FORMATION OF CHLORINE SPECIES OVER MAGNESIUM-OXIDE IN THE OXIDATIVE COUPLING OF METHANE IN THE PRESENCE OF CARBON-TETRACHLORIDE

The oxidative coupling of methane on magnesium oxide (MgO) has been studied in the presence of carbon tetrachloride (TCM) as a gas-phase additive. Addition of a small amount of TCM to the reactant stream improves the selectivity to C2H4, while the conversion of methane is not influenced by the additive. X-ray photoelectron spectra of the used MgO reveal the formation of chlorine species on the catalyst surface in quantities up to 0.20 of Cl/Mg (atomic ratio), although X-ray diffraction spectra of the catalyst show MgO only and the content of the chlorine species in the bulk phase estimated by X-ray fluorescence analysis is very low. It is concluded that the enhancement of the selectivity to C2H4 primarily results from the presence of surface chlorine species. The chlorinated species on the catalyst has been identified as MgCl2.