The oxygen-assisted transformation of propane to COx/H2 through combined oxidation and WGS reactions catalyzed by vanadium oxide-based catalysts

This paper reports about the gas-phase oxidation of propane catalyzed by bulk vanadium oxide and by alumina- and silica-supported vanadium oxide. The reaction was studied with the aim of finding conditions at which the formation of H2 and CO2 is preferred over that of CO, H2O and of products of alkane partial oxidation. It was found that with bulk V2O5 considerable amounts of H2 are produced above 400 °C, the temperature at which the limiting reactant, oxygen, is totally consumed. The formation of H2 derived from the combination of: (i) oxidation reactions, with generation of CO, CO2, oxygenates (mainly acetic acid), propylene and H2O, all occurring in the fraction of catalytic bed that operated in the presence of gas-phase oxygen, and (ii) WGS reaction, propane dehydrogenation and coke formation, that instead occurred in the fraction of bed operating under anaerobic conditions. This combination of different reactions in a single catalytic bed was possible because of the reduction of V2O5 to V2O3 at high temperature, in the absence of gas-phase oxygen. In fact, vanadium sesquioxide was found to be an effective catalyst for the WGS, while V2O5 was inactive in this reaction. The same combination of reactions was not possible when vanadium oxide was supported over high-surface area silica or alumina; this was attributed to the fact that in these catalysts vanadium was not reduced below the oxidation state V4+, even under reaction conditions leading to total oxygen conversion. In consequence, these catalysts produced less H2 than bulk vanadium oxide.