Historical Review and Recommendations on the Oxidative Coupling of Methane

The oxidative coupling of methane (OCM) to higher hydrocarbons has been under investigation for over fifty years. Some of the earliest reports were published by major chemical companies, including Exxon Research and Engineering Company [1] and Union Carbide [2]. Compared to non-oxidative routes, the major advantage of using oxygen as a reactant with methane is that the reaction is exothermic and not limited by thermodynamic constraints. Yet, the greatest challenge is to selectively control the carbon-hydrogen bond breaking process leading to the carbon-carbon coupling and to mitigate the free-radical chemistry leading to carbon oxide formation both at the catalyst surface and in the gas phase. This presentation will summarize the advances in OCM technology over the past fifty+ years and high light recent advances that might offer economical and technological advantages.

1. Mitchell, H. L., III, and Waghorne, R. H., U.S. Patents 4,172,810 (1979); 4,205,194 (1980); and 4,239,658 (1980) to Exxon Res. And Eng. Co.
2. Keller, G. E., and Bhasin, M. M., J. Catal. 73, 9 (1982).