不同粒径CAU-1/PI混合基质膜的构建与H2/CO2分离性能研究

doi:10.11949/0438-1157.20241208

摘要/Abstract

摘要：

基于金属有机骨架（MOFs）的混合基质膜兼具聚合物与MOFs材料的性能优势，是H₂/CO₂气体分离领域的研究热点。利用原位聚合法将不同粒径的CAU-1分散到聚酰亚胺（PI）基质材料中，采用XRD、SEM、TG、FTIR等手段对MOFs填料和混合基质膜进行表征，探究粒径大小和热处理温度对CAU-1/PI混合基质膜的H₂/CO₂分离性能的影响。结果表明，相较于纯聚合物膜，混合基质膜的分离效果有明显改善，原位聚合法能够显著提高MOF与聚合物的界面相容性，CAU-1粒径和热处理温度优化后的PI/CAU-1膜的H₂/CO₂分离因子可达8.4。

关键词: 混合基质膜, 金属有机骨架, 粒径, 气体分离

Abstract:

Mixed matrix membranes based on metal organic frameworks (MOFs) have the performance advantages of both polymers and MOFs materials, and are research hotspot in the field of H₂/CO₂ gas separation. In this paper, CAU-1 with different particle sizes was dispersed into polyimide (PI) substrate by in-situ polymerization, and MOFs fillers and mixed matrix films were characterized by XRD, SEM, TG, FTIR, etc., to explore the effects of particle size and heat treatment temperature on H₂/CO₂ separation performance. The results showed that, compared with the pure polymer membrane, the separation effect of mixed matrix membrane was significantly improved. In-situ polymerization could significantly improve the interfacial compatibility of MOF and polymer, and the separation factor of H₂/CO₂ of PI/CAU-1 membrane after optimization of CAU-1 particle size and heat treatment temperature could reach 8.4.

Key words: mixed matrix membrane, metal-organic frameworks (MOFs), particle size, gas separation

中图分类号:

TQ 028.8

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.

Dong GU, Xingjian PI, Die ZHANG, Ying ZHANG. Construction and H₂/CO₂ separation performance evaluation of CAU-1/PI mixed matrix membrane with different nanoparticle sizes[J]. CIESC Journal, 2025, 76(5): 2410-2418.

图/表 11

图1 两步法合成PMDA-ODA聚酰亚胺流程

Fig.1 Flow chart of two-step synthesis of PMDA-ODA polyimide

表1 纯PI膜和不同粒径CAU-1混合基质膜的合成方案

Table 1 Synthesis scheme of pure PI membrane and CAU-1 mixed matrix membrane with different particle sizes

Membrane	CAU-1	PI/g	亚酰胺化温度/℃
M0	—	0.40	150
M1	—	0.40	180
M-30-150	CAU-1-30，0.04 g	0.36	150
M-30-180	CAU-1-30，0.04 g	0.36	180
M-40-180	CAU-1-40，0.04 g	0.36	180
M-50-180	CAU-1-50，0.04 g	0.36	180
M-60-180	CAU-1-60，0.04 g	0.36	180

图2 膜气体分离性能测试装置

Fig.2 Equipment for testing membrane gas separation performance

图3 不同粒径CAU-1的X射线衍射图与SEM图

Fig.3 X-Ray diffraction patterns and SEM images of CAU-1 with different particle sizes

图4 CAU-1-50的N2吸脱附等温线

Fig.4 N2 adsorption and desorption isotherm of CAU-1-50

图5 纯PI膜和不同粒径CAU-1混合基质膜的X射线衍射、TGA与FTIR曲线

Fig.5 XRD patterns, TGA curves and FTIR spectra of pure PI membranes and CAU-1 mixed matrix membranes with different particle sizes

图6 纯PI膜和不同粒径CAU-1混合基质膜的表面SEM图（2 μm）

Fig.6 Surface SEM images of pure PI membranes and CAU-1 mixed matrix membranes with different particle sizes（2 μm）

图7 纯PI膜和不同粒径CAU-1混合基质膜的截面SEM图（10 μm）

Fig.7 Cross-sectional SEM images of pure PI membranes and CAU-1 mixed matrix membranes with different particle sizes（10 μm）

图8 （a）纯PI膜和混合基质膜的H2、CO2渗透性以及H2/CO2选择性；（b）M-40-180膜在25℃和1.5×105 Pa条件下的性能稳定性

Fig.8 （a）H2 and CO2 permeability and H2/CO2 selectivity of pure PI and mixed matrix membranes；（b） Evaluation of the performance stability of M-40-180 at 25 ℃ and 1.5×105 Pa

图9 制备的MMMs与文献报道的MMMs的H2/CO2分离性能比较

Fig.9 Comparison of H2/CO2 separation performance of the as-prepared MMMs with other MMMs

表2 文献报道的MOF基混合基质膜的H2/CO2分离性能（常压）

Table 2 H2/CO2 separation performance of MOF-based mixed matrix membranes reported in the literature（atmospheric pressure）

基体	填料及含量/%(质量)	H₂渗透性/Barrer	H₂/CO₂选择性	温度T/℃	文献
Matrimid^®5218	Zeolite 4A, 10	28.2	2.2	30	[24]
PBI	ZIF-7, 50	26.2	14.9	35	[25]
	ZIF-8, 30	82.5	12.0	35	[26]
	ZIF-8, 60	1749.9	4.1	35	[27]
	ZIF-11, 39.5	464.7	3.6	25	[28]
	ZIF-90, 45	24.5	25	35	[29]
Matrimid^®	ZIF-8, 20	32	3.5	25	[30]
6FDA-durene	ZIF-8, 33.3	2136	1.4	35	[31]
Polyimides	ZSM-5	1268	1.3	35	[32]
Polyimides	Cu(BTC)₂, 3/6	—	18/27.8	25	[33]
PMMA	CAU-1, 15	11000	13	25	[22]
PES	SAPO-34, 20	12.57	2.45	30	[34]
M-40-180	CAU-1, 10	460.0	8.4	25	本文
M-50-180	CAU-1, 10	501.1	7.0	25	本文

参考文献 34

1	Sazali N. A review of the application of carbon-based membranes to hydrogen separation[J]. Journal of Materials Science, 2020, 55(25): 11052-11070.
2	Mao D L, Griffin J M, Dawson R, et al. Metal organic frameworks for hydrogen purification[J]. International Journal of Hydrogen Energy, 2021, 46(45): 23380-23405.
3	Sidney L, Sriniva S, Weaver D E. High flow porous membranes for separating water from saline solutions: US3133137A[P]. 1964-05-12.
4	Stern S A, Mullhaupt J T, Gareis P J. The effect of pressure on the permeation of gases and vapors through polyethylene. Usefulness of the corresponding states principle[J]. AIChE Journal, 1969, 15(1): 64-73.
5	Guo H, Liu J Q, Li Y H, et al. Post-synthetic modification of highly stable UiO-66-NH₂ membranes on porous ceramic tubes with enhanced H₂ separation[J]. Microporous and Mesoporous Materials, 2021, 313: 110823.
6	Li P Y, Wang Z, Qiao Z H, et al. Recent developments in membranes for efficient hydrogen purification[J]. Journal of Membrane Science, 2015, 495: 130-168.
7	Al-Rowaili F N, Khaled M, Jamal A, et al. Mixed matrix membranes for H₂/CO₂ gas separation—a critical review[J]. Fuel, 2023, 333: 126285.
8	Wang S F, Li X Q, Wu H, et al. Advances in high permeability polymer-based membrane materials for CO₂ separations[J]. Energy & Environmental Science, 2016, 9(6): 1863-1890.
9	Butler J A V. (1) Rational approach to chemical principles (2) the elements of physical chemistry (3) physical chemistry (4) physical chemistry[J]. Nature, 1948, 162: 125-126.
10	Chui S S Y, Lo S M F, Charmant J P H, et al. A chemically functionalizable nanoporous material [Cu₃[TMA]₂(H₂O)₃] _n [J]. Science, 1999, 283(5405): 1148-1150.
11	Millward A R, Yaghi O M. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature[J]. Journal of the American Chemical Society, 2005, 127(51): 17998-17999.
12	Britt D, Furukawa H, Wang B, et al. Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites[J]. Proceedings of the National Academy of Sciences of the United States of America, 2009, 106(49): 20637-20640.
13	Valenzano L, Civalleri B, Chavan S, et al. Computational and experimental studies on the adsorption of CO, N₂, and CO₂ on Mg-MOF-74[J]. The Journal of Physical Chemistry C, 2010, 114(25): 11185-11191.
14	Song Y Y, He M G, Zhao J, et al. Structural manipulation of ZIF-8-based membranes for high-efficiency molecular separation[J]. Separation and Purification Technology, 2021, 270: 118722.
15	Guan W X, Dai Y, Dong C Y, et al. Zeolite imidazolate framework (ZIF)-based mixed matrix membranes for CO₂ separation: a review[J]. Journal of Applied Polymer Science, 2020, 137(33): 48968.
16	Li Y S, Liang F Y, Bux H, et al. Zeolitic imidazolate framework ZIF-7 based molecular sieve membrane for hydrogen separation[J]. Journal of Membrane Science, 2010, 354(1/2): 48-54.
17	Kumar S, Jain S, Nehra M, et al. Green synthesis of metal-organic frameworks: a state-of-the-art review of potential environmental and medical applications[J]. Coordination Chemistry Reviews, 2020, 420: 213407.
18	Kandiah M, Nilsen M H, Usseglio S, et al. Synthesis and stability of tagged UiO-66 Zr-MOFs[J]. Chemistry of Materials, 2010, 22(24): 6632-6640.
19	Japip S, Liao K S, Chung T S. Molecularly tuned free volume of vapor cross-linked 6FDA-durene/ZIF-71 MMMs for H₂/CO₂ separation at 150℃[J]. Advanced Materials, 2017, 29(4): 1603833.
20	Klepić M, Setničková K, Lanč M, et al. Permeation and sorption properties of CO₂-selective blend membranes based on polyvinyl alcohol (PVA) and 1-ethyl-3-methylimidazolium dicyanamide ([EMIM] [DCA]) ionic liquid for effective CO₂/H₂ separation[J]. Journal of Membrane Science, 2020, 597: 117623.
21	Li Y S, Liang F Y, Bux H, et al. Molecular sieve membrane: supported metal-organic framework with high hydrogen selectivity[J]. Angewandte Chemie International Edition, 2010, 49(3): 548-551.
22	Cao L J, Tao K, Huang A S, et al. A highly permeable mixed matrix membrane containing CAU-1-NH₂ for H₂ and CO₂ separation[J]. Chemical Communications, 2013, 49(76): 8513-8515.
23	Jia Y, Liu P X, Liu Y B, et al. In-situ interfacial crosslinking of NH₂-MIL-53 and polyimide in MOF-incorporated mixed matrix membranes for efficient H₂ purification[J]. Fuel, 2023, 339:126938.
24	Ahmad J, Hägg M B. Development of matrimid/zeolite 4A mixed matrix membranes using low boiling point solvent[J]. Separation and Purification Technology, 2013, 115: 190-197.
25	Yang T X, Xiao Y C, Chung T S. Poly-/ metal-benzimidazole nano-composite membranes for hydrogen purification[J]. Energy & Environmental Science, 2011, 4(10): 4171-4180.
26	Yang T X, Chung T S. High performance ZIF-8/PBI nano-composite membranes for high temperature hydrogen separation consisting of carbon monoxide and water vapor[J]. International Journal of Hydrogen Energy, 2013, 38(1): 229-239.
27	Yang T X, Shi G M, Chung T S. Symmetric and asymmetric zeolitic imidazolate frameworks (ZIFs)/polybenzimidazole (PBI) nanocomposite membranes for hydrogen purification at high temperatures[J]. Advanced Energy Materials, 2012, 2(11): 1358-1367.
28	Li L X, Yao J F, Wang X J, et al. ZIF-11/Polybenzimidazole composite membrane with improved hydrogen separation performance[J]. Journal of Applied Polymer Science, 2014, 131(22): 41056.
29	Yang T X, Chung T S. Room-temperature synthesis of ZIF-90 nanocrystals and the derived nano-composite membranes for hydrogen separation[J]. Journal of Materials Chemistry A, 2013, 1(19): 6081-6090.
30	Ordoñez M J C, Balkus K J, Ferraris J P, et al. Molecular sieving realized with ZIF-8/Matrimid^® mixed-matrix membranes[J]. Journal of Membrane Science, 2010, 361(1/2): 28-37.
31	Wijenayake S N, Panapitiya N P, Versteeg S H, et al. Surface cross-linking of ZIF-8/polyimide mixed matrix membranes (MMMs) for gas separation[J]. Industrial & Engineering Chemistry Research, 2013, 52(21): 6991-7001.
32	Kanehashi S, Gu H, Shindo R, et al. Gas permeation and separation properties of polyimide/ZSM-5 zeolite composite membranes containing liquid sulfolane[J]. Journal of Applied Polymer Science, 2013, 128(6): 3814-3823.
33	Hu J, Cai H P, Ren H Q, et al. Mixed-matrix membrane hollow fibers of Cu₃(BTC)₂ MOF and polyimide for gas separation and adsorption[J]. Industrial & Engineering Chemistry Research, 2010, 49(24): 12605-12612.
34	Karatay E, Kalıpçılar H, Yılmaz L. Preparation and performance assessment of binary and ternary PES-SAPO 34-HMA based gas separation membranes[J]. Journal of Membrane Science, 2010, 364(1/2): 75-81.

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不同粒径CAU-1/PI混合基质膜的构建与H₂/CO₂分离性能研究

Construction and H₂/CO₂ separation performance evaluation of CAU-1/PI mixed matrix membrane with different nanoparticle sizes

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