NiMoS加氢脱硫催化剂表面非化学计量硫物种动态平衡  

Dynamic Equilibrium of Surface Non-Stoichiometric Sulfur Species on a NiMoS Hydrodesulfurization Catalyst

作　　者：袁胜华 李唯楚 魏春金[3] 郑进保[2] 方维平[2] 伊晓东[2] 赖伟坤 YUAN Shenghua;LI Weichu;WEI Chunjin;ZHENG Jinbao;FANG Weiping;YI Xiaodong;LAI Weikun(SINOPEC(Dalian)Research Institute of Petroleum and Petrochemicals Co.,Ltd.,Dalian 116041,China;National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China;School of Science,Jimei University,Xiamen 361021,China)

机构地区：[1]中石化(大连)石油化工研究院有限公司,辽宁大连116041 [2]厦门大学化学化工学院醇醚酯化工清洁生产国家工程实验室,福建厦门361005 [3]集美大学理学院,福建厦门361021

出　　处：《石油学报（石油加工）》2023年第2期258-268,共11页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22172122,22072057,22172124,22172126,21773194);广西省科技项目(AD17195067)资助

摘　　要：加氢脱硫(HDS)催化剂NiMoS活性相表面非化学计量硫(S_(x))物种的动态变化是HDS活性的决定因素。在HDS过程中,S_(x)物种处于动态平衡,且这一平衡与催化剂、H_(2)S分压及硫化温度相关。笔者采用程序升温的方法研究了催化剂载体、助剂Ni、硫化温度、H_(2)S分压对NiMoS催化剂表面S_(x)物种的影响。结果表明:催化剂载体对S_(x)物种的总量和还原性具有显著影响,Ni的引入显著促进S_(x)物种还原,提升HDS活性;硫化气相H_(2)S分压决定了催化剂表面S_(x)物种含量,气相中H_(2)S分压升高易使S_(x)物种增多,表面可利用NiMoS活性位减少,从而导致HDS活性降低。S_(x)物种含量与H_(2)S分压及硫化温度的关系符合热力学平衡及van′t Hoff等压方程,进一步将S_(x)物种含量与HDS反应速率系数进行关联,提出H_(2)S分压-S_(x)物种含量-HDS活性之间的定量关系。The dynamic equilibrium of surface non-stoichiometric sulfur(S_(x))species between the NiMoS hydrodesulfurization(HDS)catalyst and the gas phase is a determinant of HDS activity.During HDS reaction,S_(x)species is in a dynamic equilibrium state,which is related to catalyst,H_(2)S partial pressure and sulfidation temperature.The effects of catalyst carrier,Ni promoter,sulfidation temperature and H_(2)S partial pressure on S_(x)species over the NiMoS catalysts were studied by temperature-programmed reduction.The results show that catalyst support has a significant impact on the total amount and reducibility of S_(x),and the introduction of Ni can significantly promote the reduction of S_(x)species and enhance HDS activity;the content of S_(x)species also depends on H_(2)S partial pressure in the sulfidation process:the increasing H_(2)S partial pressure in gas phase tends to increase the S_(x)species content and decrease the number of accessible NiMoS sites,thus resulting in a decrease in HDS activity.The relationship among S_(x)species amount,H_(2)S partial pressure and sulfidation temperature reasonably follows thermodynamic equilibrium and van′t Hoff isobaric equation.On this basis,S_(x)content is further correlated with HDS reaction rate coefficient,and a quantitative relationship among H_(2)S partial pressure,S_(x)species content and HDS activity is proposed herein.

关 键 词：非化学计量硫 NiMoS 硫平衡 加氢脱硫 构效关联 

分 类 号：TQ426[化学工程]