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首页> 外文期刊>Environmental Science & Technology >Kinetics of the Alkaline Hydrolysis of High Explosives RDX and HMX in Aqueous Solution and Adsorbed to Activated Carbon
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Kinetics of the Alkaline Hydrolysis of High Explosives RDX and HMX in Aqueous Solution and Adsorbed to Activated Carbon

机译：高炸药RDX和HMX在水溶液中吸附于活性炭上的碱解动力学。

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Aqueous alkaline hydrolysis of bulk quantities and wastewater contaminated with high explosives is a promising technology for treatment and disposal of the worldwide surplus of munitions. We investigated the hydrolysis kinetics of the high explosives hexahy-dro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) for temperatures ranging from 50 to 80℃ and in the pH range from 10 to 12. The experimental data were described using a pseudo-first-order model with subsequent calculation of second-order rate constants from experiments with excess hydroxide concentration. The temperature dependency of the rate constants was evaluated using the Arrhenius model. The activation energies were determined to be E_(RDX) = 99.9 ± 1.9 kJ mol~(-1) and E_(HMX) = 111.9 ± 0.8 kJ mol~(-1). The rate of HMX hydrolysis is much slower than the rate of RDX hydrolysis and may become rate limiting in the treatment of RDX/HMX mixtures. The alkaline hydrolysis of RDX yields 1.6 M NO_2~-, 1.5 M HCOO~-, 0.1 M CH_3COO~-, 1.1 M HCHO (11), 0.9 M NH_3, 1.1 M N_2O, and 0.34 M N_2 per mol of RDX hydrolyzed. Acetate ion (CH_3COO~-) is a previously unknown end product of the alkaline hydrolysis of RDX. A mass balance showed a recovery of 94% carbon and 90% nitrogen. During GC/MS analysis of the end products, no further unknown products could be found. In batch desorption studies, it was also shown that RDX-laden activated carbon can be regenerated using alkaline hydrolysis (T= 80℃, pH 12) and that the desorption of the hydrolysis products is complete.
机译：大量碱水水解和被高炸药污染的废水是一种用于处理和处置全球弹药剩余的有前途的技术。我们研究了高炸药hexahy-dro-1,3,5-trinitro-1,3,5-triazine（RDX）和octahydro-1,3,5,7-tetranitro-1,3,5的水解动力学，温度为50至80℃，pH为10至12的7-四唑辛（HMX）。使用伪一阶模型描述了实验数据，随后根据实验计算了过量的二阶速率常数氢氧化物浓度。使用Arrhenius模型评估速率常数的温度依赖性。活化能确定为E_（RDX）= 99.9±1.9 kJ mol〜（-1）和E_（HMX）= 111.9±0.8 kJ mol〜（-1）。 HMX水解速率比RDX水解速率慢得多，并且在RDX / HMX混合物的处理中可能会限制速率。每摩尔RDX水解后，RDX的碱水解产生1.6 M NO_2〜-，1.5 M HCOO〜-，0.1 M CH_3COO〜-，1.1 M HCHO（11），0.9 M NH_3、1.1 M N_2O和0.34 M N_2。乙酸根离子（CH_3COO〜-）是RDX碱性水解的最终未知产物。质量平衡表明回收了94％的碳和90％的氮。在对最终产品进行GC / MS分析期间，找不到其他未知产品。在分批解吸研究中，还表明，可以使用碱性水解（T = 80℃，pH 12）来再生载有RDX的活性炭，并且水解产物的解吸已完成。

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