CHINESE JOURNAL OF ENERGETIC MATERIALS
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FOX-7合成过程中水解反应的热危险性及反应动力学
作者:
作者单位:

1.西安近代化学研究所, 陕西 西安 710065;2.甘肃银光化学工业集团, 甘肃 白银 730900

作者简介:

许诚(1985-),女,副研究员,主要从事含能材料合成及性能研究。

通讯作者:

周诚(1975-),男,研究员,主要从事含能材料的制备及性能研究。e-mail:zhoucn@163.com

基金项目:

国家自然科学基金(21805224)


Thermal Hazard and Kinetic Study for the Hydrolysis in the Synthesis Process of FOX-7
Author:
Affiliation:

1.Xi′an Modern Chemistry ResearchI nstitute, Xi′an 710065, China;2.Gansu Yinguang Chemical Industry Group, Baiyin 730900, China

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    摘要:

    利用反应量热仪(RC1),测定了以2-(二硝基亚甲基)-5,5-二硝基-2H-嘧啶-4,6-二酮(TNMPO)为原料,经水解反应制备FOX-7工艺的热流曲线,对水解反应的工艺热危险性进行了分析,采用定温实验,利用n级反应动力学方程对不同温度下的水解反应速率进行了拟合,进而获得了水解反应的表观反应动力学参数。结果显示,20 ℃条件下,TNMPO水解制备FOX-7反应的摩尔生成焓为-46.563 kJ∙mol-1,绝热温升为9.1 K。若水解反应发生失控,反应体系可到达的最高温度(MTSR)为29.1 ℃。对2-(二硝基亚甲基)-5,5-二硝基-2H-嘧啶-4,6-二酮(TNMPO)的反应级数为0.9317,表观活化能Ea为73.2 kJ∙mol-1,指前因子A为5.03×109 s-1

    Abstract:

    To investigate the thermal hazards of the synthetic reaction process of FOX-7, the heat flow curve of the hydrolysisinvolved therein has been measured by using Reaction Calorimeter (RC1). The nth-order kinetic models were applied to different temperature systems and the apparent kinetic parameters of these processes were obtained. The results indicated that the exothermic heat of the synthesis reaction was -46.563 kJ∙mol-1, and the adiabatic temperature rise was 9.1 K. Under the thermal runaway chemical reaction condition, the maximum temperature of the synthesis reaction (MTSR) is 29.1 ℃. The reaction order is 1.21 for synthesis of 2-(dinitromethylene)-5,5-dinitrodihydropyrimidine-4,6-dione. The activation energy (Ea) of the reaction is 73.2 kJ∙mol-1, with the pre-exponential factor of 5.03×109 s-1.

    表 3 线性回归得到的指前因子和活化能Table 3 Pre-exponential factor and activation energy derived from the linear regression line
    表 1 FOX-7制备反应的反应热数据Table 1 Calorimetric data for the synthesis process of FOX-7
    表 2 不同温度条件下反应速率常数k的拟合结果Table 2 The reaction rate constants at different temperatures by a fitting method
    图1 FOX-7制备反应的热流曲线Fig.1 Heat flow curve recorded during the synthesis process of FOX-7
    图2 lnCA0(1-x)-lnqr图Fig.2 The dependences of lnqr on lnCA0(1-x) at different temperatures
    图3 lnk-1/T图Fig.3 The dependence of lnk on 1/T
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引用本文

许诚,胡建建,周诚,等. FOX-7合成过程中水解反应的热危险性及反应动力学[J].含能材料, 2022, 30(3):250-255. DOI:10.11943/CJEM2021196.
XU Cheng, HU Jian-jian, ZHOU Cheng, et al. Thermal Hazard and Kinetic Study for the Hydrolysis in the Synthesis Process of FOX-7[J]. Chinese Journal of Energetic Materials, 2022, 30(3):250-255. DOI:10.11943/CJEM2021196.

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历史
  • 收稿日期: 2021-07-23
  • 最后修改日期: 2021-09-13
  • 录用日期: 2022-01-11
  • 在线发布日期: 2022-03-17
  • 出版日期: 2022-03-25