物理化学学报 >> 2013, Vol. 29 >> Issue (02): 418-422.doi: 10.3866/PKU.WHXB201211215

光化学和辐射化学 上一篇    下一篇

辐照气氛对异丙氧基杯[4]冠-6辐解的影响

敖银勇1,2, 王茜1, 彭静2, 黄玮1, 翟茂林2, 龙兴贵1   

  1. 1 中国工程物理研究院核物理与化学研究所, 四川绵阳 621900;
    2 北京大学化学与分子工程学院应用化学系, 北京分子科学国家实验室, 北京 100871
  • 收稿日期:2012-09-25 修回日期:2012-11-20 发布日期:2013-01-14
  • 通讯作者: 翟茂林, 龙兴贵 E-mail:mlzhai@pku.edu.cn; longxingg@yahoo.com.cn
  • 基金资助:

    国家自然科学基金(91126014, 11079007, 21073008)及高等学校博士点基金(20100001110021)资助项目

Influence of Atmosphere on the Radiolysis Products of BPC6 under γ-Irradiation

AO Yin-Yong1,2, WANG Qian1, PENG Jing2, HUANG Wei1, ZHAI Mao-Lin2, LONG Xing-Gui1   

  1. 1 Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, Sichuan Province, P. R. China;
    2 Beijing National Laboratory for Molecular Sciences, Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
  • Received:2012-09-25 Revised:2012-11-20 Published:2013-01-14
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (91126014, 11079007, 21073008) and Research Fund for the Doctoral Program of Higher Education, China (20100001110021).

摘要:

异丙氧基杯[4]冠-6(1,3-交替-25,27-二(2-丙氧基)杯[4]芳烃-26,28-冠-6, 简称BPC6)对高放废液中的放射性Cs离子具有很好的选择萃取性能, 然而在萃取过程中BPC6 会受到强辐射场辐照, 所以有必要研究其辐射稳定性. 本文应用气相色谱(GC)、傅里叶变换显微红外(Micro-FTIR)和核磁共振(NMR)谱等手段分析了BPC6 固体分别在O2和N2气氛下的γ辐照效应. 结果表明, 当剂量为1 MGy时, O2气氛下BPC6 的辐解率明显高于N2(分别约为10.4%和2.5%), 而且气体辐解产物也有很大差异, 在O2气氛下主要为H2、CH4、CO和CO2,而在N2辐照气氛下还有C2H4、C2H6、C3H6和C3H8等产物. 通过综合分析气体与固体辐解产物, 我们提出BPC6在不同气氛下具有不同的辐解途径, 这将为BPC6 萃取体系的辐射效应研究提供新的方法与思路, 加深对其辐解机理的认识.

关键词: BPC6, 铯离子萃取剂, γ辐射, 辐解产物, 气相色谱分析

Abstract:

Bis(2-propyloxy)calix[4]crown-6 (BPC6) is an effective separation agent for the removal of cesium from high-level liquid wastes, because of its high selectivity and coordination capacity toward cesium ions. BPC6 will be exposed to ionizing radiation generated by radionuclides during the treatment of high-level liquid nuclear wastes, so it is necessary to investigate the radiolysis mechanism of BPC6 under γ-irradiation conditions. In this work, the radiolysis products including the gaseous and solid products of BPC6 solid were systematically assessed using gas chromatography (GC), micro Fourier transform infrared (Micro-FTIR) spectroscopy, and nuclear magnetic resonance spectroscopy. The radiolysis ratio for BPC6 in an O2 atmosphere (approximately 10.4%) was significantly higher than that in an N2 atmosphere (approximately 2.5%). The main radiolytic gas products of BPC6 under O2 were H2, CH4, CO, and CO2, while those under N2 were H2, CH4, CO, CO2, C2H4, C2H6, C3H6, and C3H8. Finally, a mechanism for the radiolysis of BPC6 under different atmospheres was suggested, in terms of the gas and solid radiolytic products. This work will be of significant help in understanding the degradation mechanism of the BPC6 extraction system.

Key words: BPC6, Cs+ extractant, γ-Radiation, Radiolytic product, Gas chromatography analysis

MSC2000: 

  • O644