A Comparative Study of the Oxides of Lanthanum, Cerium, Praseodymium, and Samarium as Catalysts for the Oxidative Dehydrogenation of Methane in the Presence and Absence of Carbon Tetrachloride

Abstract

The catalytic oxidative coupling of methane to ethane and ethene has been investigated on the rare earth oxides, i.e., La[sub 2]O[sub 3], CeO[sub 2], Pr[sub 6]O[sub 11], and Sm[sub 2]O[sub 3]. Addition of a small amount of tetrachloromethane (TCM) to the reactant stream improves the catalytic activity of these oxides. In particular, the praseodymium catalyst yields high selectivity to the C[sub 2] compounds comparable to La[sub 2]O[sub 3] or Sm[sub 2]O[sub 3] when TCM is present in the feedstream. The X-ray diffraction patterns for these catalysts after the reaction with TCM show the presence of the oxychlorides in the catalysts except for the cerium catalyst, for which the selectivity to C[sub 2] compounds is very low even in the presence of TCM. The oxychlorides can be generated on La[sub 2]O[sub 3], Sm[sub 2]O[sub 3], or Pr[sub 6]O[sub 11] by preheating under a stream including TCM. The product distribution of the reaction with these catalysts in the absence of TCM is similar to that with the oxides in the presence of TCM, while Pr[sub 6]O[sub 11] pretreated with TCM is unstable with no TCM in the feedstream. It appears that the improvement of the activity of the rare earth catalysts withmore » TCM in the feedstream is primarily due to the formation of the oxychlorides during the reaction. 49 refs., 6 figs., 5 tabs.« less