氯丙烯环氧化反应器热危险性评估

摘要

针对氯丙烯环氧化反应器存在的危险性,采用理论计算与热分析测试相结合的方法,对氯丙烯直接环氧化工艺反应器的热危险性进行了评估.实验结果表明,氯丙烯直接环氧化工艺属极危险的工艺过程;随水相 H2O2 浓度的增加,试样达到最大反应速率所需的时间逐渐缩短,H2O2 浓度过高极易造成失控反应的发生;在温度接近60℃时磷钨酸季铵盐催化剂开始分解;H2O2 与催化剂混合后,H2O2 的起始分解温度降至50℃左右;仅需150℃左右的温升,即可引发反应器内油相物料的二次反应.%Thermal safety of the process for 3-chloropropene epoxidation with H2O2 to epichlorohydrin was evaluated by combination of theoretical calculation with thermal analysis.The danger of runaway reaction and the thermal stability of liquid materials were tested by means of accelerating calorimeter and C80 calorimeter.According to the assessment criteria for chemical processes, the criticality of the 3-chloropropene epoxidation process is catastrophic.The results showed that the time to maximum reaction rate under adiabatic conditions after reaction runaway was shortened with the increase of H2O2 concentration.It is apt to result in runaway reaction that accumulative concentration of H2O2 is too high.The onset decomposition temperature of the catalyst is about 60 ℃.After mixed with the catalyst, the onset decomposition temperature of H2O2 is advanced to about 50 ℃.Secondary reaction would be triggered in the reactor in case of a temperature rise of 150 ℃ or so.