FOX⁃7合成过程中水解反应的热危险性及反应动力学

Thermal Hazard and Kinetic Study for the Hydrolysis in the Synthesis Process of FOX⁃7

利用反应量热仪(RC1),测定了以2‑(二硝基亚甲基)‑5,5‑二硝基‑2H‑嘧啶‑4,6‑二酮(TNMPO)为原料,经水解反应制备FOX‑7工艺的热流曲线,对水解反应的工艺热危险性进行了分析,采用定温实验,利用n级反应动力学方程对不同温度下的水解反应速率进行了拟合,进而获得了水解反应的表观反应动力学参数。结果显示,20℃条件下,TNMPO水解制备FOX‑7反应的摩尔生成焓为-46.563 kJ∙mol^(-1),绝热温升为9.1 K。若水解反应发生失控,反应体系可到达的最高温度(MTSR)为29.1℃。对2‑(二硝基亚甲基)‑5,5‑二硝基‑2H‑嘧啶‑4,6‑二酮(TNMPO)的反应级数为0.9317,表观活化能E_(a)为73.2 kJ∙mol^(-1),指前因子A为5.03×10^(9) s^(-1)。

To investigate the thermal hazards of the synthetic reaction process of FOX‑7,the heat flow curve of the hydrolysisinvolved therein has been measured by using Reaction Calorimeter(RC1).The n^(th)‑order kinetic models were applied to different temperature systems and the apparent kinetic parameters of these processes were obtained.The results indicated that the exothermic heat of the synthesis reaction was-46.563 kJ∙mol^(-1),and the adiabatic temperature rise was 9.1 K.Under the thermal runaway chemical reaction condition,the maximum temperature of the synthesis reaction(MTSR)is 29.1℃.The reaction order is 1.21 for synthesis of 2‑(dinitromethylene)‑5,5‑dinitrodihydropyrimidine‑4,6‑dione.The activation energy(E_(a))of the reaction is 73.2 kJ∙mol^(-1),with the pre‑exponential factor of 5.03×10^(9) s^(-1).