VPO Transient Oxidation Kinetics

Abstract

Transient and steady state reactor data for the partial oxidation of butane to maleic anhydride were collected in a fluid bed over DuPont commercial vanadium pyrophosphate catalyst (VPO) principally under butane rich, oxygen deficient operating conditions. Under moderate reducing conditions, oxygen becomes the determining factor for maleic anhydride productivity and selectivity. As the oxygen becomes depleted, minor changes in butane conversion impacts the selectivity substantially. However, when VPO catalyst is pre-exposed to oxygen for a substantial period of time (as practiced in Circulating Fluidized Bed technology), selectivity may be improved and maleic anhydride yields four times the steady state operation values are achieved. As the butane-to-oxygen ratio rises above 1, carbon deposits onto the surface of the catalyst, resulting in lower activity and selectivity. Based on a detailed reaction engineering model, the re-oxidation rate of the adsorbed carbon is 1st order with respect to the carbon adsorption sites and ½ order in oxygen. The re-oxidation rate of the reduced catalyst appears to be 1st order in sites and oxygen.