Study on the mechanism of hydrodesulfurization of tetrahydrothiophene catalyzed by nickel phosphide  

作　　者：Chuan-Tao Zhu Li-Qiang Zhang Mei-Ling Zhou Xin-Wei Wang Zheng-Da Yang Ri-Yi Lin De-Wei Yang 

机构地区：[1]College of New Energy,China University of Petroleum,Qingdao,266580,China

出　　处：《Petroleum Science》2022年第3期1390-1400,共11页石油科学（英文版）

基　　金：the financial support provided by the National Science and Technology Major Project of the Ministry of Science and Technology of China(2016ZX05012002-005);National Natural Science Foundation of China(No.51874333);Natural Science Foundation of Shandong Province,China(No.ZR2017MEE030)

摘　　要：Hydrodesulfurization(HDS)reaction can significantly reduce the viscosity and sulfur content of heavy oil,while the HDS reaction mechanism of tetrahydrothiophene as the main sulfide in heavy oil is still unclear.The HDS experiment of tetrahydrothiophene catalyzed by nickel phosphide(Ni_(2)P)is carried out at 200-300°C.The results indicate that the H_(2)S production under the catalysis of Ni_(2)P increases obviously within 200-250°C.The main gas products of HDS reaction are butane,butene and H_(2)S.Meanwhile,the mechanism of tetrahydrothiophene catalyzed by Ni_(2)P is analyzed based on Density Functional Theory(DFT).It is revealed that the adsorption model is most stable when tetrahydrothiophene is vertically adsorbed on the V-Ni-Hcp1 site of Ni_(2)P(001).The C-S bond is elongated and the C-C bond is shortened after adsorption.Hydrogenation(HYD)is the most possible reaction route of tetrahydrothiophene on Ni_(2)P(001)surface.There are two routes with the lowest activation energy,which are C_(4)H_(8)S→C_(4)H_(8)SH^(*)→C_(4)H_(9)SH^(*)→C_(4)H_(10)+H_(2)S and C_(4)H_(8)S→C_(4)H9S^(*)→C_(4)H_(9)^(*)+SH^(*)→C_(4)H_(10)+H_(2)S.Butane and H_(2)S are produced in the reaction,corresponding to the experimental results.This study provides a basis for understanding of the HDS mechanism of tetrahydrothiophene catalyzed by Ni_(2)P.

关 键 词：TETRAHYDROTHIOPHENE Nickel phosphide HYDRODESULFURIZATION Hydrogen sulfide DFT 

分 类 号：TE624.55[石油与天然气工程—油气加工工程]