液相氟化制备HFC-32过程中催化剂的失活规律及其对反应的影响  

Deactivation Law of Catalyst in the Preparation of HFC-32 by Liquid Phase Fluorination and Its Influence on the Reaction

作　　者：赵恒军 钱广[2] 朱杰[2] ZHAO Hengjun;QIAN Guang;ZHU Jie(Engineering Technology Center,Jiangsu Sanmei Chemical Industry Co.,Ltd.,Nantong 226407,China;College of Biological and Chemical Engineering,Jiaxing University,Jiaxing 314001,China)

机构地区：[1]江苏三美化工有限公司技术中心,江苏南通226407 [2]嘉兴学院生化学院,浙江嘉兴314001

出　　处：《有机氟工业》2022年第4期1-7,共7页Organo-Fluorine Industry

基　　金：国家自然科学基金项目(21773094)。

摘　　要：在液相氟化制备HFC-32的过程中会发生催化剂五氯化锑失活引发的反应转化率下降、反应釜腐蚀穿孔等现象,后者对制备过程带来了较大的安全隐患。研究了在催化剂不通氯活化条件下,采用管式反应器连续制备HFC-32过程中催化剂的变化规律及其对反应转化率的影响,确认了催化剂五氯化锑在反应过程中的失活规律及总锑和五价锑含量的变化规律,指出了五价锑含量对反应转化率的影响为正相关关系。另外,对HFC-32制备过程中反应釜中催化剂失活后的产物进行了分析,确定了失活产物的组成为SbClF2。研究了反应釜内催化剂连续活化过程中,反应液中五价锑及总锑含量的变化与反应釜穿孔失效的关系,对HFC-32的反应机理进行了推测。指出反应釜的腐蚀穿孔为化学腐蚀和电化学腐蚀的共同作用,为液相氟化安全高效制备HFC-32提供了理论支撑。During the preparation of HFC-32 by liquid phase fluorination,the reduction of reaction conversion rate and the corrosion and perforation of the reactor caused by the deactivation of SbCl5catalyst will occur,which brings great potential safety hazards to the preparation process.The change law of catalyst and its influence on the reaction conversion rate during the continuous preparation of HFC-32 in a tubular reactor without catalyst activation were studied,the deactivation law of SbCl5catalyst in the reaction process and the change law of total antimony and pentavalent antimony content were confirmed.It is pointed out that the influence of antimony pentavalent content on the reaction conversion rate is a positive correlation.Moreover,the catalyst deactivation product from the reaction kettle was analyzed in the preparation of HFC-32,and the composition of it was determined to be SbClF2.During the continuous activation of catalyst in the production of HFC-32 by reaction kettle,the relationship between the failure of the reactor perforation and the change of pentavalent antimony and total antimony content in the reaction solution was studied,and the reaction mechanism of HFC-32 was speculated.It was pointed out that the corrosion perforation of the reactor was chemical corrosion and electrical corrosion.The research provides theoretical support for the safe and efficient preparation of HFC-32 by liquid phase fluorination.

关 键 词：HFC-32 催化剂失活规律 五价锑含量 反应转化率 反应釜腐蚀穿孔 节能生产 

分 类 号：TQ222.213[化学工程—有机化工] TQ426