Selective adsorption and purification of low-concentration Kr gas using various adsorbents

doi:10.11949/0438-1157.20241317

Abstract

Abstract:

Kr-85 is a widely used and valuable β-radionuclide, mainly present in the tail gas of spent fuel reprocessing. The recovery and purification of Kr-85 not only mitigate the environmental impact of radioactive gases, but also yield high-activity radiation sources. This study proposes a method to concentrate trace amounts of Kr in off-gas streams via low-temperature adsorption using different porous adsorbents, followed by further purification through chromatography to obtain high-purity Kr gas. Nano-scale pure silica MFI zeolite (Si-MFI) was synthesized, and its low-temperature adsorption-separation capacity for Kr gas was compared with various other adsorbents. The results indicate that Si-MFI exhibits the best adsorption-separation performance for Kr gas at 195 K. Consequently, Si-MFI was selected as the adsorbent for this study. Furthermore, the feasibility of the proposed approach was validated through breakthrough experiments in a fixed-bed setup and a custom-designed low-temperature Kr recovery apparatus. The results demonstrate that the device and the cryogenic enrichment-chromatographic purification process can effectively recover Kr from simulated exhaust gas with a concentration of 0.005% (vol). The purified Kr product is virtually free of nitrogen and oxygen impurities, thereby confirming the feasibility of the process.

Key words: gas, adsorption, purification, zeolite, krypton, spent fuel gas, gas separation

摘要：

Kr-85是一种应用广泛且极具价值的β放射性核素，主要存在于乏燃料后处理过程的尾气中。Kr-85的回收和纯化不仅能够减少放射性气体对环境的危害，还能获得高活度的放射源。本文提出了利用不同多孔吸附剂对尾气中的痕量Kr进行低温吸附富集，并通过制备色谱法进一步纯化以获得高纯Kr气。合成了纳米级纯硅MFI分子筛（Si-MFI），并对比了四种吸附剂在低温下对Kr气的选择性吸附分离能力。测试结果表明在195 K条件下Si-MFI对Kr气吸附分离效果最好。进一步通过固定床穿透实验及实验室自主设计搭建的低温Kr回收装置验证了低温回收和纯化Kr气的可行性。实验结果表明，该装置及低温富集-制备色谱纯化工艺能有效回收模拟尾气中含量为0.005%（体积）的Kr，产品Kr气中基本没有氮气和氧气杂质，证明了工艺的可行性。

关键词: 气体, 吸附, 纯化, 沸石, 氪气, 乏燃料气, 气体分离

CLC Number:

TQ 028.1

Chunhui TAO, Yinhui LI, Yu FU, Ran DUAN, Zeyi ZHAO, Yufeng TANG, Gang ZHANG, Heping MA. Selective adsorption and purification of low-concentration Kr gas using various adsorbents[J]. CIESC Journal, 2025, 76(5): 2358-2366.

陶春珲, 李印辉, 傅钰, 段然, 赵泽一, 唐羽丰, 张罡, 马和平. 不同吸附剂对低浓度Kr气的选择性吸附与纯化[J]. 化工学报, 2025, 76(5): 2358-2366.

Figures/Tables 9

Fig.1 Basic characterization of Si-MFI

Fig.2 Adsorption isotherms of four adsorbents for N2, O2 and Kr

Fig.3 IAST selectivity of four adsorbents at 195 K

Fig.4 Adsorption isotherms of Si-MFI for N2, O2 and Kr at four different temperatures

Fig.5 IAST selectivity of Si-MFI at four different temperatures

Fig.6 Schematic diagram of fixed bed breakthrough device

Fig.7 Fixed bed breakthrough experiment results

Fig.8 Schematic diagram of Kr recovery and purification device

Fig.9 Time dependent graph of N2, O2, and Kr mass spectrometry signal intensity

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