辐照气氛对异丙氧基杯[4]冠-6辐解的影响

doi:10.3866/PKU.WHXB201211215

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

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 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-Yong^1,2, WANG Qian¹, PENG Jing², HUANG Wei¹, ZHAI Mao-Lin², LONG Xing-Gui¹

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/Abstract

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

敖银勇, 王茜, 彭静, 黄玮, 翟茂林, 龙兴贵. 辐照气氛对异丙氧基杯[4]冠-6辐解的影响[J]. 物理化学学报, 2013, 29(02), 418-422. doi: 10.3866/PKU.WHXB201211215

AO Yin-Yong, WANG Qian, PENG Jing, HUANG Wei, ZHAI Mao-Lin, LONG Xing-Gui. Influence of Atmosphere on the Radiolysis Products of BPC6 under γ-Irradiation[J]. Acta Phys. -Chim. Sin. 2013, 29(02), 418-422. doi: 10.3866/PKU.WHXB201211215

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201211215

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I02/418

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辐照气氛对异丙氧基杯[4]冠-6辐解的影响

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

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