噻吩Friedel-Crafts酰基化反应的研究  

Friedel-Crafts Acylation Reaction of Thiophene

作　　者：佟天下[1] 陈志华[1] 杨丽娟[2] 贾鹏飞[3] 程婧[4] 曾爱武[1] 

机构地区：[1]天津大学化学工程联合国家重点实验室,天津300072 [2]天津大学化工学院,天津市应用催化科学与工程重点实验室,天津300072 [3]天津天大天久科技股份有限公司,天津300072 [4]中国石油天然气管道工程有限公司天津滨海分公司,天津300457

出　　处：《化学工业与工程》2014年第2期1-6,共6页Chemical Industry and Engineering

基　　金：国家科技支撑项目(2007BAB24B05)

摘　　要：在常压条件下,通过对5种催化剂(HZSM-5,HY,13X,ZnCl2和C25型沸石分子筛)进行催化反应测试,最终筛选出高活性的C25型沸石分子筛作为噻吩Friedel-Crafts酰基化反应的催化剂,以醋酸酐为酰化试剂,对噻吩酰基化反应合成2-乙酰噻吩进行了研究。重点探讨了高温、原料配比、溶剂醋酸的加入量、不同浓度的硝酸改性的催化剂等因素对噻吩Friedel-Crafts酰基化反应过程的影响。确定了最适宜的反应条件,在80℃条件下,n(噻吩)∶n(醋酸酐)为1∶2时,反应5 h,噻吩的转化率高达97.23%。当加入醋酸溶剂时,催化剂的催化活性显著升高;当醋酸的加入量占原料总质量的8.72%时,反应5 h,噻吩的转化率提高1.3%;通过0.5 mol/L硝酸改性时,催化剂的活性最强。同时,采用固定床反应器研究了高温对气相噻吩酰基化反应的影响,得出反应温度为92℃时,噻吩的反应效果最好。最后,对反应产液进行精馏提纯,得到质量分数高于99.90%的产品2-乙酰噻吩。Through the catalytic reaction test of five kinds of catalysts, including HZSM-5, HY, 13X, ZnC12 and C25, and a higher activity zeolite C25 was chosen as catalyst and acetic anhydride was applied as acylating agent in the Friedel-Crafts acylation reaction of thiophene at atmospheric pressure. The effects of higher reaction temperature, the raw material ratio, the additional amount of solvent acetic acid, and the different concentrations of nitric acid modified catalysts on the Friedel-Crafis acylation reaction of thiophene were investigated principally. When the reaction temperature is 80 ℃, the suitable reactive conditions are ： the mole ratio of thiophene to acetic anhydride is 1： 2, reaction time 5 h, the conversion of thiophene up to 97.23%. The catalytic activity was greatly improved when the acetic acid was added ; the amount of acetic acid account for 8.72% of the total materials, reaction time 5 h, the conversion of thiophene was increased by 1.3% ; the catalytic activity was up to the best when the zeolite was modified by 0.5 mol/L nitric acid. Meanwhile, the research on acylation reaction of gas thiophene was conducted by fixed bed reactor, and found that the best temperature was 92℃. Finally, the reactive products were refined to get the purity of 2-acetyl thiophene up to 99.90%.

关 键 词：沸石分子筛 酰化试剂 2-乙酰噻吩 催化活性 固定床反应器 精馏提纯 

分 类 号：TQ251.2[化学工程—有机化工]