催化氟化合成反式-1,1,1,4,4,4-六氟-2-丁烯的工艺研究  

Synthesis of trans-1,1,1,4,4,4-hexafluoro-2-butene by catalytic fluorination

作　　者：韩升 曾纪珺[1,2] 赵波 贾兆华[1,2] 秦越 毛伟[1,2] 张伟 吕剑 HAN Sheng;ZENG Ji-jun;ZHAO Bo;JIA Zhao-hua;QIN Yue;MAO Wei;ZHANG Wei;Lü Jian(State Key Laboratory of Fluorine&Nitrogen Chemical,Xi’an 710065,China;Xi’an Modern Chemistry Research Institute,Xi’an 710065,China)

机构地区：[1]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065 [2]西安近代化学研究所,陕西西安710065

出　　处：《应用化工》2020年第9期2257-2260,共4页Applied Chemical Industry

基　　金：陕西省重点产业创新链项目(2019ZDLGY06-01);西安市高校人才服务企业项目(GXYD12.1)。

摘　　要：在氟化镁基催化剂作用下,以催化氟化1,1,1,3-四氯-4,4,4-三氟丁烷(HCFC-343jfd)合成反式-1,1,1,4,4,4-六氟-2-丁烯(E-HFO-1336mzz)为研究对象,开展了反应温度、物料比、接触时间及催化剂的寿命实验。结果表明,最佳反应条件为反应温度300℃,HF与HCFC-343jfd的摩尔比为15∶1,停留时间6 s,在该条件下,HCFC-343jfd的转化率为100%,E-HFO-1336mzz的选择性为95.1%,且连续反应300 h后,HCFC-343jfd的转化率>99.0%,E-HFO-1336mzz的选择性>94.5%。采用新型无铬催化剂,获得了最佳E-HFO-1336mzz反应工艺,具有较高的氟化工业应用前景。Synthesis of trans-1,1,1,4,4,4-hexafluoro-2-butene(E-HFO-1336 mzz)from 1,1,1,3-tetrachloro-4,4,4-trifluoro-butane(HCFC-343 jfd)and anhydrous hydrogen fluoride was studied by catalytic fluorination over MgF2-based catalyst.The effect factors,including reaction temperature,ratio of HF and HCFC-343 jfd,contact time and lifetime of catalyst,were researched.The results indicated the optimal reaction condition:temperature 300℃,flow ratio of HF and HCFC-343 jfd=15∶1 and the contact time of 6 s.Under the optimal reaction condition,the conversion of HCFC-343 jfd was 100%and the selectivity of E-HFO-1336 mzz was up to 95.1%.After 300 h of continuous reaction,the conversion of HCFC-343 jfd and the selectivity of E-HFO-1336 mzz were above 99.0%and 94.5%respectively.The reaction process of E-HFO-1336 mzz is optimized by using non-chromium catalyst,which has shown a great potential fluorochemical industry application.

关 键 词：顺式-1 1 1 4 4 4-六氟-2-丁烯 反式-1 1 1 4 4 4-六氟-2-丁烯 1 1 1 3-四氯-4 4 4-三氟丁烷 氟化镁基催化剂 

分 类 号：TQ222.424[化学工程—有机化工] TQ426.94