Partial Oxidation of Methane on Silica-Supported Silicomolybdic Acid Catalysts in an Excess Amount of Water Vapor

Abstract

Partial oxidation of methane into oxygenates such as methanol and formaldehyde on highly dispersed MoO3/SiO2 catalysts was studied in an excess amount of water vapor. The reaction was carried out at 873 K using gases consisting of oxygen, methane, and water vapor. The selectivity of oxygenates was found to be a strong function of water vapor, and increased as the fraction of water vapor in a feed gas increased. Inversely, the selectivity of CO and CO2 in the products decreased as the fraction of water vapor increased. This is ascribed to the formation of silicomolybdic acid (SMA: H4SiMo12O40) over the silica surface during the reaction, partially evidenced by IR measurements. Accordingly, silica-supported SMA catalysts were prepared and applied to the partial oxidation of methane under the same conditions as described above to see if SMA works as the active species for the reaction. Although SMA easily decomposed into SiO2 and MoO3 at 873 K without water vapor, it worked well for the production of oxygenates when the fraction of water vapor was more than 50% in the feed gas. The yield of oxygenates increased up to 20% of methane as the fraction of water vapor was around 60%; methane conversion was about 25% and the selectivity of oxygenates was 90%. In this paper, the authors will emphasize that SMA formed on the silica surface are the active species of silica-supported MoO3 catalysts for the partial oxidation of methane in an excess amount of water vapor.