Selective oxidation of hydrocarbons in a catalytic dense membrane reactor: Catalytic properties of BIMEVOX (Me = Ta)

Used as dense membranes in a catalytic dense membrane reactor, Bi2V0.8Ta0.2O5.5 (BITAVOX) is more or less active in the oxidation of propane, ethane and propene according to its surface roughness. When the surface roughness is low, membranes are poorly active in the oxidation of propane (conversion <2%). CO and propene are the main products and the stability is high over long experimental periods. BITAVOX membranes with increased surface roughness exhibit high conversions in the oxidation of propane, ethane and propene. Activities and selectivities evolve with time. In a first short period (<250 s), the products are similar to those of polished samples, then mainly H2 and CO are produced and subsequently H2 and coke. These evolutions are probably related to surface and sub-surface restructuring due to an insufficient oxygen supply through the membrane to face the high catalytic activity induced by the increase in surface area. The results suggest that the O2− diffusion is limited by the low electronic conductivity of BIMEVOX materials. Nevertheless the membrane is not reduced irreversibly, even in coking conditions. This is confirmed by ex situ characterisations carried out on the materials (XRD, SEM, XPS). An improvement of the electronic conductivity of this material is necessary in order to stabilize the intermediate catalytic behaviour which is interesting for syngas or H2 production from light hydrocarbons.