质量效应及热历史对硝酸铵热分解特性的影响研究
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摘要
为了研究质量效应对硝酸铵热分解特性的影响,分别采用小质量的差示扫描量热仪、中质量的微热量热仪和大质量的烤燃箱对其热分解特性进行实验研究;采用差示扫描量热仪和微热量热仪进一步研究了热历史对硝酸铵热分解特性的影响。结果表明:质量效应对硝酸铵的热稳定性有显著影响,随着样品质量的增加,样品分解温度(包括初始分解温度和最高分解温度)会逐渐降低,发生燃烧爆炸的危险程度进一步增加;经过热历史的硝酸铵分解温度会逐渐降低,且随着回归温度的增大,分解温度向低温方向的偏移越来越大。这主要是因为在热历史实验过程中,硝酸铵分解产生了一定量的中间产物,这些中间产物将对硝酸铵二次加热过程中的热分解产生催化作用,导致硝酸铵的分解温度降低。在实际工业生产存储过程中,应尽量避免大质量存放硝酸铵且存放场所防止出现热源。
The differential scanning calorimetry( DSC),microcalorimeter and cook-off( CO) oven are used to study the influence of mass on the thermal decomposition characteristics of ammonium nitrate( AN),and DSC and microcalorimenter are used to study the effect of thermal history on the thermal decomposition characteristics of AN. The results show that the mass has a significant effect on the thermal stability of AN,and the measured decomposition temperatures of samples,including onset decomposition temperature and peak decomposition temperature,decrease with the increase in their mass sizes. The large mass sample is easy to explode,which ultimately decreases the thermal stability of AN. The decomposition temperatures drifts to low temperature direction greater and greater with the increase in temperature. This is mainly due to the autocatalytic chemical reactions which generate intermediate products during heating. It is necessary to avoid the storage of large mass of AN and keep the heat source off the storage location in the process of industrial production and storage.
The differential scanning calorimetry( DSC),microcalorimeter and cook-off( CO) oven are used to study the influence of mass on the thermal decomposition characteristics of ammonium nitrate( AN),and DSC and microcalorimenter are used to study the effect of thermal history on the thermal decomposition characteristics of AN. The results show that the mass has a significant effect on the thermal stability of AN,and the measured decomposition temperatures of samples,including onset decomposition temperature and peak decomposition temperature,decrease with the increase in their mass sizes. The large mass sample is easy to explode,which ultimately decreases the thermal stability of AN. The decomposition temperatures drifts to low temperature direction greater and greater with the increase in temperature. This is mainly due to the autocatalytic chemical reactions which generate intermediate products during heating. It is necessary to avoid the storage of large mass of AN and keep the heat source off the storage location in the process of industrial production and storage.
引文
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[21]亓希国,汪旭光,夏柏如.利用DSC曲线表征添加剂对防爆硝酸铵晶变的影响[J].爆破器材,2005,34(2):1-3.QI Xi-guo,WANG Xu-guang,XIA Bai-ru. Effect of additives on crystal transition of anti-explosive ammonium nitrate using DSC curves[J]. Explosive Materials,2005,34(2):1-3.(in Chinese)
[22]李敏,陈相,谭柳,等.尺度效应对硝酸铵热分解温度特性的影响[J].爆破器材,2015,44(4):29-32.LI Min,CHEN Xiang,TAN Liu,et al. Influence of scale effect on thermal decomposition temperature characteristic of ammonium nitrate[J]. Explosive Materials,2015,44(4):29-32.(in Chinese)
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[24] Dave P N. Review on thermal decomposition of ammonium nitrate[J]. Journal of Energetic Materials,2013,31(1):1-26.
[2]陈天云,吕春绪.自敏化硝酸铵安全性能及其应用研究[J].兵工学报,2001,22(3):393-396.CHEN Tian-yun,LYU Chun-xu. A study on the safety and application of self-sensitive ammonium nitrate[J]. Acta Armamentarii,2001,22(3):393-396.(in Chinese)
[3]王树涛,霸书红,程秀莲,等.微热量热计法研究几种盐对硝酸铵晶变的影响[J].爆破器材,2017,46(5):48-51.WANG Shu-tao,BA Shu-hong,CHENG Xiu-lian,et al. Effect of four inorganic salts on crystal phase transition of ammonium nitrate detected by micro calorimeter[J]. Explosive Materials,2017,46(5):48-51.(in Chinese)
[4] Tan L,Wu Q J,Chen X,et al. The effects of sodium chloride on the explosive performance of ammonium nitrate[J]. Journal of Thermal Analysis&Calorimetry,2014,115(2):1759-1766.
[5]谭柳,刘大斌,徐森,等.氯化钾对硝酸铵爆炸性能和热稳定性的影响[J].含能材料,2017,25(6):520-528.TAN Liu,LIU Da-bin,XU Sen,et al. Effect of potassium chloride on the detonation performance and thermal stability of ammonium nitrate[J]. Chinese Journal of Energetic Materials,2017,25(6):520-528.(in Chinese)
[6] Babrauskas V. Explosions of ammonium nitrate fertilizer in storage or transportation are preventable accidents[J]. Journal of Hazardous Materials,2016,304(4):134-149.
[7] Gunawan R,Zhang D. Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite[J]. Journal of Hazardous Materials,2009,165(1/2/3):751.
[8] Sinditskii V P,Egorshev V Y,Tomasi D,et al. Combustion mechanism of ammonium-nitrate-based propellants[J]. Journal of Propulsion&Power,2008,24(5):1068-1078.
[9] Badeen C M,Kwok Q S M,Vachon M C R,et al. Hazard characterization of mixtures of ammonium nitrate with the sodium salt of dichloroisocyanuric acid[J]. Journal of Thermal Analysis&Calorimetry,2005,81(1):225-233.
[10] Tan L,Liu D B,Wu Q J,et al. Effect of potassium chloride on thermal stability of ammonium nitrate under acidic conditions[J]. Journal of Thermal Analysis and Calorimetry,2018,131(3):2719-2728.
[11]王春丽,曹雄,程松,等.杂质对硝酸铵水溶液临界爆炸温度的影响[J].工业安全与环保,2011,37(2):42-43.WANG Chun-li,CAO Xiong,CHENG Song,et al. Influence of the impurities on the critical explosion temperature of ammomium nitrate solution[J]. Industrial Safety and Environmental Protection,2011,37(2):42-43.(in Chinese)
[12]侯秀婷,曹雄.氯离子及油脂对硝酸磷钾肥水溶液安全性的研究[J].工业安全与环保,2010,36(8):62-64.HOU Xiu-ting,CAO Xiong. The study on influences of chloride ions and grease on nitric phosphate-potassium fertilizer in aqueous solution[J]. Industrial Safety and Environmental Protection,2010,36(8):62-64.(in Chinese)
[13] Wu Q J,Tan L,Xu S,et al. Study on thermal decomposition characteristics of ammonium nitrate emulsion explosive in different scales[J]. Journal of Energetic Materials,2017(4):1-9.
[14]杨庭,陈利平,陈网桦,等.分解反应自催化性质快速鉴别的实验方法[J].物理化学学报,2014,30(7):1215-1222.YANG Ting,CHEN Li-ping,CHEN Wang-hua,et al. Experimental method on rapid identification of autocatalysis in decomposition reactions[J]. Acta Physico-Chimica Sinica, 2014,30(7):1215-1222.(in Chinese)
[15] Wang K,Liu D B,Xu S,et al. Thermal history method for identification of autocatalytic decomposition reactions of energetic materials[J]. Journal of Loss Prevention in the Process Industries,2016,40:241-247.
[16]颜事龙,胡洋勇,刘锋,等.硝酸铁对高温高浓度硝酸铵水溶液热稳定性的影响[J].含能材料,2015,23(5):459-463.YAN Shi-long,HU Yang-yong,LIU Feng,et al. Influence of ferric nitrate on decomposition of ammonium nitrate solution with high temperature and concentration[J]. Chinese Journal of Energetic Materials,2015,23(5):459-463.(in Chinese)
[17]张亦安,赵省向,张为鹏.硝酸铵生产过程爆炸危险性评估[J].化肥工业,2001,28(5):31-32.ZHANG Yi-an,ZHAO Sheng-xiang,ZHANG Wei-peng. Evaluation of explosion risk in ammonium nitrate production[J]. Journal of the Chemical Fertilizer Industry,2001,28(5):31-32.(in Chinese)
[18] Turcotte R,Lightfoot P D,Fouchard R,et al. Thermal hazard assessment of AN and AN-based explosives[J]. Journal of Hazardous Materials,2003,101(1):1-27.
[19] Sim7es P N,Pedroso L M,Portugal A A,et al. Study of the decomposition of phase stabilized ammonium nitrate(PSAN)by simultaneous thermal analysis:determination of kinetic parameters[J]. Thermochimica Acta,1998,319(1/2):55-65.
[20]孙占辉,孙金华,陆守香,等.无机酸对硝酸铵热稳定性影响的研究[J].中国安全科学学报,2005,15(9):57-62.SUN Zhan-hui,SUN Jin-hua,LU Shou-xiang,et al. Study of the influence of inorganic acid on the thermal stability of ammonium nitrate[J]. China Safety Science Journal,2005,15(9):57-62.(in Chinese)
[21]亓希国,汪旭光,夏柏如.利用DSC曲线表征添加剂对防爆硝酸铵晶变的影响[J].爆破器材,2005,34(2):1-3.QI Xi-guo,WANG Xu-guang,XIA Bai-ru. Effect of additives on crystal transition of anti-explosive ammonium nitrate using DSC curves[J]. Explosive Materials,2005,34(2):1-3.(in Chinese)
[22]李敏,陈相,谭柳,等.尺度效应对硝酸铵热分解温度特性的影响[J].爆破器材,2015,44(4):29-32.LI Min,CHEN Xiang,TAN Liu,et al. Influence of scale effect on thermal decomposition temperature characteristic of ammonium nitrate[J]. Explosive Materials,2015,44(4):29-32.(in Chinese)
[23] Oxiey J C,Kaushik S M,Gilson N S. Thermal stability and compatibility of ammonium nitrate explosives on a small and large scale[J]. Thermochimica Acta,1992,212(2):77-85.
[24] Dave P N. Review on thermal decomposition of ammonium nitrate[J]. Journal of Energetic Materials,2013,31(1):1-26.