基于氯化铜的乙炔氢氯化无汞催化剂的研发及应用  

Development and commercialization of mercury-free copper-based catalyst for acetylene hydrochlorination

作　　者：钟劲光 刘星 刘瑞艳 ZHONG Jingguang;LIU Xing;LIU Ruiyan(Zhongke Yigong(Shanghai)Chemical Technology Co.,Ltd.,Shanghai 200235,China)

机构地区：[1]中科易工(上海)化学科技有限公司,上海200235

出　　处：《聚氯乙烯》2021年第6期22-24,25-27,共6页Polyvinyl Chloride

摘　　要：根据现有的乙炔氢氯化反应的机理缺陷,提出了该催化反应的反应历程,并分析了主要影响因素(包括乙炔活化和氯化氢活化两个方面)。金属与Cl^(-)络合形成的金属配合物的标准电极电势越高,乙炔越容易活化;HCl活化可以通过MCl_(n),与HCl的络合作用产生金属络合酸,解离出H^(+)和Cl^(-);或者通过引入弱碱性溶剂,利.用溶剂化效应使HCl离子化,释放出H^(+)和Cl^(-)。据此,形成了无汞催化剂研发的新思路,成功开发了以CuCl_(2)为活性组分、非质子极性溶剂作为助剂的无汞非贵金属铜基催化剂。通过优化乙炔氢氯化反应工艺条件,铜基催化剂的催化性能优于工业汞催化剂。该催化剂已在工业装置上运行8000 h,前台转化器出口乙炔体积分数约15%,后台转化器出口乙炔体积分数约2.5%。According to the mechanism defects of acetylene hydrochlorination,the reaction mecha-nism of the catalytic reaction was proposed,and the main influencing factors(including acetylene activa-tion and hydrogen chloride activation)were analyzed.The higher the standard electrode potential of metal complexes formed by complexation of metal with Cl^(-),the easier C_(2)H_(2)was activated;HCI activation can produce metal complex acid through the complexation of.MCI_(n) with HCI,and dissociate H^(+)and Cl^(-);Or by introducing weak basic solvent,HCI is ionized by solvation effect to release H^(+)andCl^(-).Therefore,a new idea of mercury free catalyst research and development was formed,and mercury free non-noble metal Cu-based catalyst with CuCl_(2)as active component and aprotic polar solvent as promoter was sucssfully developed.By optimizing the process conditions of acetylene hydrochlorination,the cata-lytic performance of Cu-based catalyst was better than that of industrial mercury catalyst.The catalyst had been in service in an industrial plant for 8000 h.The volume fraction of acetylene at the outlet of firststage reactor was about 15%,and that at the outlet of second-stage reactor was about 2.5%。

关 键 词：乙炔氢氯化 活化 反应 无汞催化剂 标准电极电势 氯化铜 

分 类 号：TQ325.3[化学工程—合成树脂塑料工业]