摘要
采用了差示扫描量热仪和加速绝热扫描量热仪对重氮乙酸乙酯的相关热力学参数进行了测量,通过相关动力学分析得到了反应最大速率的到达时间(TMR ad),利用反应量热仪对重氮乙酸乙酯合成工艺进行量热实验,并通过量热数据获得了绝热温升、反应焓变和体系在失控情形下所能到达的最高合成温度(MTSR),比较合成温度(T_(p))、失控情形下到达的最高合成温度(MTSR)、二次分解温度T_(D24)以及技术原因的最高温度(MTT),确定风险级别。结果表明,重氮乙酸乙酯起始分解温度为85℃,放热量149.146 J/g,具有潜在的分解危险性;重氮化合成工艺的风险等级为:T_(p)<MTSR<T_(D24)<MTT,由风险等级分级标准可将该工艺的风险等级确定为2级,并可根据风险等级,提出对应的防护措施,确保该工艺合成过程中的安全。
Differential scanning calorimeter and accelerated adiabatic scanning calorimeter were used to measure the relevant thermodynamic parameters of ethyl diazoacetate.The time of arrival(TMR ad)of the maximum reaction rate was obtained through correlation kinetic analysis.The reaction calorimeter was used to conduct calorimetric experiments on the synthesis process of ethyl diazoacetate,and the adiabatic temperature rise and the reaction enthalpy change and the maximum synthesis temperature(MTSR)that the system can reach in the case of out of control,compare the synthesis temperature(T_(p)),the maximum synthesis temperature(MTSR)reached in the case of out of control,the secondary decomposition temperature T_(D24)and the maximum temperature(MTT)for technical reasons,and determine the risk level.The results show that the initial decomposition temperature of ethyl diazoacetate is 85℃,and the heat release is 149.146 J/g,which has potential decomposition risk;the risk of diazotization synthesis process is:T_(p)<MTSR<T_(D24)<MTT.The risk level of the process can be determined as level 2 according to the risk level classification standard,and corresponding protective measures can be put forward according to the risk level to ensure the safety in the synthesis process of the process.
作者
任彦浩
叶启亮
马莹莹
袁佩青
REN Yan-hao;YE Qi-liang;MA Ying-ying;YUAN Pei-qing(East China University of Science and Technology,College of Chemical Engineering,Shanghai 200237,China;Thermal Safety Laboratory of Shanghai Solvay Investment Co.,Ltd.,Shanghai 201100,China)
出处
《应用化工》
CAS
CSCD
北大核心
2022年第12期3430-3433,3439,共5页
Applied Chemical Industry
基金
国家自然科学基金项目(22178113)。
关键词
重氮乙酸乙酯
反应量热
过程控制
风险评估
安全措施
ethyl diazoacetate
reaction calorimetry
process control
risk assessment
safety measures
