用C80量热仪研究重铵油炸药的热分解特性

doi:10.11949/j.issn.0438-1157.20170667

摘要/Abstract

摘要：

借助C80微量量热仪研究了多孔粒状铵油炸药、3种常用的重铵油炸药（乳化炸药/多孔粒状铵油炸药质量百分比分别为25/75、50/50、75/25）、乳化炸药的热分解特性，以升温速率0.2 K·min^-1时的C80热流速曲线数据为基础，求解了5种炸药试样热分解反应的反应热（ΔH）、表观活化能（E_a）、指前因子（lnA）等热力学和动力学参数。结果表明：乳化炸药的存在抑制了多孔粒状铵油炸药的热分解反应，使其开始发生热分解反应的温度被明显提高。重铵油炸药的表观活化能和放热反应开始温度均高于多孔粒状铵油炸药和乳化炸药，由此得出重铵油炸药的热稳定性高于多孔粒状铵油炸药和乳化炸药的热稳定性。

关键词: 重铵油炸药, C80微量量热仪, 热分解特性, 动力学理论, 热稳定性

Abstract:

A CALVET calorimeter C80 was used to analyze the thermal behavior of porous granular ANFO explosive, three commonly used heavy ANFO explosives and emulsion explosive. The mass ratios of emulsion explosive/porous granular ammonium oil blasting agent of the heavy ANFO explosives are 25/75, 50/50, and 75/25. The thermal kinetic parameters of apparent activation energy (E_a), pre-exponential factor (lnA), and thermodynamic parameter of reaction heat (ΔH) of the five explosive samples were calculated based on the heat flux data in C80 curve with the heating rate of 0.2 K·min^-1. The results show that emulsion explosive has an apparent inhibitory effect on the thermal decomposition reaction of porous granular ANFO explosive, which makes the thermal decomposition onset temperature of porous granular ANFO explosive obviously increased. The calculated values of the apparent activation energy and the onset temperature of the heavy ANFO explosives are higher than that of porous granular ANFO and emulsion explosive. It could be concluded that the thermal stability of heavy ANFO explosives is higher than that of porous granular ANFO explosive and emulsion explosive.

Key words: HANFO explosive, C80 micro calorimeter, thermal decomposition characteristics, kinetic theory, thermal stability

中图分类号:

TJ55
O69

李洪伟, 徐飞扬, 夏曼曼, 程扬帆, 龚悦. 用C80量热仪研究重铵油炸药的热分解特性[J]. 化工学报, 2018, 69(4): 1799-1805.

LI Hongwei, XU Feiyang, XIA Manman, CHENG Yangfan, GONG Yue. Thermal decomposition characteristics of HANFO by using C80 calorimeter[J]. CIESC Journal, 2018, 69(4): 1799-1805.

参考文献 30

[1]	葛韬武. 重铵油炸药的应用现状及其前景[J]. 金属矿山, 1992, 21(8):29-32. GE T W. Current status and development of heavy ANFO[J]. Metal Mine, 1992, 21(8):29-32.
[2]	郭占江, 张继东, 孟广雄, 等. 重铵油炸药混装车在神华准能公司的应用[J]. 露天采矿技术, 2008, (5):20-22. GUO Z J, ZHANG J D, MENG G X, et al. The application of mixing-loading truck of heavy ANFO explosive in Zhunneng Company[J]. Opencast Mining Technology, 2008, (5):20-22.
[3]	王树民, 任卫东, 唐秋明. 高威力乳化炸药和重铵油炸药的研制与应用[J]. 矿业研究与开发, 1996, 16(1):36-42. WANG S M, REN W D, TANG Q M. Development and application of high-strength emulsion explosive and heavy ANFO[J]. Mining Research and Development, 1996, 16(1):36-42.
[4]	刘颖歆. GWR乳化炸药和JCH重铵油炸药及其应用[J]. 爆破, 1996, 13(2):88-92. LIU Y X. GWR emulsion explosive, JCH heavy ANFO and their applications[J]. Blasting, 1996, 13(2):88-93.
[5]	FENG S R, SHAO A L. Research on high-efficiency composite oil phase material for emulsion heavy ANFO[C]//The 3rd International Conference on Machinery, Materials Science and Energy Engineering, 2015:561-569.
[6]	徐志祥, 刘大斌, 胡毅亭. 新型粉状铵油炸药实验研究[J]. 含能材料, 2011, 19(4):370-372. XU Z X, LIU D B, HU Y T. Experimental investigation of a new ANFO explosive[J]. Chinese Journal of Energetic Materials, 2011, 19(4):370-372.
[7]	LIGHTFOOT P D, VON ROSEN B, FOUCHARD R C, et al. Thermal decomposition of ANFO at low heating rates[C]//Nashville, Tennessee, USA, 2003.
[8]	龚悦, 何杰, 颜事龙, 等. 铝粉粒度对乳化炸药基质热分解特性的影响[J]. 高压物理学报, 2017, 31(2):148-154. GONG Y, HE J, YAN S L, et al. Effect of aluminum particle size on thermal decomposition characteristics of emulsion matrix[J]. Chinese Journal of High Pressure Physics, 2017, 31(2):148-154.
[9]	XU Z X, WANG Q, FU X Q. Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite[J]. Journal of Hazardous Materials, 2015, 300:702-710.
[10]	吴秋洁, 陈相, 谭柳, 等. 结晶亚硝酸钠混入对乳化炸药安全性的影响[J]. 化工学报, 2017, 68(5):2211-2215. WU Q J, CHEN X, TAN L, et al. The influence of the crystalloid NaNO2 on the safety of emulsion explosive[J]. CIESC Journal, 2017, 68(5):2211-2215.
[11]	阮继锋, 平平, 孙金华, 等. 硝酸及硫酸对硝基苯热稳定性的影响研究[J]. 兵器材料科学与工程, 2011, 34(4):37-40. RUAN J F, PING P, SUN J H, et al. Influence of nitric acid and sulfuric acid on the thermal stability of nitrobenzene[J]. Ordnance Material Science and Engineering, 2011, 34(4):37-40.
[12]	BENOIST L. New experimental vessels for the C80 calorimeter[J]. Thermochimica Acta, 1987, 119(1):223-224.
[13]	胡拥鹏, 赵旭芳, 赵宁宁, 等.DNGTZ的非等温热分解动力学及热安全性[J]. 含能材料, 2014, 22(6):767-773. HU Y P, ZHAO X F, ZHAO N N, et al. Non-isothermal thermal decomposition kinetic and thermal safety of DNGTZ[J]. Chinese Journal of Energetic Materials, 2014, 22(6):767-773.
[14]	李建军, 汪旭光, 欧育湘, 等. 乳化炸药热分解动力学研究[J]. 北京理工大学学报, 1996, 16(6):636-642. LI J J, WANG X G, OU Y X, et al. A study on the thermal decomposition kinetics of emulsion explosives[J]. Transaction of Beijing Institute of Technology, 1996, 16(6):636-642.
[15]	孙占辉, 孙金华, 邵荃. 盐酸对硝酸铵热分解的影响[J]. 中国科学技术大学学报,2006, 36(4):370-373. SUN Z H, SUN J H, SHAO Q. et al. On the decomposition of AN catalyzed by HCL[J]. Journal of University of Science and Technology of China, 2006, 36(4):370-373.
[16]	YI J H, ZHAO F Q, WANG B Z, et al. BTATz-HNIW-CMDB propellants decomposition reaction kinetics and thermal safety[J]. Journal of Thermal Analysis and Calorimetry, 2015, 115(2):1227-1234.
[17]	孙笑, 王娟, 周新利. HNF的热分解动力学和热安全性[J]. 含能材料, 2014, 22(6):774-779. SUN X, WANG J, ZHOU X L. Thermal decomposition kinetics and thermal safety of HNF[J]. Chinese Journal of Energetic Materials, 2014, 22(6):774-779.
[18]	李露明, 李兆乾, 马拥军, 等. Mn3O4微球的制备及其对高氯酸铵热分解的催化作用[J]. 含能材料, 2014, 22(6):758-761. LI L M, LI Z Q, MA Y J, et al. Preparation of Mn3O4 microspheres and their catalytic effects upon thermal decomposition of ammonium perchlorate[J]. Chinese Journal of Energetic Materials, 2014, 22(6):758-761.
[19]	王凯, 刘大斌, 徐森, 等. 硝基胍自催化热分解特性及绝热安全性[J]. 含能材料, 2016, 24(3):284-288. WANG K, LIU D B, XU S, et al. Autocatalytic thermal decomposition properties and adiabatic safety of nitroguanidine[J]. Chinese Journal of Energetic Materials, 2016, 24(3):284-288.
[20]	高大元, 何松伟, 沈永兴, 等. GI-920炸药的热分解动力学研究[J]. 含能材料, 2008, 16(1):1-5. GAO D Y, HE S W, SHEN Y X, et al. Thermal decomposition kinetics of GI-920 explosive[J]. Chinese Journal of Energetic Materials, 2008, 16(1):1-5.
[21]	罗宁, 李晓杰, 王小红, 等. 几种乳化炸药的热分解动力学行为[J]. 含能材料, 2009, 17(4):464-466. LUO N, LI X J, WANG X H, et al.Thermal decomposition kinetic behavior of emulsion explosives[J]. Chinese Journal of Energetic Materials, 2009, 17(4):464-466.
[22]	RODUIT B, HARTMANN M, FOLLY P, et al. Determination of thermal hazard from DSC measurements, investigation of self-accelerating decomposition temperature(SADT) of AIBN[J]. Journal of Thermal Analysis and Calorimetry, 2014, 117(3):1017-1026.
[23]	WANG S, XU Z X, WANG Q. Thermal decomposition mechanism of emulsion explosives with phosphatide[J]. Therm. Anal. Calorim., 2016, 124(2):1053-1062.
[24]	彭浩梁, 陈利平, 路贵斌, 等. 乌洛托品的热分解动力学[J]. 含能材料, 2016, 24(5):497-502. PENG H L, CHEN L P, LU G B, et al. Thermal decomposition kinetics of urotropin[J]. Chinese Journal of Energetic Materials, 2016, 24(5):497-502.
[25]	XUE R, SONG J H. Crystal structure and computed properties of a coordination compound[Zn(ATZ)2(N3)2]3(H2O)2(ATZ=4-amino-1, 2, 4-tria-zole)[J]. Main Group Chemistry, 2016, 15(3):287-294.
[26]	WANG J Y, LIANG J, WU B D, et al. Thermoanalysis and crystal structure of ammonium 4-amino-3-(5-tetrazolate)-furazan (NH4 AFT)[J]. Main Group Chemistry, 2016, 15(4):325-334.
[27]	ZHANG Z B, XU C X, YIN X, et al. Synthesis, crystal structures and thermal stabilities of zinc coordination polymers containing the 3-hydrazino-4-amino-1, 2, 4-triazole ligand[J]. Journal of Coordination Chemistry, 2016, 69(10):1559-1567.
[28]	FU X L, FAN X Z, WANG B Z, et al. Thermal behavior, decomposition mechanism and thermal safety of 5,7-diamino-4,6-dinitrobenzenfuroxan (CL-14)[J]. Journal of Thermal Analysis and Calorimetry, 2016, 124(2):993-1001.
[29]	WANG Y, SONG X L, SONG D, et al. Synthesis, thermolysis, and sensitivities of HMX/NC energetic nanocomposites[J]. Journal of Hazardous Materials, 2016, 312:73-83.
[30]	XIAO L B, ZHAO F Q, LUO Y, et al. Thermal behavior and safety of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate[J]. Therm. Anal. Calorim., 2016, 123(1):653-657.