2-苯基环己硫醇在γ-Al2O3和SiO2负载的WS2催化剂上的脱硫反应  

Desulfurization of 2-Phenylcyclohexanethiol Over WS2 Catalysts Supported onγ-Al2O3 and SiO2

作　　者：刘盛男 周学荣 李翔 王安杰[1,3] 王琳 LIU Shengnan;ZHOU Xuerong;LI Xiang;WANG Anjie;WANG Lin(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,China;School of Chemical Engineering and Materials Science,Tianjin University of Science and Technology,Tianjin 300457,China;Liaoning Key Laboratory of Petrochemical Technology and Experiment,Dalian 116024,China)

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116024 [2]天津科技大学化工与材料学院,天津300457 [3]辽宁省高校石油化工技术与装备重点实验室,辽宁大连116024

出　　处：《石油学报（石油加工）》2021年第1期10-23,共14页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(21673029和21603024);天津市自然科学基金重点项目(19JCZDJC31700)资助。

摘　　要：合成了2-苯基环己硫醇(2-PCHT);通过等体积浸渍法制备了分别以γ-Al2O3和SiO2作载体的WS2催化剂,采用X射线衍射(XRD)、N2物理吸附和透射电镜(TEM)技术对催化剂进行表征。在临氢和非临氢(Ar)条件下研究了2-PCHT在WS2/Al2O3和WS2/SiO2催化剂上的脱硫反应。结果表明:在240℃和5.0 MPa H2条件下,2-PCHT在WS2催化剂上主要通过β消除、氢解和脱氢3条平行路径脱硫,其中β消除和氢解并重,β消除反应速率快于氢解;非临氢条件下,主要通过β消除、C-S键均裂(或氢解)及脱氢3条平行路径脱硫,并以β消除为主;哌啶对β消除路径的抑制作用最大、对脱氢路径作用次之,但对氢解几乎没有影响,并促进了C-S键均裂;WS2/Al2O3的反应活性优于WS2/SiO2,可能与其活性组分的分散度较高有关;临氢条件下,2-PCHT的反应动力学可以用假一级模型描述;但其在非临氢条件下则不能用简单的幂函数拟合,可能归因于环烷基C-S键断裂机制的复杂性。2-Phenylcyclohexanethiol(2-PCHT)was synthesized.WS2/Al2O3 and WS2/SiO2 were prepared by the incipient wetness impregnation,and characterized by X-ray diffraction(XRD),N2 physical adsorption and transmission electron microscope(TEM).The desulfurizations of 2-PCHT over WS2 catalysts supported onγ-Al2O3 and SiO2 were investigated in the presence or absence of H2.At 240℃and under 5.0 MPa H2,2-PCHT undergoes desulfurization over the supported WS2 catalysts via three parallel pathways:β-elimination,hydrogenolysis and dehydrogenation.β-elimination and hydrogenolysis are the two major pathways,and the reaction velocity inβ-elimination pathway is much faster than that in the hydrogenolysis pathway.Under Ar atmosphere,the parallel pathways areβ-elimination,homolytic C-S bond cleavage or hydrogenolysis,and dehydrogenation,withβ-elimination serving as the dominate pathway.Piperidine strongly inhibits theβ-elimination pathway and the dehydrogenation pathway.It does not affect the hydrogenolysis pathway,and facilitates the homolytic C-S bond cleavage pathway.WS2/Al2O3 is superior to WS2/SiO2 in the desulfurization of 2-PCHT,which is due to the higher dispersion of active phase.The kinetics of the desulfurization of 2-PCHT under H2 is reasonably fitted by a pseudo-first-order model,whereas that under Ar cannot be described by the power-law rate expression,suggesting that the desulfurization of 2-PCHT is complex.

关 键 词：2-苯基环己硫醇 WS2 脱硫 环烷基C-S键 哌啶 SIO2 Γ-AL2O3 

分 类 号：TE624.9[石油与天然气工程—油气加工工程]