硝酸铵水溶液热安全性研究
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摘要
近年来发生多起硝酸铵溶液的爆炸事故,硝酸铵溶液的热安全性越来越引起学者的关注,国内外针对固体硝酸铵的危险性已经做了大量研究,而关于硝酸铵水溶液安全性的研究开展的并不多。因此,研究硝酸铵溶液的热安全性具有十分重要的意义。
本文阐述了硝酸铵水溶液热安全性的研究现状,从理论上分析了氯化物、酸和油脂等杂质对硝酸铵水溶液的影响。通过绝热加热的方法,采用硝酸铵水溶液热爆炸装置研究了高温状态下硝酸铵水溶液的热分解特性,测试了氯化物、酸和油脂等杂质对溶液临界爆温的影响规律。实验结果表明:硝酸铵水溶液在110℃和210℃左右会发生两次明显的放热过程;浓度对硝酸铵水溶液的热安全性影响不是很大,纯净的硝酸铵水溶液在一定浓度范围内,临界爆温随浓度的升高而有所降低;氯化物、酸和油脂对硝酸铵溶液的热安全性有很大影响。Cl-单独作用会在一定程度上抑制硝酸铵溶液的热分解;H+、H+和Cl-、油脂、H+和油脂对硝酸铵水溶液的热分解都有促进作用,其中H+和Cl-的协同作用对溶液热分解的促进最明显;96%的硝酸铵水溶液的热爆炸危险性与分析纯硝酸铵相似,有较高的热稳定性和临界爆炸温度。研究结果对指导硝酸铵的安全生产有重要的参考价值。
In recent years, many explosion of ammomium nitrate solution have been occurred, the thermal safety of ammomium nitrate solution caused more and more attention of scholars,Many domestic and overseas scholars made lots of research on the dangers of ammomium nitrate,however,very little study was on the dangers of its aqueous solution.Therefore,it is of great meaning to study of the thermal safety of ammonium nitrate solution.
This article briefly introduces the current research situation of the thermal safety of ammonium nitrate solution,analyzes the effects of the chloride, acid and grease and other impurities on the ammonium nitrate solution in theory.Adiabatic heating was employed to study the thermal decomposition characteristics of ammonium nitrate solution and test the influence rule of the chloride,acid and grease and other impurities on the critical explosion temperature of the solution with ammonium nitrate solution thermal explosive devices under the high temperature.The results show that: Ammonium nitrate solution occurs two distinct exothermic process at about 110℃and 210℃; Concentration has a little effects on the thermal safety of ammomium nitrate solution, at a certain concentration range, the critical explosion temperature of pure ammomium nitrate solution decreases with the increasing of concentration;The chloride,acid and grease have great effects on the thermal safety of ammomium nitrate solution.The chloride ion alone existed inhibits the thermal decomposition; Hydrogen ion,both hydrogen ion and chlorine ion,grease,both hydrogen ion and grease promote the thermal decomposition,especially the action of hydrogen ion and chlorine ion is the most obvious;The solution containing 90%ammomium nitrate has higher thermal stability and critical explosion temperature,its thermal explosion risk is similar to that of the analytical reagent.These results were of important reference to the hazard control in the process of ammomium nitrate production.
本文阐述了硝酸铵水溶液热安全性的研究现状,从理论上分析了氯化物、酸和油脂等杂质对硝酸铵水溶液的影响。通过绝热加热的方法,采用硝酸铵水溶液热爆炸装置研究了高温状态下硝酸铵水溶液的热分解特性,测试了氯化物、酸和油脂等杂质对溶液临界爆温的影响规律。实验结果表明:硝酸铵水溶液在110℃和210℃左右会发生两次明显的放热过程;浓度对硝酸铵水溶液的热安全性影响不是很大,纯净的硝酸铵水溶液在一定浓度范围内,临界爆温随浓度的升高而有所降低;氯化物、酸和油脂对硝酸铵溶液的热安全性有很大影响。Cl-单独作用会在一定程度上抑制硝酸铵溶液的热分解;H+、H+和Cl-、油脂、H+和油脂对硝酸铵水溶液的热分解都有促进作用,其中H+和Cl-的协同作用对溶液热分解的促进最明显;96%的硝酸铵水溶液的热爆炸危险性与分析纯硝酸铵相似,有较高的热稳定性和临界爆炸温度。研究结果对指导硝酸铵的安全生产有重要的参考价值。
In recent years, many explosion of ammomium nitrate solution have been occurred, the thermal safety of ammomium nitrate solution caused more and more attention of scholars,Many domestic and overseas scholars made lots of research on the dangers of ammomium nitrate,however,very little study was on the dangers of its aqueous solution.Therefore,it is of great meaning to study of the thermal safety of ammonium nitrate solution.
This article briefly introduces the current research situation of the thermal safety of ammonium nitrate solution,analyzes the effects of the chloride, acid and grease and other impurities on the ammonium nitrate solution in theory.Adiabatic heating was employed to study the thermal decomposition characteristics of ammonium nitrate solution and test the influence rule of the chloride,acid and grease and other impurities on the critical explosion temperature of the solution with ammonium nitrate solution thermal explosive devices under the high temperature.The results show that: Ammonium nitrate solution occurs two distinct exothermic process at about 110℃and 210℃; Concentration has a little effects on the thermal safety of ammomium nitrate solution, at a certain concentration range, the critical explosion temperature of pure ammomium nitrate solution decreases with the increasing of concentration;The chloride,acid and grease have great effects on the thermal safety of ammomium nitrate solution.The chloride ion alone existed inhibits the thermal decomposition; Hydrogen ion,both hydrogen ion and chlorine ion,grease,both hydrogen ion and grease promote the thermal decomposition,especially the action of hydrogen ion and chlorine ion is the most obvious;The solution containing 90%ammomium nitrate has higher thermal stability and critical explosion temperature,its thermal explosion risk is similar to that of the analytical reagent.These results were of important reference to the hazard control in the process of ammomium nitrate production.
引文
[1]中国农业科学院土壤肥料研究所主编.中国肥料.上海:科学技术出版,1994.
[2]吕春绪,刘祖亮,倪欧琪著.工业炸药.北京:兵器工业出版社,1994.
[3]唐双凌,刘祖亮,王志敏等.农用改性硝酸铵爆轰安全性的测定.爆破器材,2004, 33(1):6～8.
[4]孟广诰.硝酸铵的特性和安全保管.商品储运与养护,1994(1):26～27.
[5]王小红,郭子如.硝酸铵的热分解和热稳定性研究现状.煤矿爆破,2004(1):27～30.
[6]高之江.造粒硝铵装置改产硝酸铵钙.中氮肥,2003,3(2):7～9.
[7]荆宏健主编.冷冻法硝酸磷肥生产技术[J].北京:化学工业出版社.2002.264.
[8]韩学军,刘延义,陈静,等.直接使用硝酸铵溶液生产膨化硝酸铵炸药研究.爆破器材,2009,38(3):15～17.
[9]安全科学技术研究中心.兴化集团硝铵溶液爆炸分析.现代职业安全,2004(8): 46～47,55.
[10] Jimmie C. Oxley*, James L. Smith, Evan Rogers, Ming Yu.Ammonium nitrate: thermal stability and explosivity modifiers[J].Thermochimica Acta,2002, 384(1-2):23～45.
[11] Saunders H L.Thermal decomposition of ammonium nitrate[J].J Chem Soc, 1922,121:698～711.
[12] Keenan A G,Dimitriades B.Mechanism for the chloride-catalyzed thermal decomposition of ammonium nitrate[J].J Chem Phys,1962,37 (8):1583～1586.
[13] Keenan A G,Notz K,Franco N B.Synergistic catalysis of ammonium nitrate decomposition[J].J Am Chem Soc,1969,(4):3168～3171.
[14] R.Turcotte,P.D.Lightfoot,R.Fouchard,D.E.G.Jones.Thermal Hazard assessment of AN and AN-based explosives[J].Journal of Hazardous Merterials,2003,A101:1～27.
[15]赵东风,彭力,王文东.无机添加剂对硝酸铵拒爆性的影响研究.燃烧化学学报, 2006,34(1):113～116.
[16]李艺,惠君明.几种添加剂对硝酸铵热稳定性的影响.火炸药学报,2005,28(1): 76～80.
[17] Gunawan R,Zhang D.Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.J Hazard Mater,2008 Nov 1.
[18] P.N.Simoes,L.M.Pedroso,A.Portugal,J.L.Campos.Study of the decomposition of phase stabilized ammonium nitrate(PSAN) by simultaneous thermal analysis: determination of kinetic parameters.Thermochimica Acta,1998,319:55～56.
[19]王光龙,许秀成.硝酸铵热稳定性的研究.郑州大学学报(工学版),2003,24(1): 47～50.
[20]陆明,刘慧英.膨化硝酸铵的热分解的动力学研究[D].火炸药学报,2000(1):62～64.
[21]吕春绪等.膨化硝铵炸药[M].北京:兵器工业出版社,2001.
[22]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[D].中国安全科学学报,2005,15(9):57～62.
[23]胡琳娜,赵景利,王桂荣.硝酸铵溶液三段蒸发过程的热力学分析.海湖盐与化工, 2001,30(4):16～18.
[24]严致英,朱清昌,王君莉,等.硝酸铵溶液催化分解法机理的探讨.化学通报,1977 (1):24～28.
[25]陈网桦,陈利平,吴燕,等.硝酸及氯离子对高温硝酸铵水溶液热危险性的影响研究.中国安全科学学报,2007,17(5):101～105.
[26]张为鹏,赵省向,张亦安.杂质对硝酸铵溶液热分解特性的影响.化肥工业,2001,28 (4):12～14,45.
[27]张为鹏,赵省向,张亦安.硝酸铵溶液的氯催化分解.火炸药学报,2004,27(1):33～35.
[28]张亦安,赵省向,张为鹏.硝酸铵生产过程爆炸危险性评估.化肥工业,2001,28(5):31～33,41.
[29]崔克清.安全工程大辞典[M].北京:化学工业出版社.1995.
[30]张杰,杨荣杰,刘云飞.硝酸铵的吸湿性研究[J].火炸药学报,2001,24(3):22～25.
[31]肖代军.硝酸铵水分含量对粉状硝铵炸药质量的影响.爆破器材,2007,36(3): 14～17.
[32]吉林化学工业公司化肥厂编.硝酸铵生产工艺与操作.北京:化学工业出版,1980.
[33]曾贵玉,周建华,吕春绪等.无机物对硝酸铵相转变的影响.含能材料.2007, 15(4): 400～403.
[34]王玫,迟平.硝酸铵对社会稳定发展的影响.问题探讨.2008(3):87,89.
[35]化肥工业大全编辑委员会.化肥工业大全[M].北京:化学工业出版社,1988
[36]天津化工研究院.无机盐工业手册[M].第二版.北京:化学工业出版社,1994
[37]《化工百科全书》编辑委员会.化工百科全书[M].北京:化学工业出版社,1991
[38]В.Ю.罗兹曼.硝酸铵的稳定性[M].刘建勋译.北京:化学工业出版社,1986:36～67.
[39] MB别斯恰斯特诺夫,B M索科洛夫[苏].化工生产中事故的预防[M].杨维榕等译.北京:化学工业出版社.1986.
[40]沈立晋,汪旭光,宋锦泉.非爆炸且不可还原农用硝酸铵热分解反应动力学的研究.爆炸与冲击,2005,25(3):232～238.
[41]胡双启,张景林.燃烧与爆炸.兵器工业出版社,1992:133～268.
[42]杜志明,曾庆轩,冯长根.热爆炸转变现象及转变点的计算[J].兵工学报,1991,2(9): 2～3.
[43]冯长根.热爆炸理论.北京:科学出版社,1988,1～54.
[44]魏红兵,李权斌,王向东.自动电位滴定法测定化肥中氯离子含量.磷肥与复肥,2005,20(2):67~68.
[45]刘期成.浅析复混肥料中氯离子含量的测定方法.中国学术期刊电子出版社,2001,6:40.
[46]朱涛,李崇明.佛尔哈德法测定复混肥料中氯离子的含量[J].化肥工业,2001,29(1):23～26.
[47] MacNeil J H,Zhang H T,Berserh P.Catalytic decomposition of ammonium nit ratein superheated aqueous solution [J].J Am.Chem.Soc.,1997,119(41):9738～9744.
[2]吕春绪,刘祖亮,倪欧琪著.工业炸药.北京:兵器工业出版社,1994.
[3]唐双凌,刘祖亮,王志敏等.农用改性硝酸铵爆轰安全性的测定.爆破器材,2004, 33(1):6～8.
[4]孟广诰.硝酸铵的特性和安全保管.商品储运与养护,1994(1):26～27.
[5]王小红,郭子如.硝酸铵的热分解和热稳定性研究现状.煤矿爆破,2004(1):27～30.
[6]高之江.造粒硝铵装置改产硝酸铵钙.中氮肥,2003,3(2):7～9.
[7]荆宏健主编.冷冻法硝酸磷肥生产技术[J].北京:化学工业出版社.2002.264.
[8]韩学军,刘延义,陈静,等.直接使用硝酸铵溶液生产膨化硝酸铵炸药研究.爆破器材,2009,38(3):15～17.
[9]安全科学技术研究中心.兴化集团硝铵溶液爆炸分析.现代职业安全,2004(8): 46～47,55.
[10] Jimmie C. Oxley*, James L. Smith, Evan Rogers, Ming Yu.Ammonium nitrate: thermal stability and explosivity modifiers[J].Thermochimica Acta,2002, 384(1-2):23～45.
[11] Saunders H L.Thermal decomposition of ammonium nitrate[J].J Chem Soc, 1922,121:698～711.
[12] Keenan A G,Dimitriades B.Mechanism for the chloride-catalyzed thermal decomposition of ammonium nitrate[J].J Chem Phys,1962,37 (8):1583～1586.
[13] Keenan A G,Notz K,Franco N B.Synergistic catalysis of ammonium nitrate decomposition[J].J Am Chem Soc,1969,(4):3168～3171.
[14] R.Turcotte,P.D.Lightfoot,R.Fouchard,D.E.G.Jones.Thermal Hazard assessment of AN and AN-based explosives[J].Journal of Hazardous Merterials,2003,A101:1～27.
[15]赵东风,彭力,王文东.无机添加剂对硝酸铵拒爆性的影响研究.燃烧化学学报, 2006,34(1):113～116.
[16]李艺,惠君明.几种添加剂对硝酸铵热稳定性的影响.火炸药学报,2005,28(1): 76～80.
[17] Gunawan R,Zhang D.Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.J Hazard Mater,2008 Nov 1.
[18] P.N.Simoes,L.M.Pedroso,A.Portugal,J.L.Campos.Study of the decomposition of phase stabilized ammonium nitrate(PSAN) by simultaneous thermal analysis: determination of kinetic parameters.Thermochimica Acta,1998,319:55～56.
[19]王光龙,许秀成.硝酸铵热稳定性的研究.郑州大学学报(工学版),2003,24(1): 47～50.
[20]陆明,刘慧英.膨化硝酸铵的热分解的动力学研究[D].火炸药学报,2000(1):62～64.
[21]吕春绪等.膨化硝铵炸药[M].北京:兵器工业出版社,2001.
[22]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[D].中国安全科学学报,2005,15(9):57～62.
[23]胡琳娜,赵景利,王桂荣.硝酸铵溶液三段蒸发过程的热力学分析.海湖盐与化工, 2001,30(4):16～18.
[24]严致英,朱清昌,王君莉,等.硝酸铵溶液催化分解法机理的探讨.化学通报,1977 (1):24～28.
[25]陈网桦,陈利平,吴燕,等.硝酸及氯离子对高温硝酸铵水溶液热危险性的影响研究.中国安全科学学报,2007,17(5):101～105.
[26]张为鹏,赵省向,张亦安.杂质对硝酸铵溶液热分解特性的影响.化肥工业,2001,28 (4):12～14,45.
[27]张为鹏,赵省向,张亦安.硝酸铵溶液的氯催化分解.火炸药学报,2004,27(1):33～35.
[28]张亦安,赵省向,张为鹏.硝酸铵生产过程爆炸危险性评估.化肥工业,2001,28(5):31～33,41.
[29]崔克清.安全工程大辞典[M].北京:化学工业出版社.1995.
[30]张杰,杨荣杰,刘云飞.硝酸铵的吸湿性研究[J].火炸药学报,2001,24(3):22～25.
[31]肖代军.硝酸铵水分含量对粉状硝铵炸药质量的影响.爆破器材,2007,36(3): 14～17.
[32]吉林化学工业公司化肥厂编.硝酸铵生产工艺与操作.北京:化学工业出版,1980.
[33]曾贵玉,周建华,吕春绪等.无机物对硝酸铵相转变的影响.含能材料.2007, 15(4): 400～403.
[34]王玫,迟平.硝酸铵对社会稳定发展的影响.问题探讨.2008(3):87,89.
[35]化肥工业大全编辑委员会.化肥工业大全[M].北京:化学工业出版社,1988
[36]天津化工研究院.无机盐工业手册[M].第二版.北京:化学工业出版社,1994
[37]《化工百科全书》编辑委员会.化工百科全书[M].北京:化学工业出版社,1991
[38]В.Ю.罗兹曼.硝酸铵的稳定性[M].刘建勋译.北京:化学工业出版社,1986:36～67.
[39] MB别斯恰斯特诺夫,B M索科洛夫[苏].化工生产中事故的预防[M].杨维榕等译.北京:化学工业出版社.1986.
[40]沈立晋,汪旭光,宋锦泉.非爆炸且不可还原农用硝酸铵热分解反应动力学的研究.爆炸与冲击,2005,25(3):232～238.
[41]胡双启,张景林.燃烧与爆炸.兵器工业出版社,1992:133～268.
[42]杜志明,曾庆轩,冯长根.热爆炸转变现象及转变点的计算[J].兵工学报,1991,2(9): 2～3.
[43]冯长根.热爆炸理论.北京:科学出版社,1988,1～54.
[44]魏红兵,李权斌,王向东.自动电位滴定法测定化肥中氯离子含量.磷肥与复肥,2005,20(2):67~68.
[45]刘期成.浅析复混肥料中氯离子含量的测定方法.中国学术期刊电子出版社,2001,6:40.
[46]朱涛,李崇明.佛尔哈德法测定复混肥料中氯离子的含量[J].化肥工业,2001,29(1):23～26.
[47] MacNeil J H,Zhang H T,Berserh P.Catalytic decomposition of ammonium nit ratein superheated aqueous solution [J].J Am.Chem.Soc.,1997,119(41):9738～9744.
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