Co调变MoS2催化剂的作用本质及其FCC汽油选择性加氢脱硫机理  

Essential role of promoter Co on the MoS 2 catalyst in selective hydrodesulfurization of FCC gasoline

作　　者：LIU Bin LIU Lei CHAI Yong-ming ZHAO Jin-chong LIU Chen-guang 刘宾[1] 刘蕾 柴永明[1] 赵晋翀[1] 刘晨光[1] LIU Bin;LIU Lei;CHAI Yong-ming;ZHAO Jin-chong;LIU Chen-guang(State Key Laboratory of Heavy Oil Processing,Key Laboratory of Catalysis of China National Petroleum Corporation(CNPC),China University of Petroleum(East China),Qingdao　266580,China)

机构地区：[1]中国石油大学(华东)化学工程学院,重质油国家重点实验室,中国石油天然气集团公司催化重点实验室,山东青岛266580

出　　处：《燃料化学学报》2018年第4期441-450,共10页Journal of Fuel Chemistry and Technology

基　　金：The project was supported by the National Natural Science Foundation of China(U1662119,21776314),the National Key Research and Development Program of China(2017YFB0306600),the Shandong Provincial Natural Science Foundation of China(ZR2016BL22),the Qingdao Applied Basic Research Project(17-1-1-73-jch),the Fundamental Research Funds for the Central Universities(17CX02061)and the State Key Laboratory of Heavy Oil Processing(SLKZZ-2017005).

摘　　要：采用含硫前驱体四硫代钼酸铵直接构建MoS2催化剂，通过调变Co/Mo原子比深入认识Co调变MoS2催化剂的作用本质及其FCC汽油选择性加氢脱硫机理。借助XRD、HRTEM、XPS、H2-TPR和Py-FTIR表征发现，Co/Mo原子比能够影响催化剂的活性相微观结构组成，从而影响催化剂的加氢脱硫活性和选择性。当Co/Mo(atomicratio)<0.2时，助剂Co原子倾向于占据MoS2相的边角位而形成CoMoS活性相，明显提高了催化剂的加氢脱硫活性；当0.2<Co/Mo(atomicratio)<0.6时，助剂Co在催化剂表面形成适量的Co9S8相，其产生的溢流氢能提高硫化物的脱除活性而对烯烃饱和活性的影响较小；当Co/Mo(atomicratio)>0.6时，过量的Co会形成大颗粒的Co9S8相，阻碍硫化物和烯烃与催化剂活性中心的接触，从而降低催化剂的活性和选择性。The essential role of Co on the MoS 2 catalyst in selective hydrodesulfurization(HDS)of FCC gasoline was investigated with ammonium tetrathiomolybdate supported on alumina modified with various amount of Co sulfide.According to the data obtained by XRD,HRTEM,XPS,H 2-TPR and Py-FTIR analysis,the Co species could significantly affect the microstructure and composition proportion of the active phase,and thus induced the enormous differences in catalytic properties.The evaluation results demonstrated that the Co atoms tending to form the CoMoS phase as Co/Mo(atomic ratio)<0.2 could greatly improve the HDS activity,but slightly improve the hydrogenation(HYD)activity of olefins.The spillover hydrogen produced by the formation of Co 9S 8 phase as 0.2<Co/Mo(atomic ratio)<0.6 greatly improved the HDS activity,but showed almost no effect on the HYD of olefins.The excess Co could inevitably form some large size Co 9S 8 phase as Co/Mo(atomic ratio)>0.6,which would hinder the mutual contact of the reactants and the active sites,and thus lead to the decrease of the HDS activity and selectivity.The obtained results were useful for developing highly effective hydrotreating catalyst.

关 键 词：选择性加氢脱硫 活性相 Co/Mo原子比 溢流氢 

分 类 号：O643[理学—物理化学]