不同吸附剂对低浓度Kr气的选择性吸附与纯化

doi:10.11949/0438-1157.20241317

摘要/Abstract

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

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

中图分类号:

TQ 028.1

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.

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.

图/表 9

图1 Si-MFI的基本表征

Fig.1 Basic characterization of Si-MFI

图2 四种吸附剂对N2、O2和Kr的吸附等温线

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

图3 195 K下四种吸附剂的IAST选择性

Fig.3 IAST selectivity of four adsorbents at 195 K

图4 四种温度下Si-MFI对N2、O2和Kr的吸附等温线

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

图5 四种温度下Si-MFI的IAST选择性

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

图6 固定床穿透装置示意图

Fig.6 Schematic diagram of fixed bed breakthrough device

图7 固定床穿透实验结果

Fig.7 Fixed bed breakthrough experiment results

图8 Kr回收纯化装置示意图

Fig.8 Schematic diagram of Kr recovery and purification device

图9 N2、O2和Kr质谱信号强度随时间变化

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

参考文献 30

1	Zhang H P, Fan Y L, Krishna R, et al. Robust metal-organic framework with multiple traps for trace Xe/Kr separation[J]. Science Bulletin, 2021, 66(11): 1073-1079.
2	李大明. 氪-85的性质和应用[J]. 中国照明电器, 2000(9): 20.
	Li D M. Properties and applications of krypton-85[J]. China Light & Lighting, 2000(9): 20.
3	王伟, 罗娟, 杨淼, 等. 锂电池制造企业氪-85涂覆密度仪放射防护改造效果评价[J]. 中国工业医学杂志, 2019, 32(3): 230-231.
	Wang W, Luo J, Yang M, et al. Assessment and analysis on transformation effect of radiological protection facilities for overstandard krypton-85 coated densitometers in a lithium battery manufacturing enterprise[J]. Chinese Journal of Industrial Medicine, 2019, 32(3): 230-231.
4	Musy S, Meyzonnat G, Barbecot F, et al. In-situ sampling for krypton-85 groundwater dating[J]. Journal of Hydrology X, 2021, 11: 100075.
5	Denisova N, Gavare Z, Revalde G, et al. A study of capillary discharge lamps in Ar-Hg and Xe-Hg mixtures[J]. Journal of Physics D: Applied Physics, 2011, 44(15): 155201.
6	Schoeppner M, Glaser A. Present and future potential of krypton-85 for the detection of clandestine reprocessing plants for treaty verification[J]. Journal of Environmental Radioactivity, 2016, 162: 300-309.
7	郭贵银. 核电厂气态流出物中氪-85的分析方法研究及应用[R]. 苏州: 苏州热工研究院有限公司, 2020.
	Guo G Y. Research and application of analysis method for krypton-85 in gaseous outflow of nuclear power plant[R]. Suzhou: Suzhou Nuclear Power Research Institute Co., Ltd., 2020.
8	Ahlswede J, Hebel S, Ross J O, et al. Update and improvement of the global krypton-85 emission inventory[J]. Journal of Environmental Radioactivity, 2013, 115: 34-42.
9	Smethie W M, Solomon D K, Schiff S L,et al.Tracing groundwater flow in the Borden aquifer using krypton-85[J]. Journal of Hydrology, 1992, 130(1/2/3/4): 279-297.
10	陈彬, 武山, 宋晓靓, 等. 用于氙氪吸附分离的金属-有机骨架材料耐辐照性能的初步研究[J]. 核技术, 2022, 45(1): 51-57.
	Chen B, Wu S, Song X J, et al. Preliminary study on irradiation stability of metal-organic skeleton materials for the adsorption and separation of xenon and krypton[J]. Nuclear Techniques, 2022, 45(1): 51-57.
11	Holdsworth A, Eccles H, Sharrad C, et al. Spent nuclear fuel—waste or resource? The potential of strategic materials recovery during recycle for sustainability and advanced waste management[J]. Waste, 2023, 1(1): 249-263.
12	宋凤丽, 刘志辉, 吕丹, 等. 乏燃料后处理厂废气处理系统化学安全问题分析[J]. 核科学与工程, 2015, 35(3): 560-567.
	Song F L, Liu Z H, Lv D, et al. Analysis on chemical safety problems of radioactive gas waste treatment system in nuclear fuel reprocessing plant[J]. Nuclear Science and Engineering, 2015, 35(3): 560-567.
13	何军勇, 张双全, 任勇, 等. 动力堆乏燃料后处理厂三废处理调研报告[R]. 嘉峪关: 中国核科技信息与经济研究院, 2006.
	He J Y, Zhang S Q, Ren Y, et al. Research Report on the Treatment of Three Wastes in Spent Fuel Reprocessing Plant of Power Reactor[R]. Jiayuguan: China Institute of Nuclear Science and Technology Information and Economics, 2006.
14	熊顺顺, 闫钊通, 刘博煜, 等. 放射性惰性气体分离与分离材料研究进展[J]. 核化学与放射化学, 2020, 42(6): 478-497.
	Xiong S S, Yan Z T, Liu B Y, et al. Research progress on radioactive noble gas separation and separation materials[J]. Journal of Nuclear and Radiochemistry, 2020, 42(6): 478-497.
15	逄锦鑫, 尹玉国, 孙尔雁. 乏燃料后处理中氪-85处理技术研究[J]. 广东化工, 2022, 49(11): 78-80.
	Pang J X, Yin Y G, Sun E Y. Understanding the treatment technology of Kr-85 during the spent fuel reprocessing[J]. Guangdong Chemical Industry, 2022, 49(11): 78-80.
16	放射性废物管理[Z]. 嘉峪关: 核工业总公司四〇四厂与核科学技术情报研究所, 1996: 6.
	Radioactive waste management[Z]. Jiayuguan: CNNC 404 Corporation and Institute of Nuclear Science and Technology Information, 1996: 6.
17	陆治美. 放射性同位素提取及制源工艺[M]. 北京: 中国原子能出版社, 2012: 2-10.
	Lu Z M. Radioisotope Extraction and Source Preparation Technology[M]. Beijing: China Atomic Energy Publishing, 2012: 2-10.
18	Mckayh A C. Background consideration in the immobilization of volatile radionuclides. Management of gaseous wastes from nuclear facilities[C]// Proc Int Symp. Vienna: IAEA, 1980: 59-78.
19	陈莉云, 武山, 张昌云,等. 用制备色谱法分离氪氙[J]. 核技术, 2012, 35(6): 442-446.
	Chen L Y, Wu S, Zhang C Y, et al. Separation of Xe and Kr using preparative chromatography method[J]. Nuclear Techniques, 2012, 35(6): 442-446.
20	玛依热·阿不力提甫, 钟子豪, 白希. 制备气相色谱在挥发性成分分离中的应用研究进展[J]. 色谱, 2023, 41(1): 37-46.
	Mayira A, Zhong Z H, Bai X. Progress in the application of preparative gas chromatography in separating volatile compounds[J]. Chinese Journal of Chromatography, 2023, 41(1): 37-46.
21	王兆程, 程瑾, 王宜迪, 等. 1,4-环己烷二甲酸二甲酯顺反异构体的气相色谱分析[J]. 当代化工, 2023, 52(4): 1006-1008.
	Wang Z C, Cheng J, Wang Y D, et al. Gas chromatographic analysis of dimethyl 1, 4-cyclohexanedicarboxylate cis-trans isomers[J]. Contemporary Chemical Industry, 2023, 52(4): 1006-1008.
22	杜伯犀, 龚艳艳. 高温煤焦油轻质组分的高压制备色谱分离研究[J]. 煤质技术, 2019, 34(4): 10-13.
	Du B X, Gong Y Y. Separation of light components in high-temperature coal tar by high performance liquid chromatography[J]. Coal Quality Technology, 2019(4): 10-13.
23	张震, 和文龙, 张罡, 等. 基于低温制备色层法的溶解尾气中氪-85纯化装置与方法[J]. 当代化工, 2024, 53(7): 1525-1529+1534.
	Zhang Z, He W L, Zhang G, et al. Research on purification device and method of krypton-85 in dissolved tail gas based on low temperature preparation chromatography[J]. Contemporary Chemical Industry, 2024, 53(7): 1525-1529, 1534.
24	胡波, 张雪平, 苏鸣皋, 等. 放射性气体中⁸⁵Kr/¹³³Xe的吸附与分离技术研究现状[J]. 应用化工, 2018, 47(9): 2010-2014, 2019.
	Hu B, Zhang X P, Su M G, et al. Study on adsorption and separation technology for ⁸⁵Kr and ¹³³Xe in radioactive gases[J]. Applied Chemical Industry, 2018, 47(9): 2010-2014, 2019.
25	Zhou Y C, Chen X F, Lin Y, et al. Removal of nitrogen pollutants in the chemical looping process: a review[J]. Energies, 2024, 17(14): 3432.
26	Kancharlapalli S, Natarajan S, Ghanty T K. Confinement-directed adsorption of noble gases (Xe/Kr) in MFM-300(M)-based metal–organic framework materials[J]. The Journal of Physical Chemistry C, 2019, 123(45): 27531-27541.
27	Xiong J B, Li A L, Fan Y L, et al. Creating uniform pores for xenon/krypton and acetylene/ethylene separation on a strontium-based metal-organic framework[J]. Journal of Solid State Chemistry, 2020, 288: 121337.
28	Li Y H, Min X B, Li W H, et al. Experimental and computational evaluation of Ag-exchanged ZSM-5 and SSZ-13 for xenon capture[J]. Microporous and Mesoporous Materials, 2022, 330: 111631.
29	Grand J, Talapaneni S N, Vicente A, et al. One-pot synthesis of silanol-free nanosized MFI zeolite[J]. Nature Materials, 2017, 16(10): 1010-1015.
30	胡苏阳, 刘鑫博, 唐建峰, 等. 13X沸石分子筛对低浓度CO₂动态吸附[J]. 化工进展, 2022, 41(1): 153-160.
	Hu S Y, Liu X B, Tang J F, et al. Dynamic adsorption of low concentration CO₂ over 13X zeolite[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 153-160.

[1]	胡嘉朗, 姜明源, 金律铭, 张永刚, 胡鹏, 纪红兵. 机器学习辅助MOFs高通量计算筛选及气体分离研究进展[J]. 化工学报, 2025, 76(5): 1973-1996.
[2]	齐昊, 王玉杰, 李申辉, 邹琦, 刘轶群, 赵之平. 双金属Co/Zn-ZIFs中C₃H₆和C₃H₈吸附和扩散行为分子模拟研究[J]. 化工学报, 2025, 76(5): 2313-2326.
[3]	赵浩帆, 任豪杰, 刘宗凯, 董冠英, 张亚涛. MOFs玻璃膜在气体分离领域的研究进展[J]. 化工学报, 2025, 76(5): 2042-2054.
[4]	张越, 刘佳鑫, 马敬, 刘毅. 金属有机骨架膜应用于海水提铀研究进展[J]. 化工学报, 2025, 76(5): 2087-2100.
[5]	茅雨洁, 路晓飞, 锁显, 杨立峰, 崔希利, 邢华斌. 工业气体中微量氧深度脱除催化剂研究进展[J]. 化工学报, 2025, 76(5): 1997-2010.
[6]	时任泽, 丁秋燕, 袁振军, 那健, 刘见华, 郭树虎, 赵雄, 李洪, 高鑫. 4N电子级二乙氧基甲基硅烷的纯化技术研究[J]. 化工学报, 2025, 76(5): 2186-2197.
[7]	马瑞洁, 黄子轩, 关雪倩, 陈光进, 刘蓓. ZIF-8/DMPU浆液分离C₂H₆/ CH₄混合气研究[J]. 化工学报, 2025, 76(5): 2262-2269.
[8]	徐智超, 俞镇东, 吴昊峰, 吴沛文, 武洪翔, 巢艳红, 朱文帅, 刘植昌, 徐春明. 富酸位13X分子筛的制备及其超深度吸附脱除生物柴油中硫醇[J]. 化工学报, 2025, 76(5): 2198-2208.
[9]	顾栋, 皮行健, 张叠, 张瑛. 不同粒径CAU-1/PI混合基质膜的构建与H₂/CO₂分离性能研究[J]. 化工学报, 2025, 76(5): 2410-2418.
[10]	郭彭涛, 王婷, 薛波, 应允攀, 刘大欢. 用于CH₄/N₂分离的多吸附位点超微孔MOF[J]. 化工学报, 2025, 76(5): 2304-2312.
[11]	唐磊, 王振菲, 李聪利, 杨佳辉, 郑浩, 石琪, 董晋湘. Co-MOF-74和Mg-MOF-74的CO工作吸附容量及操作条件[J]. 化工学报, 2025, 76(5): 2279-2293.
[12]	李艳, 雷美丽, 李鑫钢. 基于分离性能的顺序式模拟移动床结构调控策略[J]. 化工学报, 2025, 76(5): 2219-2229.
[13]	巴雅琪, 吴涛, 邸安頔, 陆安慧. 多孔炭材料用于低碳烃分离的研究进展[J]. 化工学报, 2025, 76(5): 2136-2157.
[14]	谈朋, 李雪梅, 刘晓勤, 孙林兵. 基于柔性MOFs的磁响应复合材料及其丙烯吸附性能研究[J]. 化工学报, 2025, 76(5): 2230-2240.
[15]	晋伊浩, 罗俊欣, 胡章茂, 王唯, 殷谦. 亲水改性硫酸镁/膨胀蛭石复合材料的吸附储热性能[J]. 化工学报, 2025, 76(4): 1852-1862.