Propylene Production via Oxidative Dehydrogenation of Propane with Carbon Dioxide over Composite M_xO_y-TiO₂ Catalysts

The CO₂-assisted oxidative dehydrogenation of propane (ODP) was investigated over titania based composite metal oxides, 10% M_xO_y-TiO₂ (M: Zr, Ce, Ca, Cr, Ga). It was found that the surface basicity of composite metal oxides was significantly higher than that of bare TiO₂ and varied in a manner which depended strongly on the nature of the M_xO_y modifier. The addition of metal oxides on the TiO₂ surface resulted in a significant improvement of catalytic performance induced by a synergetic interaction between M_xO_y and TiO₂ support. Propane conversion and propylene yield were strongly influenced by the nature of the metal oxide additive and were found to be superior for the Cr₂O₃-TiO₂ and Ga₂O₃-TiO₂ catalysts characterized by moderate basicity. The reducibility of the latter catalysts was significantly increased, contributing to the improved catalytic performance. This was also the case for the surface acidity of Ga₂O₃-TiO₂ which was found to be higher compared with Cr₂O₃-TiO₂ and TiO₂. A general trend was observed whereby catalytic performance increased significantly with decreasing the primary crystallite size of TiO₂. DRIFTS studies conducted under reaction conditions showed that the adsorption/activation of CO₂ was favored on the surface of composite metal oxides. This may be induced by the improved surface basicity observed with the M_xO_y addition on the TiO₂ surface. The Ga₂O₃ containing sample exhibited sufficient stability for about 30 h on stream, indicating that it is suitable for the production of propylene through ODP with CO₂ reaction.