Preliminary Exploration Of Gas-phase Epoxidation Of Ethylene/ Butylene With TS-1

Gas-Phase HPPO of propylene have achieved preliminary results, which is realized by combination of in situ H2O2 synthesis via plasma and TS-1 catalyst. Gas-phase epoxidation method has better industrial prospect than liquid-phase epoxidation method, because it can effectively avoid the problems caused by liquid solvent. We preliminarily explored the gas-phase epoxidation of ethylene/butylene with H2O2 generated by plasma and TS-1 catalyst. In this work, the effect of reaction conditions, kind of parent TS-1 and modification of TS-1 on gas-phase epoxidation of olefin were studied.1、At the conditions of 110 ℃ and 5.09 h-1 ethylene WHSV, the conversion of ethylene was 0.40%, and the selectivity and yield of ethylene oxide were 84.0% and 26.88 g/(KgTS-1·h), respectively. At the conditions of 110 ℃ and 7.09 h-1 butylene WHSV, the conversion of butylene was 0.68%,and the selectivity and yield of epoxybutane were 84.1% and 52.13 g/(KgTS-1·h), respectively.2、Compared with the TS-1 catalysts with Si/Ti ratio of 50 and 120, the performance of TS-1 with Si/Ti ratio of 33 on gas-phase epoxidation of olefin was best. The conversion of ethylene was 0.40%, and the selectivity and yield of ethylene oxide were 84.0% and 26.88 g/(KgTs-i h), respectively. The conversion of butylene was 0.68%, and the selectivity and yield of epoxybutane were 84.1% and 52.13 g/(KgTS-1·h), respectively.3、The TS-1 catalyst with crystal size of 6.1μm×3.8 μm×1.7 μm had good performance in ethylene epoxidation, the conversion of ethylene was 0.61%, and the selectivity and yield of ethylene oxide were 97.9% and 47.77 g/(KgTS-1·h), respectively. The TS-1 catalyst with crystal size of 13.6 μm×5.8μm×2.7μm had good performance in butylene epoxidation, the conversion of butylene was 0.82%,and the selectivity and yield of epoxybutane were 88.0% and 65.78 g/(KgTS-1·h), respectively.4、The TS-1 catalyst modified by TPAOH-Na2SO3 solution (0.10 mol/L TPAOH and 0.02 mol/L Na2SO3) for 24h had the best catalytic performance in gas-phase ethylene/butylene epoxidation. The conversion of ethylene was 0.44%, and the selectivity and yield of ethylene oxide were 96.9% and 34.10 g/(KgTS-1·h), respectively. The conversion of butylene was 4.05%, and the selectivity and yield of epoxybutane were 95.4% and 352.20 g/(KgTS-1·h), respectively.