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Thioetherification of isoprene and butanethiol on transition metal phosphides

查看全文 作　　者：Tianyu [1]Ren;Mingfeng [2]Li;Yang [2]Chu;Jixiang [1]Chen 高影响力作者 机构地区：[1]Tianjin Key Laboratory of Applied Catalysis Science and Technology, Department of Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University;[2]Research Institute of Petroleum Processing, SINOPEC高影响力机构 出　　处：《Journal of Energy Chemistry》索引2018年第27卷第3期,共10页高影响力期刊 基　　金：supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC) 摘　　要：Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120 °C and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former. 关 键 词：金属性 磷化物 二烯 NH3-TPD 选择加氢 HRTEM 反应堆 地点
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