硝化甘油制备过程中反应热危险性分析  

Thermal Hazard Analysis in the Preparation Process of Nitroglycerin

作　　者：周新建 毛智鹏 李洋[3] 朱隆懿 钱华[3] 李芳[3,4] Zhou Xinjian;Mao Zhipeng;Li Yang;Zhu Longyi;Qian Hua;Li Fang(Jiangsu Jia'an Safety Technology Limited Company,Jiangsu,224055;Liaoning Qingyang Special Chemicals Co.,Ltd.,Liaoning,111018;School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Jiangsu,210094;China National Civil Explosives Quality Inspection and Testing Center,Jiangsu,210094)

机构地区：[1]江苏佳安安全科技有限公司,江苏224055 [2]辽宁庆阳特种化工有限公司,辽宁111018 [3]南京理工大学化学与化工学院,江苏210094 [4]国家民用爆破器材质量检验检测中心,江苏210094

出　　处：《当代化工研究》2025年第6期1-5,共5页Modern Chemical Research

摘　　要：硝化甘油作为一种广泛运用的推进剂和发射药原料,具有高能高感的特性。为分析硝化甘油制备过程的热危险性,利用反应量热仪(RC)、差式扫描量热仪(DSC)和加速绝热量热仪(ARC)测定了甘油硝化反应过程中的放热及反应后硝化液和硝化甘油的热分解行为。结果表明:反应体系的绝热温升(ΔT_(ad))为39.5℃,表观比放热量为62.0 kJ·kg^(-1)(以反应体系总质量计);DSC和ARC测试结果都表明反应后硝化液的热稳定性比硝化甘油差,初始分解温度提前40.0℃;通过反应后硝化液的ARC测试数据,获得最大反应速度到达时间(TMR_(ad))和温度之间的关系,计算出绝热诱导期为24 h时所对应的温度TD_(24),反应的TD_(24)、技术最高温度(MTT)与理论最高可达温度(MTSR)分别为74.4℃、83.0℃和23.1℃。基于精细化工反应安全风险评估规范,该反应在冷却失效的情况下,体系不易触发二次放热分解。Nitroglycerin,as a widely used propellant and raw material for gunpowder,possesses the characteristics of high energy and high sensitivity.To analyze the thermal hazards during the nitroglycerin preparation process,reaction calorimetry(RC),differential scanning calorimetry(DSC),and accelerating rate calorimetry(ARC)were employed to measure the exothermic behavior of the glycerin nitration reaction,as well as the thermal decomposition characteristics of the nitroglycerin and nitrated solution after the reaction.The results demonstrated that the adiabatic temperature rise(ΔT_(ad))of the reaction system was 39.5℃,with an apparent specific heat release of 62.0 kJ·kg^(-1)(based on the total mass of the reaction system).Both DSC and ARC tests revealed that the post-reaction nitrated solution exhibited poorer thermal stability compared to pure nitroglycerin,with an initial decomposition temperature 40.0℃lower.Using ARC data from the post-reaction nitrated solution,the relationship between the time to maximum reaction rate(TMR_(ad))and temperature was established,enabling the calculation of TD_(24)(the temperature corresponding to an adiabatic induction period of 24 hours).The determined TD_(24),maximum technical temperature(MTT),and maximum theoretical attainable temperature(MTSR)were 74.4℃,83.0℃,and 23.1℃,respectively.According to the Specification for Safety Risk Assessment of Fine Chemical Reactions,the system is less likely to trigger secondary exothermic decomposition under cooling failure conditions.

关 键 词：硝化甘油 硝化反应 反应量热 热分析动力学 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] X93[环境科学与工程—安全科学]