硫化物双功能催化剂上四氢萘加氢裂化制备BTX反应动力学和选择性研究  

Study on Kinetics and Selectivity of Sulfide Bifunctional Catalysts for Hydrocracking of Tetrahydronaphthalene to BTX

作　　者：党辉 陈胜利[1] 王磊[1] 张燕挺 蒋波 吴志杰[1] DANG Hui;CHEN Shengli;WANG Lei;ZHANG Yanting;JIANG Bo;WU Zhijie(State Key Laboratory of Heavy Oil Processing,College of Chemical Engineering and Environment,China University of Petroleum,Beijing 102249,China)

机构地区：[1]中国石油大学(北京)化学工程与环境学院重质油国家重点实验室,北京102249

出　　处：《石油学报（石油加工）》2023年第6期1215-1230,共16页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点研发计划项目(2021YFA1501203);中国石油天然气集团公司创新基金(2021DQ02-0702)资助。

摘　　要：在反应温度400℃和反应压力6 MPa条件下,在Beta分子筛负载不同加氢活性中心(Co、Mo、Ni和W)的硫化物双功能催化剂上对四氢萘选择性加氢裂化(HDC)制备苯、甲苯和二甲苯(BTX)反应行为进行研究。通过建立四氢萘加氢裂化反应的九集总反应动力学模型,结合各反应速率常数,探讨不同双功能催化剂的反应性能。研究表明:NiW(Ni(5)W(20)/Beta-40)和NiMo(Ni(5)Mo(20)/Beta-40)催化剂中,Beta分子筛载体上活性金属和酸中心含量高,在四氢萘转化率分别为98%和96%时,表现出较高的BTX选择性(63%和56%,摩尔分数)。结合反应结果和反应速率常数数据可以发现:虽然Ni(5)W(20)/Beta-40和Ni(5)Mo(20)/Beta-40催化剂上积炭速率高,但是BTX生成速率与BTX过度加氢裂化反应速率的比值、BTX生成速率与催化剂积炭速率的比值也都高于其他催化剂,表现出优异的BTX选择性。A study was performed on the selective hydrocracking(HDC)reaction of tetrahydronaphthalene(THN)into benzene,toluene and xylene(BTX)over sulfides bifunctional HDC catalysts with different hydrogenation active centers(Co,Mo,Ni and W)at the reaction temperature of 400℃and reaction pressure of 6 MPa.A nine-lump reaction kinetic model for the THN HDC reaction,and all the reaction rate constants in the reaction network were used to clarify the performance of bifunctional catalysts.The results show that Beta zeolite supported NiW(Ni(5)W(20)/Beta-40)and NiMo(Ni(5)Mo(20)/Beta-40)catalysts exhibit high contents of active metal species and acid sites,respectively,leading to a high BTX selectivity(63%and 56%,molar fraction)at 98%and 96%THN conversion.Based on the reaction results and reaction rate constants,it can be concluded that although the coking rates over Ni(5)W(20)/Beta-40 and Ni(5)Mo(20)/Beta-40 catalysts are relatively high,the ratio of BTX formation reaction rate to the excessive hydrocracking rate of BTX and the ratio of BTX formation reaction rate to the coking rate of catalyst are higher than those of other catalysts,resulting in a high BTX selectivity.

关 键 词：加氢裂化 双功能催化剂 四氢萘(THN) 反应动力学 苯、甲苯和二甲苯(BTX) 

分 类 号：O643.1[理学—物理化学] TQ241.1[理学—化学]