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丁酮肟盐酸盐热分解反应动力学及危险性研究

Thermal decomposition kinetics and hazard of butanone oxime hydrochloride
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摘要 为探究丁酮肟盐酸盐的热危险性,利用差示扫描量热仪(Differential Scanning Calorimeter,DSC)获得热分解特性与分解反应类型;并利用Kissinger、KAS(Kissinger Akahira Sunose)线性回归法和非线性回归法求解动力学模型及参数;利用所得动力学参数推算其最大反应速率到达时间(Time to Maximun Rate,TMR)、转换限制时间(Conversion Limit Time,TCL)和自加速分解温度(Self-Accelerating Decomposition Temperature,SADT)。结果表明:随升温速率提高,初始分解温度和分解的峰值温度提高,平均比放热量为749.01 kJ/kg;丁酮肟盐酸盐的热分解具有自催化特征,包含两个自催化反阶段,且第1阶段产生的热量诱导第2阶段的发生,第1阶段的Ea为99.02 kJ/mol,第2阶段的Ea为93.46 kJ/mol;丁酮肟盐酸盐的SADT为39.51℃,控制温度为29.51℃,因此在生产、运输和储存过程中应加强温度的监控。 To explore the thermal hazard of butanone oxime hydrochloride,a thermodynamic analysis was carried out for the first time.Dynamic scanning calorimetry was used to study the thermal decomposition process of butanone oxime hydrochloride at different heating rates,and the decomposition reaction type was determined by the“interruption and re-scanning”method.The linear regression method of Kissinger and KAS(Kissinger Akahira Sunose)was used to analyze the relationship between activation energy and conversion rate,and the characteristics of thermal decomposition reaction were preliminarily determined.The thermodynamic model was established by using the obtained kinetic parameters.The Time to Maximun Rate(TMR),Conversion Limit Time(TCL),and Self-Accelerating Decomposition Temperature(SADT)were calculated.The results show that the initial decomposition temperature ranges from 130.22℃to 155.17℃.With the increase in heating rate,the initial decomposition temperature and the peak temperature of decomposition also increase.The average specific heat release is 749.01 kJ/kg,and the decomposition heat evaluation grade is 2,indicating that the decomposition heat of butanone oxime hydrochloride is larger and the potential explosion risk is higher.Butanone oxime hydrochloride has autocatalytic properties,including two autocatalytic reverse stages.The reaction temperature of the first stage is low,the reaction is preferentially carried out,and heat is generated to induce the second stage.The Ea of the first stage is 99.02 kJ/mol,and the Ea of the second stage is 93.46 kJ/mol.At 71.5℃,butanone oxime hydrochloride reached the maximum reaction rate within 1.7 days,and the conversion rate reached the limit value(10%)within 1.8 days.The SADT of butanone oxime hydrochloride under 250 kg packaging was 39.52℃,the control temperature was 29.51℃,and the alarm temperature should be 34.51℃.Therefore,attention must be paid to the thermal stability of butanone oxime hydrochloride.Temperature monitoring should be strengthened during production,transportation,and storage,and cooling devices should be installed in the relevant process flow.
作者 黄勇 张玉雯 黄安麒 崔嘉伟 刘烨铖 HUANG Yong;ZHANG Yuwen;HUANG Anchi;CUI Jiawei;LIU Yecheng(School of Safety Science and Engineering,Changzhou University,Changzhou 213164,Jiangsu,China;School of Materials Science and Engineering,Changzhou University,Changzhou 213164,Jiangsu,China)
出处 《安全与环境学报》 CAS CSCD 北大核心 2023年第11期3936-3943,共8页 Journal of Safety and Environment
基金 2021年江苏省重点研发计划(社会发展)项目(BE2021641) 安全生产重特大事故防治关键技术科技项目(jiangsu 00142017AQ) 2022年江苏省产学研合作项目(BY2022782)。
关键词 安全工程 热危险性 热分解 动力学 自催化反应 safety engineering thermal hazard thermal decomposition dynamics autocatalytic reaction
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