CHINESE JOURNAL OF ENERGETIC MATERIALS
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甲基肼热分解的动力学特性及热安全性
作者:
作者单位:

南京理工大学 化学与化工学院, 江苏 南京 210094

作者简介:

徐飞扬(1992-),博士生,主要从事液体推进剂安全性方面研究。e-mail: 2443634307@qq.com

通讯作者:

徐森(1981-),副教授,主要从事爆炸力学,含能材料爆轰、危险性分级方面的研究。e-mail:xusen@njust.edu.cn

基金项目:

装备预研国防科技重点实验室基金项目(6142603200509,6142603180408)


Kinetic Characteristics of Thermal Decomposition and Thermal Safety for Methylhydrazine
Author:
Affiliation:

School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

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    摘要:

    为了评估甲基肼液体推进剂在生产、贮存、运输以及使用过程中的热安全,借助差示扫描量热法(DSC)研究了甲基肼的热分解特性和热安全性,分别计算了甲基肼的动力学、热力学和热安全性参数,并获得了半径为1 m的球形甲基肼液体推进剂在不同超临界环境温度下的热爆炸延滞期,基于等转化率法使用AKTS软件进一步计算得到了甲基肼的绝热诱导期以及自加速分解温度。结果表明:甲基肼的热分解过程只有一个较强的放热峰,采用Kissinger法和Ozawa法计算得到甲基肼的活化能值分别为159.13 kJ·mol-1和158.89 kJ·mol-1,自加速分解温度为451.53 K,热爆炸临界温度为469.55 K,热力学参数活化熵(ΔS)、活化焓(ΔH)和吉布斯活化自由能(ΔG)分别为73.93 J·mol-1,155.32 kJ·mol-1和121.46 kJ·mol-1;使用AKTS软件计算得到8、24 h和168 h绝热诱导期对应的温度分别为429.55,424.05 K和414.95 K;包装质量分别为5,25,50 kg和100 kg时,甲基肼的自加速分解温度依次为415.15,414.15,413.15 K和412.15 K。研究结果为评价甲基肼在生产、储运和使用过程中的热安全性提供了必要的理论基础。

    Abstract:

    The thermal decomposition characteristics and thermal safety of methylhydrazine (MMH) were studied by means of differential scanning calorimetry (DSC). The kinetics, thermodynamics and thermal safety parameters of MMH were calculated, respectively. The thermal explosion delay period of MMH of ball shaped with radius of 1 m at different supercritical ambient temperatures were also obtained. Based on the isoconversion rate method, the adiabatic induction period and self-accelerating decomposition temperature of MMH were further evaluated by using AKTS software. The results show that the thermal decomposition process of MMH has only one strong exothermic peak. The apparent activation energy values of MMH calculated by Kissinger and Ozawa methods are 159.13 kJ·mol-1 and 158.89 kJ·mol-1, respectively. The values of Tbp0 of MMH is 469.55 K. The values of entropy of activation (ΔS), enthalpy of activation (ΔH), and free energy of activation (ΔG) are 73.93 J·mol-1, 155.32 kJ·mol-1 and 121.46 kJ·mol-1, respectively. The corresponding temperatures for adiabatic induction period at 8, 24 h and 168 h are 429.55, 424.05 K and 414.95 K, respectively. When the packing mass was 5, 25, 50 kg and 100 kg, the self-accelerating decomposition temperatures of MMH are 415.15, 414.15, 413.15 K and 412.15 K in turn. The results provide the necessary theoretical basis for evaluating the thermal safety of MMH in the processes of production, storage, transportation and use.

    表 2 基于DSC曲线不同升温速率下试样放热分解反应的动力学参数Table 2 Kinetic parameters from the exothermic decomposition reaction for MMH at various heating rates based on DSC curves
    表 1 不同升温速率下甲基肼放热分解阶段的热特征参数Table 1 Thermal characteristic parameters of the exothermic decomposition stage-determined from DSC curves at various heating rates
    图1 甲基肼的DSC曲线Fig.1 DSC curves of MMH at four different heating rates
    图2 Friednman计算获得的Ea、ln(A(α)·f(α))随转化率的关系Fig.2 Relationship between Ea and ln(A(α)·f(α)) calculated by Friednman with conversion rate
    图3 甲基肼在不同起始温度下的绝热温度历程Fig.3 Adiabatic temperature courses of MMH at different starting temperatures
    图4 甲基肼在不同起始温度下的绝热诱导期Fig.4 Adiabatic induction periods of MMH at different starting temperatures
    图5 甲基肼自加速分解温度计算结果(25 kg包装)Fig.5 Calculation results of SADT of MMH(25 kg package)
    图6 甲基肼自加速分解温度与包装质量关系Fig.6 Relation between SADT temperature and packaging quality of MMH
    表 4 甲基肼在不同超临界环境温度下的延滞期Table 4 Different times to ignition under different super critical ambient temperatures for MMH
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引用本文

徐飞扬,吴星亮,王旭,等.甲基肼热分解的动力学特性及热安全性[J].含能材料, 2022, 30(2):171-177. DOI:10.11943/CJEM2021103.
XU Fei-yang, WU Xing-liang, WANG Xu, et al. Kinetic Characteristics of Thermal Decomposition and Thermal Safety for Methylhydrazine[J]. Chinese Journal of Energetic Materials, 2022, 30(2):171-177. DOI:10.11943/CJEM2021103.

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  • 收稿日期: 2021-04-21
  • 最后修改日期: 2021-05-16
  • 录用日期: 2021-07-28
  • 在线发布日期: 2022-03-17
  • 出版日期: 2022-02-25