Oxydehydrogenation of propane over Mg-V-Sb-oxide catalysts. I. Reaction network

Magnesium vanadates have been shown by various groups to be active oxydehydrogenation catalysts for the conversion of light paraffins to the corresponding olefins. The olefins produced have significant commercial value in petroleum and petrochemical industry. Recently, we reported that doping of the magnesium vanadates with antimony, antimony-phosphorus, or boron, produces catalysts with significantly better selectivities to olefins than those of the parent undoped catalysts. Among these, the composition Mg₄V₂SbO_x was selected for further study of propane oxydehydrogenation and its reaction network. At 500°C and atmospheric pressure, the selectivity to propylene decreases monotonically from 75% to 5% as propane conversion is increased from 2% to 68%. An analysis of the reaction network reveals, that propylene is the only useful first formed product, that CO_x is produced largely by sequential oxidation of the in situ formed propylene, but also to a lesser extent direct from propane by a deep oxidation route. The presence of two parallel pathways for CO_x formation is of interest, as it suggests that partial and deep oxidations may occur at different surface sites or involve different forms of reactive oxygens. Both of these might be amenable to electronic modification by substitution or doping to achieve higher propylene selectivities and yields at higher propane conversions, or their catalytic behavior might be advantageously alterable through site isolation of the paraffin activation centers.