MOF材料在芳烃同分异构体分离中的研究进展

doi:10.16085/j.issn.1000-6613.2024-1127

摘要/Abstract

摘要：

芳烃同分异构体因其具有相似的分子结构和物化性质，在工业分离中面临着较大挑战。金属有机框架（MOF）材料具有高比表面积、高度可调性及结构可控性等特性，在芳烃同分异构体吸附分离领域中展现出巨大的应用潜力。本文介绍了芳烃吸附分离应用中研究较多的几个典型MOF结构，探讨了芳烃同分异构体分离机制。从C₈芳烃同分异构体及其他关键芳烃异构体的角度出发，介绍了不同系列和不同分离机制的MOF材料，系统回顾了MOF材料的吸附特性、吸附机制及其在分离过程中的应用。针对MOF材料在芳烃异构体吸附分离领域的应用问题，比较了MOF膜分离芳烃异构体的效率，剖析了分子模拟优化材料吸附性能的案例。最后，总结了MOF材料在吸附分离芳烃同分异构体应用中存在的问题，并对MOF材料的创新与吸附性能的提升所面临的挑战进行了展望。

关键词: 芳烃同分异构体, 金属有机框架, 吸附, 分离, 分子模拟

Abstract:

Industrial separation of aromatic isomers is challenging due to their similar molecular structure and physicochemical properties. Metal-organic framework (MOF) materials, bearing high specific surface area, high adjustability and structural controllability, have shown great application potential in the field of adsorption and separation of aromatic isomers. This review introduced several typical MOF structures that had been extensively studied in the adsorption of aromatic isomers and explored the corresponding separation mechanism. From the viewpoint of C₈ aromatic isomers and other key aromatic isomers, MOF materials which had different series and separation mechanisms were introduced, and the adsorption characteristics, adsorption mechanisms and applications of MOF materials in the separation process were systematically reviewed. To address the application of MOF materials in adsorption and separation of aromatic isomers, the separation efficiency of aromatic isomers by MOF membrane were compared and the case of optimizing the adsorption performance of materials by molecular simulation were analyzed. Finally, the problems existing in the application of MOF materials in adsorption separation of aromatic isomers were summarized, and the challenges faced by MOF materials in innovation and improvement of adsorption performance were prospected.

Key words: aromatic isomers, metal organic framework, adsorption, separation, molecular simulation

中图分类号:

O6-1

符红梅, 刘定华, 刘晓勤. MOF材料在芳烃同分异构体分离中的研究进展[J]. 化工进展, 2025, 44(9): 5006-5017.

FU Hongmei, LIU Dinghua, LIU Xiaoqin. Research progress on the separation of aromatic isomers using MOF materials[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5006-5017.

图/表 9

参考文献 61

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二甲苯异构体	沸点/℃	熔点/℃	动力学直径/nm	偶极矩/×10¹⁸esu·cm	极性/×10²⁵cm^-3
邻二甲苯	144.44	-25.2	0.68	0.64	141~149
间二甲苯	139.19	-47.9	0.68	0.37	142
对二甲苯	138.38	13.2	0.58	0.10	137~149
乙苯	136.19	-95.0	0.58	0.59	142

二甲苯异构体	沸点/℃	熔点/℃	动力学直径/nm	偶极矩/×10¹⁸esu·cm	极性/×10²⁵cm^-3
邻二甲苯	144.44	-25.2	0.68	0.64	141~149
间二甲苯	139.19	-47.9	0.68	0.37	142
对二甲苯	138.38	13.2	0.58	0.10	137~149
乙苯	136.19	-95.0	0.58	0.59	142

材料	比表面积/m²·g^-1	孔径/Å	选择性			温度/K	PX吸附量/mmol·g^-1	文献
材料	比表面积/m²·g^-1	孔径/Å	PX/MX	PX/OX	PX/EB	温度/K	PX吸附量/mmol·g^-1	文献
NH₂-MIL-125(Ti)	1305	5~7	3.0	2.2	1.6	298	1.20	[25]
Co(aip)(bpy)_0.5	—	—	30.0	16.0	—	298	1.47	[44]
Mn(dhbq)(H₂O)₂	470	5.6	66.8	25.5	—	393	1.33	[30]
MIL-101(Cr)	3990	6	—	—	—	313	12.31	[51]
DUT-8(Cu)	2685	9.3	5.4	7.2	5.9	298	1.80	[43]
Zn-ETTOB	2594.9	7	3.9	6.2	1.2	298	8.00	[48]
MIL-47(V)	750	—	1/1.2	1/1.1	1	368	3.68	[54]
MIL-125	1560	6	1.08	1.03	0.76	298	4.65	[29]
ZIF-8	—	3.4~6	3.9	1.6	—	398	1.50	[38]
MX偏好			MX/PX	MX/OX	OX/PX		MX
ZU-61	1384	7.8	2.9	—	—	333	3.37	[28]
OX偏好			OX/PX	OX/MX	OX/EB		OX
MIL-53(Al)	1706	—	5.2	5.1	8.2	323	3.10	[32]
Co₂(dobdc)	1410	8	3.9	2.5	1.2	423	3.50	[47]
ZUL-C3	1200	6.2	20.06	7.92	7.51	303	3.41	[55]
UiO-66	885	5~7	2.4	1.8	—	313	—	[35]

材料	比表面积/m²·g^-1	孔径/Å	选择性			温度/K	PX吸附量/mmol·g^-1	文献
材料	比表面积/m²·g^-1	孔径/Å	PX/MX	PX/OX	PX/EB	温度/K	PX吸附量/mmol·g^-1	文献
NH₂-MIL-125(Ti)	1305	5~7	3.0	2.2	1.6	298	1.20	[25]
Co(aip)(bpy)_0.5	—	—	30.0	16.0	—	298	1.47	[44]
Mn(dhbq)(H₂O)₂	470	5.6	66.8	25.5	—	393	1.33	[30]
MIL-101(Cr)	3990	6	—	—	—	313	12.31	[51]
DUT-8(Cu)	2685	9.3	5.4	7.2	5.9	298	1.80	[43]
Zn-ETTOB	2594.9	7	3.9	6.2	1.2	298	8.00	[48]
MIL-47(V)	750	—	1/1.2	1/1.1	1	368	3.68	[54]
MIL-125	1560	6	1.08	1.03	0.76	298	4.65	[29]
ZIF-8	—	3.4~6	3.9	1.6	—	398	1.50	[38]
MX偏好			MX/PX	MX/OX	OX/PX		MX
ZU-61	1384	7.8	2.9	—	—	333	3.37	[28]
OX偏好			OX/PX	OX/MX	OX/EB		OX
MIL-53(Al)	1706	—	5.2	5.1	8.2	323	3.10	[32]
Co₂(dobdc)	1410	8	3.9	2.5	1.2	423	3.50	[47]
ZUL-C3	1200	6.2	20.06	7.92	7.51	303	3.41	[55]
UiO-66	885	5~7	2.4	1.8	—	313	—	[35]

混合物	在0.14mol/L时的吸收量/%	不同浓度时的选择性
混合物	在0.14mol/L时的吸收量/%	0.02mol/L	0.14mol/L	0.28mol/L
对乙基甲苯	10	1.9	1.8	1.6
间乙基甲苯	6	1.9	1.8	1.6
对二氯苯	24	1.5	5.1	—
间二氯苯	6	1.5	5.1	—
对甲苯胺	30	1.7	1.8	1.8
间甲苯胺	18	1.7	1.8	1.8
对甲酚	28	1.2	0.9	—
间甲酚	29	1.2	0.9	—