Metal effects in Mn-Na2WO4/SiO2 upon the conversion of methane to higher hydrocarbons

The roles of Na, Mn, W and silica, and the synergistic effects between each metal in the $MnNa_2WO_4/SiO_2$ catalyst have been investigated for oxidative coupling of methane (OCM). The crystallisation of amorphous silica during calcination at $900^{\circ}C$ was promoted primarily by Na, but Mn and W also facilitated this process. The interaction between Na and Mn tended to increase the extent of conversion of $Mn_3O_4$ to $Mn_2O_3$. The formation of $Na_2WO_4$ was dependent on the order in which Na and W were introduced to the catalyst. The impregnation of W before Na resulted in the formation of $Na_2WO_4$, but this did not occur when the impregnation order was reversed. $MnWO_4$ formed in all cases where Mn and W were introduced into the silica support, regardless of the impregnation order; however, the formation of $MnWO_4$ was inhibited in the presence of Na. Of the prepared samples in which a single metal oxide was introduced to silica, only $Mn/SiO_2$ showed OCM activity with significant oxygen conversion, thus demonstrating the important role that Mn plays in promoting oxygen transfer in the reaction. The impregnation order of W and Na is critical for catalyst performance. The active site, which involves a combination of Na-Si-W-O, can be formed in situ when distorted $WO_4^{2-}$ interacts with silica during the crystallisation process facilitated by Na. This can only occur if the impregnation of W occurs before Na addition, or if the two components are introduced simultaneously.