尿素改性新疆煤基炭负载铜催化剂的乙炔氢氯化性能  

Hydrochlorination of acetylene performance over urea-modified Xinjiang coal-based carbon supported copper catalyst

作　　者：杨海龙 王璐[1,2,3] 闫海军 司建鑫 武荣兰 李小飞[3] 王吉德 关清卿[1] 孙辉 梁长海[4] YANG Hailong;WANG Lu;YAN Haijun;SI Jianxin;WU Ronglan;LI Xiaofei;WANG Jide;GUAN Qingqing;SUN Hui;LIANG Changhai(State Key Laboratory of Oil and Gas Fine Chemicals,Ministry of Education and Xinjiang Uyghur Autonomous Region,School of Chemical Engineering and Technology,Xinjiang University,Urumqi830017,China;State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources,Xinjiang University,Urumqi830017,China;Xinjiang Uygur Autonomous Region Product Quality Supervision and Inspection Institute,Urumqi830011,China;State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian116086,China)

机构地区：[1]新疆大学化工学院石油天然气精细化工教育部和新疆维吾尔自治区重点实验室,新疆维吾尔自治区乌鲁木齐830017 [2]新疆大学碳基能源资源化学与利用国家重点实验室,新疆维吾尔自治区乌鲁木齐830017 [3]新疆维吾尔自治区产品质量监督检验研究院,新疆维吾尔自治区乌鲁木齐830011 [4]大连理工大学精细化工国家重点实验室,辽宁大连116086

出　　处：《洁净煤技术》2024年第6期142-148,共7页Clean Coal Technology

基　　金：国家自然科学基金资助项目(22366036,21968033);新疆维吾尔自治区自然科学基金资助项目(2022D01C375);大连理工大学精细化工国家重点实验室开放课题基金资助项目(KF2304);新疆维吾尔自治区科研计划资助项目(2022A01006-3)。

摘　　要：研发环保、高效、稳定、低成本的无汞催化剂是我国基于煤化工路线的乙炔氢氯化法生产聚氯乙烯(PVC)的关键。针对铜基催化剂在乙炔氢氯化反应中活性低、稳定性差的问题,利用尿素小分子改性策略制备了一系列以新疆煤基炭负载的铜基催化剂(Cu/Urea-CAC),探究铜物种和尿素的加入量对铜基催化剂乙炔氢氯化催化性能的影响。结果表明,当铜负载量为20%、尿素引入量为15%,反应温度为160℃,乙炔空速为120 h-1,氯化氢和乙炔原料的体积比为1.25的反应条件下,20Cu/15Urea-CAC催化剂的乙炔转化率可达92.6%,选择性始终大于98.2%,具有良好的催化性能。利用X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电镜(SEM)、N_(2)物理吸脱附、等离子体发射光谱(ICP-OES)和热重(TG)技术对催化剂进行表征分析,认为适量尿素改性可抑制催化反应过程中Cu活性物种的还原、流失及催化剂表面积碳的形成,进而提升了新疆煤基炭负载铜催化剂的乙炔氢氯化催化性能。研究结果进一步拓展了新疆煤基炭的应用,也为乙炔氢氯化无汞新催化体系的设计合成及其催化作用提供了数据支撑。Developing of environmental friendly,high-efficiency,stable and low-cost non-mercury catalyst is the key to PVC production using coal-route-based acetylene hydrochlorination.To improve the current problems of low catalytic activity and poor stability of copper(Cu)-based catalysts applied in the acetylene hydrochlorination reactions,a series of Cu/Urea-CAC catalysts were prepared by urea mod-ification strategies and the effects of the urea addition and Cu loading on the catalytic performances of catalysts for acetylene hydrochlorina-tion were investigated.When the urea content is 15%and the Cu loading is 20%,the Cu/Urea-CAC catalyst reveal the optimal catalytic performance with the 92.6%C2H2 conversion and 98.2%vinyl chloride selectivity under the reaction conditions of 160℃,a C2 H2 gas hourly space velocity of 120 h-1 and molar ratio of hydrogen chloride to acetylene is 1.25.Combination with the characterization results of XPS,XRD,SEM,N_(2) adsorption and desorption,ICP-OES and TG techniques,it is suggested that the enhanced catalytic performance is mainly related to the appropriate urea addition,which can effectively inhibit Cu species reduction and loss,and decrease the carbon dep-osition,thereby improving the catalytic performance activity of Cu-supported on Xinjiang coal-based carbon catalysts for acetylene hydro-chlorination.The results will expand the application of Xinjiang coal-based carbon and provide theoretical support for the design,synthesis and catalysis of a new catalytic system for acetylene hydrochlorination.

关 键 词：煤基炭 乙炔氢氯化 铜催化 尿素 

分 类 号：TQ032.4[化学工程]