MOFs基膜材料的研究现状及其在H2/CH4分离中的应用

doi:10.16085/j.issn.1000-6613.2022-0404

化工进展 ›› 2022, Vol. 41 ›› Issue (12): 6395-6407.DOI: 10.16085/j.issn.1000-6613.2022-0404

MOFs基膜材料的研究现状及其在H₂/CH₄分离中的应用

高逸飞¹^,²(), 易群³, 齐凯¹^,²(), 高丽丽¹^,²(), 李雪莲¹^,²

^1.太原理工大学环境科学与工程学院，山西晋中 030600
^2.太原理工大学二氧化碳捕集封存利用研究中心，山西晋中 030600
^3.武汉工程大学化工与制药学院，湖北武汉 430074

收稿日期:2022-03-16 修回日期:2022-04-14 出版日期:2022-12-20 发布日期:2022-12-29
通讯作者: 齐凯,高丽丽
作者简介:高逸飞（1998—），男，硕士研究生，研究方向为气体分离纯化材料开发与设计。E-mail：1197182162@qq.com。
基金资助:
山西省基础研究计划青年基金(20210302124003)

Research status and application in H₂/CH₄ separation of MOFs-based membrane

GAO Yifei¹^,²(), YI Qun³, QI Kai¹^,²(), GAO Lili¹^,²(), LI Xuelian¹^,²

^1.Department of Environmental Science & Technology, Taiyuan University of Technology, Jinzhong 030600, Shanxi, China
^2.CO2 Capture, Utilization & Storage Research Center, Taiyuan University of Technology, Jinzhong 030600, Shanxi, China
^3.Department of Chemical Technology & Pharmaceutics, Wuhan Institute of Technology, Wuhan 430074, Hubei, China

Received:2022-03-16 Revised:2022-04-14 Online:2022-12-20 Published:2022-12-29
Contact: QI Kai, GAO Lili

摘要/Abstract

摘要：

氢气的生产、分离和储存已经成为世界绿色能源经济的重要组成部分。通过膜分离法从工业副产物中提纯氢气，不但操作简便，且显著降低了分离的能耗，是一种有前景的分离技术。金属有机框架（metal-organic frameworks，MOFs）因具有晶态、有序、明确的多孔结构和较大的比表面积，被认为是理想的气体分离膜材料。本文以MOFs基分离膜为研究对象，对比综述了MOFs膜的常规制备技术，总结了水热/溶剂热法、界面合成法、二次生长法和浇铸法的合成机理及应用。简述了在H₂/CH₄分离方面MOFs膜的设计原理及应用。针对MOFs膜当前存在的柔性、孔径、晶界结构、稳定性等问题，重点介绍了对制备方法与改良和对薄膜的后修饰策略，以期实现对MOFs膜性能的调控。最后，指出了目前该技术存在的难以大规模生产、分离性能不足的缺点，开发低成本的大规模生产方法同时提高薄膜的分离性能将会是未来MOFs膜实现工业应用的关键。

关键词: 金属有机框架, 膜材料, 膜分离, 气体分离, 氢气/甲烷分离

Abstract:

The production of hydrogen, its separation and storage for use is an important component of the green energy economy of the world. It is a promising separation technology to purify hydrogen from industrial by-products by membrane separation, which is not only easy to operate, but also significantly reduces the energy consumption of separation. Metal-organic frameworks (MOFs) materials possess crystal phase, ordered well-defined porous structure and large surface area, which are considered as an ideal membrane material for gas separation. Based on the literature, the recent progresses in conventional MOFs-based membrane preparation techniques of hydrothermal/solvothermal method, interfacial synthesis method, secondary growth method and casting method are reviewed, including the synthesis mechanism and application. Moreover, the design principle and application of MOFs membrane for H₂/CH₄ separation are also reviewed. Aiming at the problems of the flexibility, pore size, grain boundary structure and stability in order to realize the regulation of MOFs membrane’s performance, the improvement of preparation method and the post-modification strategy for MOFs membrane are introduced. By analyzing and comparing the key technologies, it is pointed that the challenges of MOFs membrane is difficult for large-scale production and the separation performance is insufficient. The effort to promote application of the MOFs membrane in the future is to develop large-scale and low-cost preparation methods and to improve MOFs membrane’s separation performance.

Key words: metal-organic frameworks (MOFs), membrane materials, membrane separation, gas separation, H₂/CH₄ separation

中图分类号:

高逸飞, 易群, 齐凯, 高丽丽, 李雪莲. MOFs基膜材料的研究现状及其在H₂/CH₄分离中的应用[J]. 化工进展, 2022, 41(12): 6395-6407.

GAO Yifei, YI Qun, QI Kai, GAO Lili, LI Xuelian. Research status and application in H₂/CH₄ separation of MOFs-based membrane[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6395-6407.

图/表 10

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分离材料	孔径/Å	设计原理	制备方法	分离条件/℃	H₂/CH₄选择性	H₂通量/mol·m^-2·s^-1·Pa^-1	参考文献
Cu₂(bza)₄(pyz)	2	尺寸差异	粉末MOF沉积法	RT	19*	6.88×10^-9	［63］
HKUST-1	9	极化率	晶种法	RT	5.9	1.0×10^-6	［64］
ZIF-7	3	尺寸差异	晶种法	20~200	5.9	8.0×10^-8	［25］
ZIF-8	3.4	尺寸差异	晶种法	RT	31.5	2.45×10^-8	［65］
ZIF-8	3.4	尺寸差异	晶种法	RT	4.0	4.80×10^-7	［66］
ZIF-8	3.4	尺寸差异	溶剂热法	RT	11.2	6.70×10^-8	［20］
ZIF-9	2.4	尺寸差异	非同源金属诱导	RT	7.6*/6.6	1.80×10^-7	［67］
ZIF-22	3	尺寸差异	溶剂热法	50	5.2	1.60×10^-7	［68］
ZIF-67	3.4	尺寸差异	非同源金属诱导	RT	45.4*/41.8	2.30×10^-7	［67］
ZIF-67	3.4	尺寸差异	非同源金属诱导	RT	6.6*	2.48×10^-7	［69］
ZIF-90	3.5	尺寸差异	晶种法	25~225	15.3	2.50×10^-7	［32］
UiO-66	6	尺寸差异	溶剂热法	RT	3.9*	6.11×10^-8	［70］

分离材料	孔径/Å	设计原理	制备方法	分离条件/℃	H₂/CH₄选择性	H₂通量/mol·m^-2·s^-1·Pa^-1	参考文献
Cu₂(bza)₄(pyz)	2	尺寸差异	粉末MOF沉积法	RT	19*	6.88×10^-9	［63］
HKUST-1	9	极化率	晶种法	RT	5.9	1.0×10^-6	［64］
ZIF-7	3	尺寸差异	晶种法	20~200	5.9	8.0×10^-8	［25］
ZIF-8	3.4	尺寸差异	晶种法	RT	31.5	2.45×10^-8	［65］
ZIF-8	3.4	尺寸差异	晶种法	RT	4.0	4.80×10^-7	［66］
ZIF-8	3.4	尺寸差异	溶剂热法	RT	11.2	6.70×10^-8	［20］
ZIF-9	2.4	尺寸差异	非同源金属诱导	RT	7.6*/6.6	1.80×10^-7	［67］
ZIF-22	3	尺寸差异	溶剂热法	50	5.2	1.60×10^-7	［68］
ZIF-67	3.4	尺寸差异	非同源金属诱导	RT	45.4*/41.8	2.30×10^-7	［67］
ZIF-67	3.4	尺寸差异	非同源金属诱导	RT	6.6*	2.48×10^-7	［69］
ZIF-90	3.5	尺寸差异	晶种法	25~225	15.3	2.50×10^-7	［32］
UiO-66	6	尺寸差异	溶剂热法	RT	3.9*	6.11×10^-8	［70］

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MOFs基膜材料的研究现状及其在H₂/CH₄分离中的应用

Research status and application in H₂/CH₄ separation of MOFs-based membrane

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