Pt催化N2H4还原U(Ⅵ)制备U(Ⅳ)过程中N2H4断键机制研究

Study on Bond Breaking Mechanism for Process of U(Ⅳ) Produced by N2H4 Reducing U(Ⅵ) with Platinum as Catalyst

  • 摘要: 为优化硝酸介质下Pt催化N2H4还原U(Ⅵ)制备U(Ⅳ)的工艺条件,确定此反应过程的控制步骤,有针对性地提高控制步骤的反应速率,以确定N2H4还原U(Ⅵ)制备U(Ⅳ)过程中的反应历程以及反应机理,通过实验研究确定了N2H4在Pt催化剂上的断键方式和分解机理。采用气相色谱法、分光光度法、滴定法及排水法对硝酸介质下Pt催化N2H4还原U(Ⅵ)制备U(Ⅳ)过程中的产物进行分析,确定反应过程中N2H4的断键机制。结果表明,硝酸介质下Pt催化N2H4还原U(Ⅵ)制备U(Ⅳ)反应过程中没有叠氮酸、氮氧化物及氢气生成,产物主要是N2,生成的N2的量与消耗的N2H4的量接近1∶1;当存在U(Ⅵ)时,生成的NH+4产量较低,当U(Ⅵ)反应完全后,NH+4的产生速率急剧增大;N2H4以N—N断键和N—H断键两种方式共存;反应温度升高有利于加快由U(Ⅵ)制备U(Ⅳ)还原反应的进行。

     

    Abstract: In order to optimize the process conditions of U(Ⅳ) produced by N2H4 reducing U(Ⅵ) with platinum as catalyst in the nitric acid environment, determine the control steps of the reaction process, improve the rate of controlling step in the reaction, and determine the reaction path and reaction mechanism, it is necessary to confirm the manner of bond breaking and decomposition mechanism of the N2H4 with Pt as catalyst. In order to determine the bond breaking mechanism of N2H4 in this process, gas chromatography, spectrophotometry, titration and drainage method were used in this paper to analyze the product in the process of U(Ⅳ) produced by N2H4 reducing U(Ⅵ) with Pt as catalyst in the nitric acid environment. The results show that there is no hydrazoic acid, nitrogen oxides or hydrogen product in the process. The main product is N2, and the consumption ratio of N2 to N2H4 is close to 1∶1. When there is U(Ⅵ), the yield of NH+4 is low, and the production rate of NH+4 increases sharply when the U(Ⅵ) reaction is complete. N—N bond breaking and N—H bond breaking coexist. Increasing temperature is conducive to speed up the reduction reaction.

     

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