二硝基脲法合成HMX的过程监测及动力学分析

Process Monitoring and Kinetics Analysis of Synthesizing HMX by Dinitrocarbamide Method

采用反应量热仪(RC1)对二硝基脲法合成HMX各步放热过程进行测定,并分析其放热参数以及严重度;利用绝热加速量热仪(ARC)测定了中间产物的分解温度及放热速率,并进行了动力学分析。结果表明,加入尿素后反应体系立即放热,硝化反应在2s内发生,部分反应到达成熟期才完成;其余各步反应进行很快,也都在2s内发生,主要热量用于中和硫酸放热;得到的绝热温升越高,发生失控反应的严重度越高;加水的过程要在0℃下进行,加硝酸铵的过程要在10℃下进行,加尿素的合成反应温度较原工艺可以适当提高2℃,加DPT反应过程最为安全,合成反应的最高温度(MTSR)为40.8℃;经ARC测定得中间产物的相关动力学参数:活化能(Ea)为254kJ/mol,指前因子(A)为1.26×10^(30)s^(-1),反应级数(n)为0.88。

The exothermic process for synthesizing HMX with dinitrocarbamide method was measured by a RC1 reaction calorimetry and the exothermic parameters and risk degree were analyzed. The decomposition temperature and exothermic rate of intermediate products were measured by ARC, and the kinetic analysis was carried out. The results show that after adding urea, the reaction system is exothermic immediately. Nitrification reaction is carried out in 2s, part of the reaction arrives at the mature period to complete only. The rest of various step reactions were carried out quickly in 2s,and the main heat is used to neutralize the exothermicity of sulfuric acid. The higher the adiabatic temperature rise, the higher the severity of the runaway reaction. The process of adding water should be carried out at 0℃ and the process of ammonium nitrate should be carried out at 10℃. The synthetic reaction temperature of adding urea can be appropriately increased by 2℃ and the reaction process of adding DPT is the most safe. The maximum temperature of the synthetic reaction （MTSR） is 40.8℃. The activation energy （E a）, pre-exponential factor （A） and the reaction order （n） of the intermediate products obtained by ARC measurement are 254 kJ/mol, 1.26 ×10^30 s^-1 and 0.88, respectively.