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

doi:10.11949/0438-1157.20241208

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 11

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

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

Fig.2 Equipment for testing membrane gas separation performance

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

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

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

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

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

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

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

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

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

不同粒径CAU-1/PI混合基质膜的构建与H₂/CO₂分离性能研究

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