Ag-Ga/ZSM-5催化剂对沙特中质原油的催化性能和产物中轻质芳烃的形成机制  

Catalytic performance on upgrading saudi medium crude oil over Ag-Ga/ZSM-5 catalyst and the formation mechanistic study of light aromatics product

作　　者：钟杰 雷杰 李康[1,2] 王慧敏 彭鹏 王有和[1] 阎子峰[1] ZHONG Jie;LEI Jie;LI Kang;WANG Huimin;PENG Peng;WANG Youhe;YAN Zifeng(State Key Laboratory for Heavy Oil Processing in China University of Petroleum(East China),Qingdao 266580,China;Luoyang R&D Center of Technology of SINOPEC Engineering(Group)Company Limited,Luoyang 471003,China)

机构地区：[1]中国石油大学(华东)重质油国家重点实验室,山东青岛266580 [2]中国石化炼化工程集团洛阳技术研发中心,河南洛阳471003

出　　处：《中国石油大学学报（自然科学版）》2023年第3期181-189,共9页Journal of China University of Petroleum(Edition of Natural Science)

基　　金：国家自然科学基金项目(21776311);中央高校基本科研业务费专项(22CX03001A);国家重点研发计划政府间国际科技创新合作重点专项(2018YFE0118200);山东省重点研发计划(重大科技创新工程)项目(2019JZZY010506)。

摘　　要：以商业ZSM-5分子筛为载体,通过等体积浸渍法制备负载双金属Ag和Ga的重油改质催化剂,采用X-射线衍射、氮气吸附脱附、吡啶吸附红外和NH3程序升温脱附等手段对样品进行表征,考察所制备催化剂在不同反应温度(380~420℃)下甲烷和氮气气氛中对沙特中质原油改质效果和产物轻质芳烃的影响。结果表明,Ag-Ga/ZSM-5催化剂上Ag、Ga等负载金属高度分散,且B酸性位减少和L酸性位增加;高度分散的负载金属物种及其产生的L酸性位和载体上的B酸性位协同作用可以取得良好的原油改质效果;适度提升温度(380~400℃)有利于油品改质,但过高温度(410~420℃)会降低产物油液体收率并严重结焦;当反应温度为400℃时取得最佳改质效果,在此温度下产物油性质明显改善,轻质芳烃质量分数增加11.32%;催化剂上高度分散的Ag、Ga等负载金属物种及B酸性位减少和L酸性位增加能有效活化甲烷,同时参与汽油馏分共芳构化和烷基化及柴油馏分裂解并促进轻质芳烃的生成。Catalysts for heavy oil upgrading were prepared through incipient wetness impregnation method using one commercial ZSM-5 zeolite as a carrier with Ag-Ga loadings.The catalysts were characterized by XRD,Py-FTIR,N 2 adsorption-desorption isotherms and temperature-programmed desorption of ammonia.The effects of reaction temperature(380-420℃)on Saudi medium crude oil upgrading and light aromatics production under methane were studied.The results indicate that the supported metals such as Ag and Ga are highly dispersed on the Ag-Ga/ZSM-5 catalyst,and there are less Br nsted acid sites and more Lewis acid sites.It is found that the synergistic effect of highly dispersed supported metal species,the generated Lewis acid sites and Br nsted acid sites on the supports can achieve good performance for crude oil upgrading.Also,proper increasing of reaction temperature(380-400℃)is favorable to upgrading performance.However,high temperature(410-420℃)will reduce the liquid yield of product oil and cause serious coke formation.The best upgrading performance is obtained when the reaction temperature is 400℃,at which the properties of the product oil can be significantly improved and the mass fraction of light aromatics increased by 11.32%.The catalysts with highly dispersed Ag,Ga metal species,less Br nsted acid and more Lewis acid can effectively activate methane,which participates in the co-aromatization and alkylation of gasoline fractions and the cracking of diesel fractions to produce a large number of light aromatics.

关 键 词：重油改质 甲烷活化 催化剂 模型化合物 轻质芳烃 

分 类 号：O611.4[理学—无机化学]