微量热法研究硝酸体系中N,N-二甲基羟胺的热稳定性

    Thermal Stability of N, N-Dimethylhydroxylamine in Nitric Acid Solution by Microcalorimetry

    • 摘要: 采用微量热仪研究了硝酸溶液中NN-二甲基羟胺(DMHAN)的热稳定性,考察了溶液中硝酸浓度、DMHAN浓度和甲基肼(MMH)、空气和氮气气氛、金属元素等对DMHAN热稳定性的影响,并比较了相同条件下DMHAN和羟胺(HAN)的热稳定性。研究结果表明,HNO3浓度在1.5~3.0 mol/L和DMHAN浓度在0.05~0.8 mol/L时,DMHAN/HNO3体系起始反应温度(t0)随硝酸浓度的降低或随DMHAN浓度的升高而增加。当HNO3/DMHAN摩尔浓度比值分别为2.5~10和12.5~20时,DMHAN/HNO3体系反应热分别约为865.5 kJ/mol和683.4 kJ/mol,说明不同的HNO3/DMHAN摩尔浓度比值,引发DMHAN/HNO3体系内的各个反应权重不同从而导致体系放热不同。MMH作为支持还原剂,使DMHAN发生分解反应的时间明显滞后;空气、氮气气氛以及后处理流程中的铁和裂片元素锆、钌对DMHAN/HNO3体系分解反应无明显影响,不锈钢容器对DMHAN/HNO3分解反应有催化作用。

       

      Abstract: The thermal stability of N, N-dimethylhydroxylamine(DMHAN) in the nitric acid solution was studied using micro calorimeter. The main influence factors including the nitric acid concentration, the concentration of DMHAN, MMH, atmosphere(air and nitrogen) and metals were studied and compared the thermal stability of DMHAN with HAN under the same conditions. The results show that the initial reaction temperature(t0) of DMHAN/HNO3 (HNO3: 1.5-3.0 mol/L, DMHAN: 0.05-0.8 mol/L) is improved as the acidity reduces or the concentration of DMHAN increases. The reaction heat of DMHAN/HNO3 is 865.5 kJ/mol and 683.4 kJ/mol respectively when the mole concentration ratios of HNO3 to DMHAN are 2.5-10 and 12.5-20. This indicates the different ratio of HNO3 to DMHAN makes the scale of reactions different in the DMHAN/HNO3, so it makes the different reaction heat. Holding reductant MMH make the induction period of the autocatalytic reaction become longer. The air, nitrogen atmosphere, Fe and the fission products (Zr, Ru) do not affect the decomposition of DMHAN, but the stainless steel make the DMHAN/HNO3 show higher reactivity.

       

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