丙烯环氧化反应中TS-1催化剂失活研究  

Deactivation of catalyst TS-1 in propene epoxidation

作　　者：沈本贤[1] 赵基钢[1] 肖卫国[2] 王雷[1] 张策[1] 

机构地区：[1]华东理工大学石油加工研究所,上海200237 [2]天津大沽化工股份有限公司,天津300455

出　　处：《燃料化学学报》2007年第5期609-614,共6页Journal of Fuel Chemistry and Technology

摘　　要：采用丙烯气相进料,在预混段中先与双氧水的甲醇溶液混合后进入固定床反应器,考察了进料液中pH值、丙二醇单甲醚、乙硫醇以及铁锈等对丙烯环氧化连续反应中TS-1分子筛催化剂性能的影响。结果表明,进料液体pH值对催化剂的催化性能有影响,适宜的进料液体pH值在7左右;副产物丙二醇单甲醚含量的增加不会对催化剂性能产生影响;乙硫醇量的增加使环氧丙烷选择性下降,但不会引起催化剂的失活;而进料液体中铁锈的引入会导致催化剂中部分孔堵塞,使催化剂部分失活。当进料液中的pH值用0.1mol/L的氨水调节为7左右,在反应温度55℃,反应压力0.7MPa,TS-1催化剂具有较好的稳定性,经130h的连续试验考察,双氧水的转化率和环氧丙烷的选择性约为90%。The effects of pH value of liquid feed as well as the presence of monomethyl ether(MME),ethyl thiol and rust in the feed on the catalytic performance of TS-1 in propene epoxidation were investigated,where the epoxidation was carried out in a continuous fixed-bed reactor and gaseous propene was pre-mixed with dilute solution of hydrogen peroxide in methanol.It was shown that the presence of MME in feed has no impact on the catalytic performance of TS-1.The addition of ethyl thiol in the feed exhibits little effect on the catalytic activity,but may cause a decrease in propylene oxide(PO) selectivity.The pH value of liquid feed influences the catalytic performance significantly;an optimum pH value is about 7.The rust in the feed may block the pores of TS-1 and then cause a partial deactivation.With a liquid feed pH value of 7(adjusted with 0.1 mol/L ammonia water),the catalyst TS-1 exhibits excellent stability at 55 ℃ and 0.7 MPa;both H2O2 conversion and PO selectivity exceeded 90% in a 130 h catalytic test.

关 键 词：丙烯 环氧化 钛硅分子筛 催化剂失活 稳定性 环氧丙烷 

分 类 号：O643[理学—物理化学]