|本期目录/Table of Contents|

[1]张乐,王志,许建新,等.二硝基脲法合成HMX的过程监测及动力学分析[J].火炸药学报,2018,41(3):303-307,313.[doi:10.14077/j.issn.1007-7812.2018.03.016]
 ZHANG Le,WANG Zhi,XU Jian-xin,et al.Process Monitoring and Kinetics Analysis of Synthesizing HMX by Dinitrocarbamide Method[J].,2018,41(3):303-307,313.[doi:10.14077/j.issn.1007-7812.2018.03.016]
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二硝基脲法合成HMX的过程监测及动力学分析()
     
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《火炸药学报》[ISSN:1007-7812/CN:61-1310/TJ]

卷:
41卷
期数:
2018年第3期
页码:
303-307,313
栏目:
出版日期:
2018-06-29

文章信息/Info

Title:
Process Monitoring and Kinetics Analysis of Synthesizing HMX by Dinitrocarbamide Method
作者:
张乐 王志 许建新 王建龙 曹端林
1. 中北大学化学工程与技术学院, 山西 太原 030051;
2. 甘肃银光化学工业集团有限公司, 甘肃 白银 730900
Author(s):
ZHANG Le WANG Zhi XU Jian-xin WANG Jian-long CAO Duan-lin
1. School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China;
2. Gansu Yinguang Chemical Industry Group Co. Ltd., Baiyin Gansu 730900, China
关键词:
二硝基脲法HMX在线监测绝热温升动力学
Keywords:
dinitrocarbamide methodHMXonline monitoringadiabatic temperature risekinetics
分类号:
TJ55;TQ564
DOI:
10.14077/j.issn.1007-7812.2018.03.016
文献标志码:
-
摘要:
采用反应量热仪(RC1)对二硝基脲法合成HMX各步放热过程进行测定,并分析其放热参数以及严重度;利用绝热加速量热仪(ARC)测定了中间产物的分解温度及放热速率,并进行了动力学分析。结果表明,加入尿素后反应体系立即放热,硝化反应在2s内发生,部分反应到达成熟期才完成;其余各步反应进行很快,也都在2s内发生,主要热量用于中和硫酸放热;得到的绝热温升越高,发生失控反应的严重度越高;加水的过程要在0℃下进行,加硝酸铵的过程要在10℃下进行,加尿素的合成反应温度较原工艺可以适当提高2℃,加DPT反应过程最为安全,合成反应的最高温度(MTSR)为40.8℃;经ARC测定得中间产物的相关动力学参数:活化能(Ea)为254 kJ/mol,指前因子(A)为1.26×1030s-1,反应级数(n)为0.88。
Abstract:
The exothermic process for synthesizing HMX with dinitrocarbamide method was measured by a RC1 reaction calorimetry and the exothermic parameters and risk degree were analyzed. The decomposition temperature and exothermic rate of intermediate products were measured by ARC, and the kinetic analysis was carried out. The results show that after adding urea, the reaction system is exothermic immediately. Nitrification reaction is carried out in 2s, part of the reaction arrives at the mature period to complete only. The rest of various step reactions were carried out quickly in 2s,and the main heat is used to neutralize the exothermicity of sulfuric acid. The higher the adiabatic temperature rise, the higher the severity of the runaway reaction. The process of adding water should be carried out at 0℃ and the process of ammonium nitrate should be carried out at 10℃. The synthetic reaction temperature of adding urea can be appropriately increased by 2℃ and the reaction process of adding DPT is the most safe. The maximum temperature of the synthetic reaction (MTSR) is 40.8℃. The activation energy (Ea), pre-exponential factor (A) and the reaction order (n) of the intermediate products obtained by ARC measurement are 254 kJ/mol,1.26×1030s-1 and 0.88, respectively.

参考文献/References:

[1] 曹新茂,李福平.奥克托今高能炸药及其应用[M].北京:兵器工业出版社,1993:218-240.
[2] 边小果,潘葆,高志强,等. 奥克托今炸药在螺压改性双基推进剂中的应用研究[J].含能材料,2004,18(3):187-190. BIAN Xiao-guo, PAN Bao, GAO Zhi-qiang, et al. Application research of octogen explosives in screw extrusion composite modefied double base propellant[J]. Chinese Journal of Energetic Material, 2004, 18(3):187-190.
[3] 罗帅,曹雄,侯向军,等. 奥克托今在丙酮中的热安全性研究[J].中国安全科学学报,2015, 19(3):66-70. LUO Shuai, CAO Xiong, HOU Xiang-jun, et al. Research on thermal safety of HMX in acetone[J]. China Safety Science Journal, 2015, 19(3):66-70.
[4] 彭浩梁. 醋酐法合成奥克托今工艺的热危险性研究[D].南京:南京理工大学,2016. PENG Hao-liang. Process safety assessment for the synthesis of HMX by acetic anhydride method[D]. Nanjing:Nanjing University of Science and Technology,2016.
[5] Radhakrishnan S, Talawar M B, Venugopalan S, et al. Synthesis, characterization and thermolysis studies on 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1] nonane (DPT):a key precursor in the synthesis of most powerful benchmark energetic materials(RDX/HMX) of today[J]. Journal of Hazardous Materials, 2008, 152(3):1317-1324.
[6] 朱鹏,刘惠平,周波,等. 过氧化环己酮的热稳定性研究[J].上海应用技术学院学报,2011, 4(11):330-334. ZHU Peng, LIU Hui-ping, ZHOU Bo, et al. An investigation on the thermal stability of cyclohexanone peroxide[J]. Journal of Shanghai Institute of Technology, 2011, 4(11):330-334.
[7] 庄众. 醋酸酐水解反应热失控危险性研究[D].南京:南京理工大学,2009. ZHUANG Zhong. Study on risk of heat controlled by hydrolysis of acetic acid[D]. Nanjing:Nanjing University of Science and Technology, 2009.
[8] 杨建明,余秦伟,薛云娜,等. 二硝基脲的合成、表征及热力学的理论研究[J].含能材料,2011, 19(2):160-164. YANG Jian-ming, YU Qin-wei, XUE Yun-na, et al. Synthesis characterization and theoretical research of thermodynamics on dinirourea[J]. Chinese Journal of Energetic Material, 2011, 19(2):160-164.
[9] 王鹏,宋红燕,孟子晖,等. 一锅法合成二硝基五亚甲基四胺工艺研究[J].北京理工大学学报,2011, 31(5):603-605. WANG Peng, SONG Hong-yan, MENG Zi-hui, et al. Reaction process of synthesizing dinitro pentamethylene tetttramine by one-pot mnthod[J]. Transactions of Beijing Institute of Technology, 2011, 31(5):603-605.
[10] 宋红燕,王鹏,覃光明,等. 一锅法合成二硝基五亚甲基四胺反应机理的研究[J].有机化学,2010, 30:414-418. SONG Hong-yan, WANG Peng, QIN Guang-ming, et al. Reaction mechanism of one-pot synthesis of dinitro pentamethylene tetramine[J]. Chinese Journal of Organic Chemistry, 2010, 30:414-418.
[11] 程春生,秦福涛,魏振云,等. 氟吗啉合成工艺热危险性及动力学研究[J].化学学报,2012, 70:1227-1231. CHENG Chun-sheng, QIN Fu-tao, WEI Zhen-yun, et al. Thermal hazard and kinetic study for synthesis process of flumorph[J]. Acta Chimica Sinica, 2012, 70:1227-1231.
[12] 高宇鹏,陈丽珍,王建龙,等. 反应量热仪在线探究硝酸硝解乌洛托品反应过程[J]. 科学技术与工程,2007, 17(17):288-291. GAO Yu-peng, CHEN Li-zhen, WANG Jian-long, et al. The exploration of the reaction process of nitrifying methenamine by reaction calorimeter[J]. Science Technology and Engineering, 2017,17(17):288-291.
[13] 陈网桦,陈利平,李春光,等. 苯和甲苯硝化及磺化反应热危险性分级研究[J].中国安全科学学报,2010, 20(5):67-73. CHEN Wang-hua, CHEN Li-ping, LI Chun-guang, et al. Classification investigation on thermal hazards in nitration and sulfonation reactions of benzene and toluene[J]. China Safety Science Journal, 2010, 20(5):67-73.

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备注/Memo

备注/Memo:
收稿日期:2017-09-01;改回日期:2017-10-03。
作者简介:张乐(1993-),女,硕士研究生,从事含能材料合成及热分析研究。E-mail:405881994@qq.con
通讯作者:王建龙(1969-),男,教授,从事含能材料合成及应用研究。E-mail:wangjianlong@nuc.edu.cn
更新日期/Last Update: 1900-01-01