探讨膨化硝铵炸药生产过程的安全问题与措施

一、引言 膨化硝铵炸药是一种工业硝铵炸药,从1994年诞生,经产业化开发,在全国得到推广应用.但是,膨化硝铵炸药在生产过程中存在的安全问题却没有引起人们的足够重视.近两年来,多家民爆生产企业在生产过程中发生爆炸事故,造成严重后果,党和国家领导高度重视并作出重要批示,要求民爆生产企业切实采取有效措施解决炸药生产过程的安全问题,严防爆炸事故的发生.     

探讨膨化硝铵炸药生产过程的安全问题与措施

一、引言膨化硝铵炸药是一种工业硝铵炸药,从1994年诞生,经产业化开发,在全国得到推广应用。但是,膨化硝铵炸药在生产过程中存在的安全问题却没有引起人们的足够重视。近两年来,多家民爆生产企业在生产过程中发生爆炸事故,造成严重后果,党和国家领导高度重视并作出重要批示,要求民爆生产企业切实采取有效措施解决炸药生产过程的安全问题,严防爆炸事故的发生。     

硝铵共浆溶液热安全性研究

为防止硝铵共浆溶液在配制、储存、运输和生产复合肥过程中发生爆炸事故,利用自制实验装置对硝铵共浆溶液的热安全性进行了实验研究.结果表明,硝铵共浆溶液低于纯硝酸铵水溶液的临界爆炸温度,具有很大的危险性；硝酸铵的浓度对硝铵共浆溶液的临界爆炸温度的影响很大,硝酸铵浓度越高,其临界爆炸温度就越低,也越易爆炸；氯离子有促进硝铵共浆溶液爆炸的作用；油脂会降低硝铵共浆溶液的热稳定性,降低其临界爆炸温度.研究结果对相关化肥企业的安全生产有指导意义.     

兴化集团硝铵溶液爆炸分析

陕西兴化集团有限责任公司是以重油为原料制合成氨、硝铵的中型化肥厂。1期工程生产硝铵11万吨/年,于1970年建成投产;11期工程生产硝铵11万吨/年,于1982年底建成投产。该厂硝铵的原料是气氨和稀硝酸,其工艺流程:常压中和,一段蒸发、造粒。Ⅰ、Ⅱ期生产工艺相同。事故概况:1月6日,Ⅱ期硝铵三班,自16∶50接班至21∶00,整个工艺平稳,生产正常。21∶00以后,Ⅰ、Ⅱ期硝铵中和岗位均发生气氨压力和流量波动,Ⅱ期波动较大。班长商青于21∶30左右用电话通知在家的车间代生产主任周德虎:岗位气氨波动,原因不清。     

硝酸铵与硝铵磷热稳定性对比研究

为了研究硝铵磷的热稳定性,用DSC－TG同步热分析仪测试了硝酸铵的热分解过程,根据升温速率分别为5,10,15 K／min的DSC和TG－DTG曲线,利用Ozawa法和Kissinger法求得的硝酸铵的活化能基本一致。用Rogers公式和Arrhenius公式求得指前因子和速率常数分别为1．62×1010 s－1,1．07×10－18 s－1（120℃）;硝酸铵在升温速率为5 K／min时,分解峰值温度的活化焓、活化熵、活化自由能分别为102．76 kJ／mol ,－62．35 J／（K·mol ）,134．98 kJ／mol;对比了硝酸铵和硝铵磷的DSC曲线,结果表明硝铵磷的吸热分解峰值温度低于硝酸铵,热稳定性更好。     

基于ARC的自制硝铵炸药热危险性评价研究

为了提高公安机关处置涉爆案事件的理论水平与技术能力,基于氧平衡设计并配制了典型配方的硝铵炸药,开展了ARC量热分析,通过动力学计算,得到了自制硝铵炸药的T_(D24)、T_(NR)、T_(SADT)等特征参数。测试结果表明:硝酸铵/柴油/木粉体系硝铵炸药的绝热分解过程分为两个阶段,负氧平衡状态时的初始分解温度和绝热温升分别为140.2℃和3 647.81℃,热稳定性最差;硝酸铵/柴油/铝粉体系较硝酸铵/柴油/木粉体系的初始分解温度略有上升,绝热温升明显增大,表现为稳定性稍高,爆炸性更强;负氧平衡状态时硝酸铵/柴油/木粉体系硝铵炸药的自加速分解温度为89.34℃,因自分解放热引发热失控,从而导致火灾、爆炸事故发生的可能性较大,应尽量避免硝铵炸药在负氧状态下的存储。     

澜沧铅矿硫化矿炸药自爆危险性分析

通过对澜沧铅矿矿石理化性质分析及其与硝铵炸药接触试验和现场条件测试等研究。对矿山使用硝铵炸药爆破产生自爆的危险性进行了分析与评价。根据分析，评价的结果，提出了防止炸药自爆的技术措施与管理措施。以确保矿山使用硝铵炸药爆破作业时的安全生产。     

乳化炸药高压热分解试验研究

为分析压力在乳化炸药泵送事故中的影响,运用高压加速量热仪对乳化炸药、硝酸铵和含有10%水分的硝酸铵样品热分解特性进行研究。结果表明:压力对于乳化炸药,硝酸铵和含有10%水分硝酸铵样品的热分解有着显著的影响,压力条件下虽然起始分解温度基本没有变化,但是样品反应速率有了显著的升高,导致放热量增大。水分的存在阻碍硝酸铵的热分解,在乳化炸药配方中适当增加水份含量可以提高乳化炸药生产安全性。分析认为相比于温度,压力对于泵送事故的影响更为关键。     

双氧水爆炸事故机理分析及预防措施研究

为了对双氧水引起的爆炸事故的机理进行分析,用加速量热仪对双氧水进行了热危险性测试.通过对数据校正和分析,得到了浓度为30%的双氧水初始热分解温度为34.5 ℃,热分解可达到的最高温度为246 ℃,最大温升速率时间为100 min.结果表明,双氧水极易发生爆炸,并且爆炸威力很大.针对双氧水的爆炸危险,提出采取适当的预防措施,如冷却水法,以避免爆炸事故的发生.     

强化源头管理 实行统一爆破

盱眙地处淮河下游，洪泽湖南岸。山多，石头多，是盱眙一大特色。采石是盱眙的传统产业、支柱产业，多少年来石头在养育了一代又一代盱眙人的同时，也给多少个家庭带来灾难和不幸。1998年8月之前，盱眙县在采石生产上存在“三多”现象较为突出，即私造炸药多，私自放炮多，爆炸事故多。并且流传着这样的顺口溜：“十家忙开山，九家炒硝铵，一家不会造，不傻有点憨”。     

Investigation of ammonium nitrate based emulsion ignition characteristic

This paper presents an analysis of the observed ignition behaviors of ammonium nitrate (AN) and emulsion explosives (EE). Pure AN and EE locally ignited by a heat source do not undergo sustained combustion when the pressure is lower than some threshold value usually called the Minimum Burning Pressure (MBP). A reason for pure AN's and EE's incapable of burning was suggested, and the roles of sample water, inorganic salts, oil phase, and sensitizer were discussed. Accelerating rate calorimeter (ARC) was used to study the thermal stability of EE and AN. The results also showed that MBP is of vital importance and useful for the manufacture and application of AN and EE in terms of accident prevention.     

敞开气氛中硝酸铵热分解过程危险特性的实验研究

利用差热分析仪分析和研究了敞开气氛中硝酸铵的热分解过程，通过在硝酸铵样品中加入酸性物质、KCl、有机物等各种杂质，研究硝酸铵热分解过程的影响因素。结果表明，在敞开气氛中，酸性物质和KCl对硝酸铵热分解过程具有催化作用，有机物会降低硝酸铵的热稳定性，研究结论可以为解决硝酸铵的生产、储存和运输过程中的安全问题提供重要参考。     

Effect of urea on detonation characteristics and thermal stability of ammonium nitrate

A study has examined the effect of urea on the thermal stability and detonation characteristics of ammonium nitrate (AN). The thermal decomposition temperature and surface morphology of samples were investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). For further research on the thermal sensitivity and shock sensitivity of the samples, the Koenen test and UN gap test were conducted. The results indicate that urea can substantially increase the thermal stability of AN (the greatest exothermic peak is increased by more than 100 °C) and reduce the thermal sensitivity of AN. However, AN-50wt. % urea mixtures can still produce a steady detonation in the UN gap test. Urea cannot reduce the ability to propagate a detonation. Possible explanations for these results are discussed.     

硝酸及氯离子对高温硝酸铵水溶液热危险性的影响研究

国内外学者对硝酸铵的危险性进行了大量的研究,而对其水溶液的危险性至今开展不多。笔者采用差示扫描量热仪(DSC)及全自动反应量热仪(RC1e)对高温状态下的硝酸铵水溶液的热分解危险性、杂质离子对其稳定性的影响进行了研究。纯硝酸铵和90%硝酸铵水溶液的DSC实验表明,90%硝酸铵溶液和分析纯硝酸铵具有相似的热爆炸危险;90%硝酸铵水溶液在140~180℃之间的RC1e试验表明:硝酸或氯离子单独存在时,对硝酸铵分解都有不同程度的抑制作用,而同时存在时则大大降低体系的热稳定性。该结果对保障硝酸铵在生产、使用过程中的安全具有重要的参考价值。     

硝酸铵水溶液热稳定性研究

采用加速度量热法(ARC)对高温状态下的硝酸铵水溶液的热分解危险性、杂质对其稳定性的影响进行了研究.实验结果表明,硝酸促进硝酸铵的分解,而氯离子对其有抑制作用;当两者同时存在时大大降低系统的稳定性,且硝酸对硝酸铵的影响远大于氯离子.     

Ammonium nitrate thermal decomposition with additives

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na₂SO₄) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.     

TA-FTIR/MS用于硝酸铵及其混合物的热化学行为研究

为评价物料混合对危险化学品热化学行为的影响,采用热分析-红外/质谱联用技术(TA-FTIR/MS)研究硝酸铵、柠檬酸和蔗糖的混合物的热化学行为。通过对硝酸铵及其混合物的分解温度和分解过程中逸出气体的分析,发现硝酸铵、柠檬酸和蔗糖的混合物热分解温度分别降低至135℃和153℃,而硝酸铵与甲基纤维素的混合物分解温度与硝酸铵基本相同为201℃,且各混合体系的气相分解产物均有氮氧化物(NOX),H2O和CO2。结果表明,混合物受热后其中的硝酸铵首先分解为硝酸和氨气;酸性物质和还原性物质由于对硝酸的分解反应有催化作用,使得混合物的热稳定性下降。     

Calorimetry studies of ammonium nitrate – Effect of inhibitors,confinement, and heating rate

Ammonium nitrate (AN) has been widely used as a fertilizer for almost a century because it is an excellent nitrogen source. However, AN related explosions continue to occur time and again, despite the fact that AN has been extensively investigated. There have been more than 70 AN-related incidents during the last century, which reemphasize the dire need for further research on AN reactive hazards. This research focuses on the alternatives to make AN safer as a fertilizer by reducing its explosivity, by studying the effect of inhibitors, confinement, and heating rate on AN thermal decomposition using the Reactive Systems Screening Tool (RSST). First, the thermal decomposition of AN in the presence of different types of additives, including sodium bicarbonate, potassium carbonate, and ammonium sulfate, was studied under two concentrations, i.e., 2.8 wt.% and 12.5 wt.%. The results show that they are good inhibitors for AN. Second, the effect of confinement was tested by observing AN decomposition under five different initial pressures, varying from ambient pressure to 187 psig. It is concluded that confinement is dangerous to AN, which should be avoid in AN storage and transportation. Lastly, the effect of heating rate was studied by heating up AN under two heating rates of 0.25 °C min⁻¹ and 2 °C min⁻¹. The lower the heating rate, the lower the “onset” temperature detected.     

无机酸对硝酸铵热稳定性影响的研究

为了研究硫酸、盐酸两种无机酸对含能材料硝酸铵热稳定性的影响,使用绝热加速量热仪ARC和微量量热仪C80,对纯硝酸铵及硝酸铵和硫酸、盐酸的混合物进行了热分析实验并研究各种样品在恒温以及升温条件下的吸、放热特性。根据化学反应动力学和热力学理论,确定了硝酸铵及其与无机酸的混合物发生放热分解反应的反应动力学参数和热力学参数。基于Semenov热爆炸模型,计算并比较了各样品标准包装的自加速分解反应温度。     

提高铵梯炸药生产安全性的技术途径

本采用粗制TNT代替军工TNT应用于工业炸药中,不仅可减少环境的污染,而且可提高生产安全性。实验证明由粗制TNT制成的炸药,其性能可满足使用要求。