偶氮二甲酸二异丙酯的热分解及动力学特征研究
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摘要
采用差示扫描量热仪(DSC)研究了偶氮二甲酸二异丙酯(DIAD)在动态条件下的热稳定性。DSC的测试结果表明:在测试过程中只检测到一段放热信号,且随着升温速率的增加(2℃/min、4℃/min、8℃/min和10℃/min),DIAD样品放热分解的起始温度从199.3℃升至218.4℃,峰值温度从218.5℃升至246.0℃;不同升温速率条件下DIAD样品热分解的平均比放热量■为681.8 J/g。基于动态DSC测试数据,利用TSS软件模拟确定了DIAD样品的热分解反应动力学参数。模拟结果表明:DIAD样品的热分解过程遵循自催化反应机理,且拟合得到的DIAD样品热分解反应的动力学参数结果与基于等转化率微分算法计算得到的结果十分接近。基于求取的DIAD热分解动力学模型(自催化反应模型),通过热爆炸模拟对DIAD样品的热危险性进行评估,并利用TSS软件对DIAD样品的若干热危险性和热爆炸性能参数进行了预测,获取了TD_(24)、TD_8、TCL、SADT、ET和CT等参数。本研究有助于优化化学品的运输和储存条件,以尽可能地减少工业灾难。
This paper studies the thermal stability of DIAD under dynamic conditions by Differential Scanning Calorimeter(DSC).The DSC results show that only one exothermic peak is identified,and with the increase of the heating rate(2℃/min、4℃/min、8℃/min and 10℃/min),the onset decomposition temperatures are increased from 199.3℃ to 218.4℃,and the peak temperatures are increased from 218.5℃ to 246.0℃.Also the average decomposition enthalpy ■ of exothermic peak detected in dynamic tests is 681.8 J/g.Based on dynamic DSC data,the paper also applies TSS software to determining some thermal decomposition kinetic parameters,and the simulation results show that DIAD underwent an autocatalytic reaction and these simulated kinetic parameters are close to these values calculated by Friedman method based on the dynamic data.Based on the thermal decomposition kinetics model obtained above,the paper evaluates the thermal hazard of DIAD by thermal explosion simulation,and predicts several thermal hazard parameters,such as TD_(24),TD_8,TCL,SADT,ET and CT.The study helps to optimize the transport and storage conditions of chemicals while minimizing industrial disasters.
This paper studies the thermal stability of DIAD under dynamic conditions by Differential Scanning Calorimeter(DSC).The DSC results show that only one exothermic peak is identified,and with the increase of the heating rate(2℃/min、4℃/min、8℃/min and 10℃/min),the onset decomposition temperatures are increased from 199.3℃ to 218.4℃,and the peak temperatures are increased from 218.5℃ to 246.0℃.Also the average decomposition enthalpy ■ of exothermic peak detected in dynamic tests is 681.8 J/g.Based on dynamic DSC data,the paper also applies TSS software to determining some thermal decomposition kinetic parameters,and the simulation results show that DIAD underwent an autocatalytic reaction and these simulated kinetic parameters are close to these values calculated by Friedman method based on the dynamic data.Based on the thermal decomposition kinetics model obtained above,the paper evaluates the thermal hazard of DIAD by thermal explosion simulation,and predicts several thermal hazard parameters,such as TD_(24),TD_8,TCL,SADT,ET and CT.The study helps to optimize the transport and storage conditions of chemicals while minimizing industrial disasters.
引文
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[15]梅辉辉,曹雄.热爆炸理论在硝酸铵水溶液热安全性研究中的应用[J].安全与环境工程,2012,19(2):128-131.
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[19]邢志祥,汪李金,钱辉,等.Al2O3-SiO2气凝胶隔热材料的研究进展[J].安全与环境工程,2018,25(3):177-182.
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[3] 江美丽,郑俊鹤,王犇.过氧化二异丙苯的热稳定性及安全性研究 [J].安全与环境学报,2014,14(1):117-121.
[4] 王炎,陈利平,陈网桦.易燃易爆危险化学品DSC鉴别方法的研究[J].安全与环境工程,2018,25(2):143-149.
[5] Kossoy A A,Akhmetshin Y G.Identification of kinetic models for the assessment of reaction hazards[J].Process Safety Progress,2007,26(3):209-220.
[6] Kossoy A A,Sheinman I.Evaluating thermal explosion hazard by using kinetics-based simulation approach[J].Process Safety and Environmental Protection,2004,82(6):421-430.
[7] Cheng Y F,Liu S H,Shu C M,et al.Energy estimation and modeling solid thermal explosion containment on reactor for three organic peroxides by calorimetric technique[J].Journal of Thermal Analysis and Calorimetry,2017,130:1201-1211.
[8] 吕家育,陈网桦,陈利平,等.2,4-二氯过氧化苯甲酰的热分解及等温动力学模型[J].化工学报,2013,64 (11):4044-4059.
[9] Friedman H L.Kinetics of thermal degradation of char-forming plastics from thermogravimetry.Application to a phenolic plastic[J].Journal of Polymer Science Part C:Polymer Symposia,1964,6(1) :183-195.
[10]ChemInform Saint Petersburg-CISP Ltd.Thermal Safety Software (TSS).[EB/OL].(2018-10-22).http://www.cisp.spb.ru.
[11]黄飞,金满平,孙峰.BIPB 的热分解动力学和失控反应模拟[J].安全与环境学报,2012,12(2):217-223.
[12]周德红,冯豪,冯文斌,等.基于GA-BP神经网络的化工园区应急救援能力的可靠性分析[J],安全与环境工程,2017,24(5):43-49.
[13]Wang S Y,Kossoy A A,Yao Y D,et al.Kinetics-based simulation approach to evaluate thermal hazards of benzaldehyde oxime by DSC tests[J].Thermochimica Acta,2017,655:319-25.
[14]高海素,陈网桦,陈利平,等.BPO在等温条件下的热稳定性研究[J].安全与环境学报.2014,14(1):109-112.
[15]梅辉辉,曹雄.热爆炸理论在硝酸铵水溶液热安全性研究中的应用[J].安全与环境工程,2012,19(2):128-131.
[16]Frank-Kamenetskii D A.Diffusion and Heat Exchange in Chemical Kinetics[M].2nd ed.New York,USA:Plenum Press,1969.
[17]Bowes P C.Self-heating:Evaluating and Controlling the Hazards[M].New York,USA:Elsevier,1984.
[18]Kosoy A A,Sheinman I.Comparative analysis of the methods for SADT determination[J].J.Hazard.Mater,2007,142:26-38.
[19]邢志祥,汪李金,钱辉,等.Al2O3-SiO2气凝胶隔热材料的研究进展[J].安全与环境工程,2018,25(3):177-182.