Hydrolysis of Dimethyl Methylphosphonate (DMMP) in Hot-Compressed Water.
Hydrolysis of Dimethyl Methylphosphonate (DMMP) in Hot-Compressed Water.
复制标题
甲基膦酸二甲酯 (DMMP) 在热压缩水中的水解。
DOI：
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发表时间：
2020
影响因子：
2.9
通讯作者：
I. Novosselov
中科院分区：
文献类型：
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作者：
Brian R. Pinkard;Shreya Shetty;J. Kramlich;P. Reinhall;I. Novosselov
甲基膦酸二甲酯(DMMP)因其具有相似的物理化学性质和明显较低的毒性而经常被用作有机磷神经毒剂的化学替代品。在温度为200~300℃，压力为20~30 MPa，停留时间为30~80℃的条件下，考察了压力和温度对反应动力学的影响，考察了温度和压力对反应动力学的影响。观察到DMMP的水解遵循准一级反应行为，生成甲基膦酸和甲醇作为唯一可检测的反应产物。这对于实际实施用于化学战剂中和的连续水热反应堆具有重要意义，因为该过程只产生稳定、毒性较低的化合物。压力对压缩液态水中的水解率没有明显影响。测得其拟一级阿累尼乌斯参数，其活化能为90.17±5.68kJmol-1，指前因子为107.51±0.58kJmol-1。
Dimethyl methylphosphonate (DMMP) is often used as a chemical surrogate for organophosphate nerve agents, as it exhibits similar physiochemical properties while having significantly lower toxicity. Continuous hydrolysis of DMMP in hot-compressed water is performed at temperatures from 200 to 300 °C, pressures of 20 and 30 MPa, and residence times from 30 to 80 s to evaluate the effects of pressure and temperature on reaction kinetics. DMMP hydrolysis is observed to follow pseudo-first-order reaction behavior, producing methylphosphonic acid and methanol as the only detectable reaction products. This is significant for the practical implementation of a continuous hydrothermal reactor for chemical warfare agent neutralization, as the process only yields stable, less-toxic compounds. Pressure has no discernible effect on the hydrolysis rate in compressed liquid water. Pseudo-first-order Arrhenius parameters are determined, with an activation energy of 90.17±5.68 kJ mol-1 and a pre-exponential factor of 107.51±0.58 s-1.