oxygen over platinum and rhodium surfaces in metalcoated ceramic monoliths can be made to produce mostly hydrogen and carbon monoxide (greater than 90% selectivity for both) with almost complete conversion of methane and oxygen at reaction times as short as 10–3 seconds. This process has great promise for conversion of abundant natural gas into liquid products such as methanol and hydrocarbons, which can be easily transported from remote locations. Rhodium was considerably superior to platinum in producing more H2 and less H2O, which can be explained by the known chemistry and kinetics of reactants, intermediates, and products on these surfaces.

https://science.sciencemag.org/content/sci/259/5093/343.full.pdf

Production of Syngas by Direct Catalytic Oxidation of Methane

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.

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

This review summarizes different catalytic options for the production of syngas and hydrogen starting from simple hydrogen-containing molecules. Particular attention is given to new direct catalytic alternatives in natural gas conversion. Improvements in syngas technology are discussed, including partial oxidation, autothermal reforming, combined reforming and carbon dioxide reforming, and the energy efficiencies of direct and indirect methane conversion are compared. Processes, issues and practical difficulties are discussed with academic and applied efforts presented in parallel. It is emphasized that most of the ongoing research related to the direct processes is at the exploratory stage while technology utilizing indirect approach has advanced to semi-works and initial commercialization plants. The new emerging processes based on partial oxidation features are unique for syngas generation. Further enhancement of such processes plus improvements in other second generation technologies and advances in direct processes are anticipated to provide additional, new attractive paths to the chemical conversion of natural gas. Similarly, on board generation of hydrogen-rich gaseous fuels either for spark ignition engines or for coupled-fuel-cells electric engines is discussed within the scope of both partial oxidation and catalytic decomposition of methanol. A concept based in the thermochemical water splitting, which provides a renewable portable fuel from water in the form of H2, is also presented. Above all, as the chemistry involved in most of these catalytic alternatives takes place under extreme conditions, highly stable catalysts and engineering concepts are being developed.

R.F. Blanks

Papers

Bidirectional adiabatic synthesis gas generator