物理化学学报 >> 2015, Vol. 31 >> Issue (3): 559-565.doi: 10.3866/PKU.WHXB201501092

光化学和辐射化学 上一篇    下一篇

硝酸对N,N-二甲基羟胺γ-辐解及液态辐解产物的影响

王锦花1, 曹晓军1, 李春1, 吴明红1, 包伯荣1, 郑卫芳2, 何辉2, 张生栋2   

  1. 1. 上海大学环境与化学工程学院, 射线应用研究所, 上海 200444;
    2. 中国原子能科学研究院放射化学研究所, 北京 102413
  • 收稿日期:2014-09-23 修回日期:2015-01-09 发布日期:2015-03-06
  • 通讯作者: 王锦花 E-mail:jinhuawang@staff.shu.edu.cn
  • 基金资助:

    国家自然科学基金(20771074, 11025526)和创新团队发展计划(IRT13078)资助项目

Effect of HNO3 on the γ Radiolysis and Radiolytic Liquid Products of N, N-Dimethylhydroxylamine

WANG Jin-Hua1, CAO Xiao-Jun1, LI Chun1, WU Ming-Hong1, BAO Bo-Rong1, ZHENG Wei-Fang2, HE Hui2, ZHANG Sheng-Dong2   

  1. 1. Shanghai Applied Radiation Institute, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, P. R. China;
    2. Radiochemistry Department, China Institute of Atomic Energy, Beijing 102413, P. R. China
  • Received:2014-09-23 Revised:2015-01-09 Published:2015-03-06
  • Contact: WANG Jin-Hua E-mail:jinhuawang@staff.shu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20771074, 11025526) and Program for Innovative Research Team in University, China (IRT13078).

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摘要：

N,N-二甲基羟胺(DMHA)是用于动力堆乏燃料后处理U与Pu和Np分离的新型无盐还原剂, 本文研究了硝酸对DMHA γ-辐解及液态辐解产物的影响. 研究结果表明: 在U、Pu分离循环和Pu纯化循环的辐照剂量下, 在0.3-1.0 mol·L-1的硝酸溶液中, 0.1 和0.5 mol·L-1 DMHA具有较好的辐照稳定性. 当吸收剂量为5-25kGy时, DMHA硝酸溶液的液态辐解产物主要有单甲基羟胺、甲醛、甲酸和亚硝酸. 有机物的浓度远远高于亚硝酸浓度, 且随着剂量和硝酸浓度的增加而增大. 对于相同的硝酸浓度和剂量, 0.1 mol·L-1 DMHA辐解产生的一甲基羟胺的浓度高于0.5 mol·L-1 DMHA, 但前者辐解产生的甲醛浓度低于后者; 当硝酸浓度较高时, 0.1 mol·L-1 DMHA辐解产生的甲酸浓度高于0.5 mol·L-1 DMHA. 亚硝酸浓度与硝酸浓度及剂量的关系取决于起始DMHA和硝酸浓度.

关键词: N,N-二甲基羟胺, 硝酸, γ-辐解, 液相辐解产物, 乏燃料后处理

Abstract:

N,N-dimethylhydroxylamine (DMHA) is a novel salt-free reductant used for the separation of U from Pu and Np in the reprocessing of spent fuel. We investigated the effect of HNO3 on the radiolysis of DMHA and its radiolytic liquid product. Results show that 0.1 and 0.5 mol·L-1 DMHA containing 0.3-1.0 mol· L-1 HNO3 have good radiation stability at a reasonable dose level during the U/Pu separation cycle and the Pu purification cycle. For 5-25 kGy the main radiolytic liquid products are N-methyl hydroxylamine, HCHO, HCOOH, and HNO2. The concentration of these organic compounds is much higher than that of HNO2 and increases with both HNO3 concentration and absorbed dose. At the same HNO3 concentration and dose, the concentration of N-methyl hydroxylamine in irradiated 0.1 mol·L-1 DMHA-HNO3 is higher than that in irradiated 0.5 mol·L-1 DMHA-HNO3. However, the HCHO concentration in 0.1 mol·L-1 DMHA-HNO3 is lower than that in 0.5 mol·L-1 DMHA-HNO3. The HCOOH concentration in 0.1 mol·L-1 DMHA-HNO3 is higher than that in 0.5 mol·L-1 DMHA-HNO3 at higher HNO3 concentrations. The relationship of HNO2 concentration with HNO3 concentration and dose depends on the original DMHA and HNO3 concentrations.

Key words: N,N-dimethyl hydroxylamine, Nitric acid, γ-Radiolysis, Radiolytic liquid product, Reprocessing of spent fuel