2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学

doi:10.3866/PKU.WHXB201212141

物理化学学报 >> 2013, Vol. 29 >> Issue (03): 479-485.doi: 10.3866/PKU.WHXB201212141

2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学

鲍士龙, 陈网桦, 陈利平, 高海素, 吕家育

南京理工大学化工学院安全工程系, 南京 210094

收稿日期:2012-09-28 修回日期:2012-12-13 发布日期:2013-02-25
通讯作者: 陈网桦 E-mail:chenwh_nust@163.com
基金资助:
国家自然科学基金(51204099)资助项目

Identification and Thermokinetics of Autocatalytic Exothermic Decomposition of 2,4-Dinitrotoluene

BAO Shi-Long, CHEN Wang-Hua, CHEN Li-Ping, GAO Hai-Su, LÜ Jia-Yu

Department of Safety Engineering, Institute of Chemical Technology, Nanjing University of Technology and Science, Nanjing 210094, P. R. China

Received:2012-09-28 Revised:2012-12-13 Published:2013-02-25
Supported by:
The project was supported by the National Natural Science Foundation of China (51204099).

摘要/Abstract

摘要：

为研究2,4-二硝基甲苯(2,4-DNT)的热危险性及其分解反应的特征, 利用差示扫描量热仪(DSC)对该物质进行了动态扫描测试, 得到其起始分解温度T₀范围为272.4-303.5℃, 分解热ΔH_d约为2.22 kJ·g^-1. 在此基础上, 采用瑞士安全技术与保障研究所提出的快速鉴别法(瑞士方法)及数值模拟技术, 对其分解反应的特性参数进行了推算, 结果表明其分解具有自催化性. 采用Malek法分析了该物质分解反应的最概然机理函数并得出了相关动力学参数, 表明其分解具有自催化性且符合Sestak-Berggren 双参数自催化模型(SB模型), 这与瑞士方法所得结论一致. 采用等温DSC测试获得了该物质的‘钟形’热解曲线, 从而验证了两种方法的结论.

关键词: 自催化分解反应, 差示扫描量热仪, 快速鉴别, Malek法, 分解反应动力学

Abstract:

The thermal stability and autocatalytic decomposition of 2,4-dinitrotoluene (2,4-DNT) is investigated under dynamic and isothermal conditions using differential scanning calorimetry (DSC). The temperature range of initial exothermic temperature (T₀) is 272.4-303.5℃, and its decomposition enthalpy (ΔH_d) is about 2.22 kJ·g^-1. An identification method based on a numerical simulation technique from the Swiss Institute for the Promotion of Safety and Security (Swiss method) is used to determine the characteristic parameters of the decomposition reaction, revealing that the decomposition of 2,4-DNT is potentially autocatalytic. The Malek method is used to determine the most probable mechanism function and kinetic parameters of 2,4-DNT decomposition. The Sestak-Berggren model with two parameters is suitable to describe the autocatalytic decomposition of 2,4-DNT, which is consistent with the results of the Swiss method and isothermal experimental results. Isothermal DSC experiments confirmed that the decomposition of 2,4-DNT is autocatalytic.

Key words: Autocatalytic decomposition reaction, Differential scanning calorimeter, Rapid identification, Malek method, Decomposition kinetics

鲍士龙, 陈网桦, 陈利平, 高海素, 吕家育. 2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学[J]. 物理化学学报, 2013, 29(03): 479-485.

BAO Shi-Long, CHEN Wang-Hua, CHEN Li-Ping, GAO Hai-Su, LÜ Jia-Yu. Identification and Thermokinetics of Autocatalytic Exothermic Decomposition of 2,4-Dinitrotoluene[J]. Acta Phys. -Chim. Sin., 2013, 29(03): 479-485.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201212141

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I03/479

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2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学

Identification and Thermokinetics of Autocatalytic Exothermic Decomposition of 2,4-Dinitrotoluene

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