复合膜在CO2分离领域的研究进展

doi:10.3969/j.issn.1674-1951.2021.11.014

摘要/Abstract

摘要：

为实现“双碳”目标,应积极发展CO₂捕集、封存与资源化利用（CCUS）技术,控制CO₂的排放。膜分离技术作为最常见的气体分离技术之一,相比于吸收法、吸附法、低温法等,具有能耗低、便于操作、占地面积小、易于放大、运行成本低等优点,被广泛用于燃煤电厂烟气CO₂捕集与天然气脱碳纯化等工艺。然而纯无机膜与高分子膜受制于各自的缺点,无法大规模推广应用,开发气体分离性能优越的复合膜成为研究的热点。综述了国内外关于复合膜在CO₂捕集领域的研究进展,以膜结构类型进行分类,重点介绍了混合基质膜、支撑液膜等不同复合膜的制备过程及原理。对比了不同复合膜的分离表现,对其优缺点进行了总结,并对制约复合膜发展的关键问题进行了分析讨论。最后,展望了复合膜气体分离技术未来的发展方向。

关键词: 碳中和, CO₂捕集、封存与利用, 膜分离, 混合基质膜, 支撑膜, 离子液体, 碳酸酐酶

Abstract:

In order to achieve carbon peak and carbon neutrality, it is necessary to develop CO₂ capture, storage and resource utilization （CCUS） technology to control CO₂ emissions. As one of the most common gas separation technologies, membrane-based separation has been widely used in the CO₂ capture of flue gas from power plants and the purification of natural gas. It has the advantages of low energy consumption, easy operation, small site area, easy expansion and low operating costs,compared to absorption, adsorption and cryogenic methods. However, pure inorganic membranes and polymer membranes can hardly be used in large-scale applications for their own shortcomings. The development of composite membranes with superior gas separation performance has become the hotspot.The research progress of composite membranes on CO₂ capture was reviewed. Being sorted by their structures,composite membranes include mixed-matrix membranes and supported liquid membranes. The separation performances of different composite membranes were compared. Based on their advantages and disadvantages,the key issues restricting the development of composite membranes were analyzed and discussed. Finally, the development direction of composite membrane-based gas separation technology was also prospected.

Key words: carbon neutrality, CCUS, membrane-based separation, mixed-matrix membrane, supported liquid membrane, ionic liquid, carbonic anhydrase

中图分类号:

X701.7

连少翰, 李润, 张泽洲, 刘庆岭, 韩瑞, 赵军, 宋春风. 复合膜在CO₂分离领域的研究进展[J]. 华电技术, 2021, 43(11): 128-137.

LIAN Shaohan, LI Run, ZHANG Zezhou, LIU Qingling, HAN Rui, ZHAO Jun, SONG Chunfeng. Advances of composite membranes in CO₂ separation[J]. Huadian Technology, 2021, 43(11): 128-137.

图/表 5

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填料/聚合物基质	CO₂的渗透性/Barrer	CO₂/N₂ 选择性	参考文献
GO/HCM	474	56.0	[12]
ZIF-8/Pebax	100	60.0	[13]
ZIF-67/Pebax	162	81.0	[14]
MIL-101/Pebax	71	47.0	[15]
MIL-53/Pebax	129	58.0	[16]
OH-ZIF/Pebax	273	38.0	[17]
NH₂-MIL-101/Pebax	74	43.0	[15]
NH₂-MIL-53/CA	53	23.0	[18]
NH₂-MIL-53/Pebax	149	55.0	[16]
COF-5/Pebax	493	49.0	[19]
SNW-1/PIM-1	7 954	20.0	[20]

填料/聚合物基质	CO₂的渗透性/ Barrer	CO₂/N₂ 选择性	参考文献
Glycerol/Pebax	50	233.0	[46]
[BMIM][CF₃SO₃] /Pebax	300	40.0	[41]
[Bmim][BF₄]/Nexar	200	130.0	[40]
Poly([Pyr11][C(CN)3]/[C2mim][C(CN)3]	439	64.0	[38]
Poly([Pyr11][C(CN)3]/[C2mim][B(CN)4]	472	54.0	[39]
mPEG/Nafion	446	31.0	[45]

成分	CO₂的渗透性/Barrer	CO₂/N₂ 选择性	CO₂/CH₄ 选择性	参考文献
Pebax/ILs/NiZnFe₄O₄	300	248.0	—	[56]
Pebax/Glycerol/Cu	64	200.0	—	[46]
Matrimid/PEG 200/ZSM-5	11	—	60.0	[59]
Pebax/[Hmim][NTf]/LDHN	644	—	34.0	[55]
PES/[EMIM][NTf₂]/h-BN	747 252	—	1.8	[54]
PES/[EMIM][NTf₂]/MoS₂	153 112	—	1.4	[54]

成分	CO₂的渗透性/Barrer	CO₂/N₂ 选择性	参考文献
[Benz][Ac]/PI	19	40.0	[67]
[BMIM][AC]/PVDF	520	22.0	[66]
[EtDBN][B(CN)4]/PES	1 583	48.0	[64]
SspCA/[C4mim][Tf2N]/PVDF	734	36.0	[75]

成分	CO₂的渗透性/GPU	CO₂/N₂ 选择性	参考文献
Mico/[BMIM][BF₄]	80	87.0	[72]
GO/[BMIM][BF₄]	68	382.0	[71]
WS₂/[BMIM][BF₄]	47	153.0	[70]
MoS₂/[BMIM][BF₄]	47	131.0	[69]
uGO/[EMIM][Ac]	37	130.0	[74]

复合膜在CO₂分离领域的研究进展

Advances of composite membranes in CO₂ separation

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