Direct conversion of methane to higher hydrocarbons via an oxygen free, low-temperature route

Abstract

The direct conversion of methane to higher hydrocarbons over a silica-supported Ru catalyst has been investigated via an oxygen free, two-step route. The reaction consists of decomposition of methane over a 3% silica-supp orted Ru catalyst at temperatures\((T_{CH_4 } )\) between 400 and 800 K to produce surface carbonaceous species followed by rehydrogenation of these species to higher hydrocarbons at\(T_{H_2 } \) of 368 K. It was found that the Ru/SiO2 catalyst exhibits a trend similar to that for single-crystal Ru catalysts. However, the temperature at which a maximum in ethane selectivity occurs shifts toward a higher temperature. It was also found that the ethane yield can be optimized by changing the surface carbon coverage. Under optimum conditions a net ethane yield of about 13–15% has been realized. For this two-step reaction sequence, only a few reaction cycles could be operated without intermediate high temperature rehydrogenation and without significant loss in ethane yield. This is attributed to large amounts of inactive carbon that could not be hydrogenated at 368 K. Higher methane partial pressures were found to be desirable for this reaction. The activity of the catalyst could also be maintained at total pressures up to 10 atm.