Pressure Calcination of VPO Catalyst

Abstract

Calcination and activation are critical steps in the transformation of vanadyl hydrogen phosphate hemihydrate (VPO precursorVOHPO4·0.5H2O) to vanadyl pyrophosphate (VPO catalyst(VO)2P2O7). Whereas many published kinetics studies for butane oxidation over VPO demonstrate the relationship between catalytic activity and reaction conditions, the relationship between calcination conditions and activity has only received superficial attention in the open literature. This study delineates the operating boundaries in which to optimize catalytic performance. The control variables included temperature, pressure, time, and gas-phase composition (principally, oxygen and water vapor partial pressures), and their effects on surface area, oxidation state, and catalytic activity were measured. The experimental plan included several hundred calcination experiments. The commercial-design operating conditions were chosen as the base-case conditions: temperatures from 330 to 460 °C, pressures up to 6 atm, and oxygen and water concentrations between 0 and 20% and 0−3%, respectively. The optimal temperature was found to be about 390 °C. Catalyst performance declines with increasing pressure, but the pressure−time relationship allows a range of conditions: optimal catalytic performance was achieved within 20 h of calcination at atmospheric pressure, but it took less than 4 h to achieve this high level of performance when precursor was calcined at 3.5 atm (at longer times, the catalytic performance deteriorated). Co-feeding steam (in the presence of oxygen) generally had a deleterious affect on catalyst performance and, in particular, maleic anhydride yield. Moreover, oxidation states higher than 4.5 were achieved with steam/oxygen mixtures in as little as 20 h. Catalyst performance declined linearly with oxidation state for precursor calcined to vanadium oxidation states exceeding 4.5.