金属有机骨架材料吸附SF6的研究进展及展望

doi:10.16085/j.issn.1000-6613.2024-1299

摘要/Abstract

摘要：

SF₆在超大规模集成电路和超高压电力设备等工业技术领域具有重要的应用。但SF₆也是最强效的温室气体之一，具有极长的大气寿命和超高的全球变暖潜能值，过度排放对全球变暖和环境恶化存在极高的威胁。因此，在“节能减排”和“双碳”政策的国家战略背景下，从低浓度的SF₆/N₂混合气体中高效率和低能耗地回收SF₆对半导体制造业的发展和环境保护具有重要的意义。在众多的SF₆/N₂混合气体分离技术中，基于多孔材料的吸附分离是一种节能环保的优选方案。本文介绍了当前对SF₆/N₂混合气体的分离方法，重点阐述了采用沸石、金属有机骨架（MOFs）和多孔有机聚合物（POCs）以及共价有机框架（COFs）等多孔吸附材料对SF₆的吸附分离。在这些吸附材料中，MOFs具有较高的SF₆吸附能力、吸附选择性和良好的可再生性能，但由于MOFs对SF₆的吸附量和选择性之间权衡性较差，高选择性和高吸附量不能同时存在，所以权衡性差是MOFs吸附SF₆气体的一个挑战。因此，本文着重综述了MOFs材料对SF₆/N₂分离的研究进展及如何解决权衡性问题。最后，对SF₆吸附分离领域发展面临的问题进行归纳总结，并对该领域未来的发展方向进行了展望。

关键词: 六氟化硫, 吸附分离, 多孔材料, 金属有机骨架, 权衡性

Abstract:

SF₆has important applications in industrial technology such as ultra-large-scale integrated circuits and ultra-high voltage power equipment. However, SF₆is also the most potent greenhouse gas with an extremely long atmospheric lifetime and an extremely high global warming potential. Excessive emissions would pose a high threat to global warming and environmental degradation. Therefore, under the national strategic background of "energy conservation and emission reduction" and "dual carbon" policy, achieving high-efficiency and low-energy separation and recovery of SF₆ from low-concentration SF₆/N₂mixed gas is of great significance to the development of semiconductor manufacturing industry and environmental protection. Among the numerous SF₆/N₂ mixed gas separation technologies, adsorption separation based on porous materials is an energy-saving and environmentally friendly preferred solution. This paper introduced the current separation methods of SF₆/N₂ mixed gas, focusing on the adsorption separation of SF₆ using porous adsorption materials such as zeolites, metal organic frameworks (MOFs), porous organic polymers (POCs) and covalent organic frameworks (COFs). Among these adsorption materials, MOFs had higher SF₆ adsorption capacity, adsorption selectivity and good regeneration performance. However, due to the poor tradeoff between adsorption capacity and selectivity of SF6 by MOFs and the fact that high selectivity and high adsorption capacity cannot exist simultaneously, it was believed that tradeoff was a challenge for the adsorption of SF6 gas by MOFs. Therefore, this paper focused on reviewing the research progress of MOFs materials for SF₆/N₂ separation. Finally, the development problems of SF₆ adsorption separation were summarized, and the future development direction of this field was prospected.

Key words: sulfur hexafluoride, adsorption separation, porous material, metal organic frameworks (MOFs), tradeoff

中图分类号:

TQ117

杨宇, 赵文波, 徐志勇. 金属有机骨架材料吸附SF₆的研究进展及展望[J]. 化工进展, 2025, 44(10): 5771-5788.

YANG Yu, ZHAO Wenbo, XU Zhiyong. Research progress and prospect of SF₆ adsorption by metal-organic frame materials[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5771-5788.

图/表 11

参考文献 107

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吸附气体	全球变暖潜能值	动力学直径/Å	标准熔点/℃	标准沸点/℃	极化率/cm³	四极矩/esu·cm²
SF₆	22800	5.13	-64	-50	6.54×10^-24	0
N₂	0	3.64	-198	-210	1.74×10^-24	1.52×10^-26
CO₂	1	3.30	-78	—	2.91×10^-24	4.30×10^-26

吸附气体	全球变暖潜能值	动力学直径/Å	标准熔点/℃	标准沸点/℃	极化率/cm³	四极矩/esu·cm²
SF₆	22800	5.13	-64	-50	6.54×10^-24	0
N₂	0	3.64	-198	-210	1.74×10^-24	1.52×10^-26
CO₂	1	3.30	-78	—	2.91×10^-24	4.30×10^-26

分离方法	工作原理	典型工况	SF₆回收率/%	所用材料/溶剂	优点	缺点	已工业化的技术	文献
低温蒸馏技术	SF₆和N₂之间的沸点差异	0.4MPa，-30℃	99.0	冷媒	可以达到较高的SF₆纯度（99.999%，体积分数）；通过热集成可以提高能源效率	投资和运营成本高，设备庞大，能耗高	由KEPCO开发的模型	[27]
低温冷冻技术	SF₆和N₂之间的熔点差异	-196℃	99.0	液氮	SF₆冻结后融化成液相，其他杂质可以通过过滤器去除	要将SF₆从气体转变为固体，需要采用非常特殊的低温	由ABB开发的模型由KEPCO开发的模型	[32]
膜分离技术	利用混合气体在通过膜时传递速率的不同	101325Pa或更高	90.0	聚合物膜、无机膜、混合基质膜	由于不涉及相变，具有较高的膜比表面积	进料中的杂质会降低分离效率	膜分离装置（Solvay Fluor and Derivate GmbH）	[31]
离子液体吸收技术	独特的阴阳离子与气体分子之间的相互作用	—	90.0	离子溶剂	高稳定性、溶解性能可调节、不易挥发、可再生	成本高、黏度高、制备工艺复杂	离子液体烟气脱硫	[37]
吸附分离技术	通过吸附剂与气体混合物各组分之间的相互作用力	101325Pa或更高	80.0~90.0	沸石分子筛、金属有机骨架、活性炭	使用高比表面积的吸附剂可以吸附大量的SF₆	SF₆吸附-解吸循环可能需要较高的吸附压力	沸石13X（Solvay Fluor and Derivate GmbH）	[40]

分离方法	工作原理	典型工况	SF₆回收率/%	所用材料/溶剂	优点	缺点	已工业化的技术	文献
低温蒸馏技术	SF₆和N₂之间的沸点差异	0.4MPa，-30℃	99.0	冷媒	可以达到较高的SF₆纯度（99.999%，体积分数）；通过热集成可以提高能源效率	投资和运营成本高，设备庞大，能耗高	由KEPCO开发的模型	[27]
低温冷冻技术	SF₆和N₂之间的熔点差异	-196℃	99.0	液氮	SF₆冻结后融化成液相，其他杂质可以通过过滤器去除	要将SF₆从气体转变为固体，需要采用非常特殊的低温	由ABB开发的模型由KEPCO开发的模型	[32]
膜分离技术	利用混合气体在通过膜时传递速率的不同	101325Pa或更高	90.0	聚合物膜、无机膜、混合基质膜	由于不涉及相变，具有较高的膜比表面积	进料中的杂质会降低分离效率	膜分离装置（Solvay Fluor and Derivate GmbH）	[31]
离子液体吸收技术	独特的阴阳离子与气体分子之间的相互作用	—	90.0	离子溶剂	高稳定性、溶解性能可调节、不易挥发、可再生	成本高、黏度高、制备工艺复杂	离子液体烟气脱硫	[37]
吸附分离技术	通过吸附剂与气体混合物各组分之间的相互作用力	101325Pa或更高	80.0~90.0	沸石分子筛、金属有机骨架、活性炭	使用高比表面积的吸附剂可以吸附大量的SF₆	SF₆吸附-解吸循环可能需要较高的吸附压力	沸石13X（Solvay Fluor and Derivate GmbH）	[40]

材料	BET比表面积/m²·g^-1	IAST选择性SF₆/N₂（10∶90）	SF₆吸附量（10kPa）/mmol·g^-1	SF₆吸附量(100kPa)/mmol·g^-1	Q_st/kJ·mol^-1	参考文献
Ni(adc)(dabco)_0.5	743.9	948.2	2.23	2.38	47.6	[79]
Ni(NDC)(TED)_0.5	1306.6	748	2.76	4.37	32.15	[80]
Cu-MOF-NH₂	2145	266	3.39	7.88	55.2	[71]
V-TCPB	1107	360.7	2.29	3.07	30.08	[92]
GA-TCPB	1144	418.5	2.26	2.95	30.44	[92]
Ni(ina)₂	470	375.1	2.39	2.84	33.4	[8]
SBMOF-1	150	325.0	0.93	1.02	32.5	[11]
Ni(3-mpba)₂	835.1	221	—	2.83	38.4	[74]
Ni(pba)₂	807.2	156.5	1.69	3.47	38.2	[74]
CAU-10-H	684.4	122.6	0.68	1.00	24.9	[73]
CAU-10-Py	935.9	203.6	1.13	1.76	32.6	[73]
HBU-21	381.44	184.05	1.34	—	24.52	[91]
MIL-101	—	70	—	2.23	—	[60]
DUT-9	—	70	—	2.32	—	[60]
Mg-MOF-74	1631	19	1.34	6.42	—	[67]
Co-MOF-74	1219	37	1.32	5.34	—	[67]
Zn-MOF-74	992	45	1.02	3.76	42.3	[67]
HKUST-1a	1090	37	0.86	3.46	57.4	[68]
HKUST-1b	1135	49	1.32	4.12	34.5	[68]
HKUST-1c	1328	70	1.50	4.98	30.2	[68]
CAU-17	530	31	—	1.61	27.6	[84]
SU-100	385	36	—	2.07	20.4	[85]
ZIF-7-8s	1624	40	—	2.08	—	[87]
UiO-66-Br₂	616	220	0.8	1.63	45	[69]
Zn(TMBDC)(DABCO)_0.5	975.9	239	2.48	4.61	46	[14]
UiO-66-Br₂@PS/DVB	59	—	—	0.18	—	[70]
YTU-29-NH₂	1269.5	36.7	—	4.26	28.9	[72]
Ni(3-min)(bdc)_0.5	628	91	—	2.25	31.3	[75]
GNU-3a	930.08	317.6	—	2.63	22.9	[81]
SNNU-204	2170	49	—	6	21.0	[82]
YTU-30	714.0	68	—	1.65	27	[83]
Sc-cage-MOF	580	22.7	—	1.59	30.7	[86]
UU-200	115	44.81	—	1.19	—	[93]
BUT-53	866	2485	—	3.62	23.8	[94]

金属有机骨架材料吸附SF₆的研究进展及展望

Research progress and prospect of SF₆ adsorption by metal-organic frame materials

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