芳香烃/环烷烃吸附分离材料研究进展

doi:10.16085/j.issn.1000-6613.2023-0533

摘要/Abstract

摘要：

吸附法由于其节能环保的特性有潜力替代萃取精馏成为分离同碳数芳香烃/环烷烃的新方法，目前采用的吸附分离材料已从传统的沸石分子筛发展到包括金属-有机框架材料（MOFs）、共价有机框架（COFs）和多孔分子晶体（PMCs）在内的新型多孔材料，体现出优异的选择性、优先吸附芳香烃或环烷烃的能力。本文综述了近年来MOFs、COFs和PMCs在苯/环己烷和甲苯/甲基环己烷分离中的研究进展，重点介绍了三类材料结构的设计思路、吸附分离性能及其机理，包括热力学平衡、分子排阻等两类不同的机理。在取得较大研究进展的同时，该领域也存在一些较为突出的问题，如对吸附质扩散传质规律和混合物固定床分离性能研究不足、对材料稳定性和杂质敏感性关注较少、多孔材料结构复杂、经济性有待提升等，在未来的研究中需予以重视。

关键词: 多孔材料, 金属-有机框架材料, 吸附分离, 芳香烃, 环烷烃

Abstract:

Due to its energy efficiency and environmental friendliness, adsorption has the potential to replace extractive distillation as a new method for the separation of aromatics/cycloalkanes with the same amount of carbon atoms. The materials used for adsorption separation have evolved from the traditional molecular sieves to new porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and porous molecular crystals (PMCs), which show preferential adsorption of aromatics or cycloalkanes and excellent selectivity. This review investigated the recent progress of MOFs, COFs and PMCs for the separation of benzene/cyclohexane and toluene/methylcyclohexane, focusing on the ideas of structural design, the adsorption and separation performance and mechanisms of the three types of materials. These mechanisms included two different types of mechanisms such as thermodynamic equilibrium and molecular exclusion. Though remarkable progress had been made, some prominent issues still existed in this field. The laws of diffusion and mass transfer of adsorbent as well as the separation performance of materials loaded in fixed bed for mixtures were inadequately researched, the stability and impurity sensitivity of materials were not caught enough attention, the structures of porous materials were overly complex, and the costs of materials needed to be reduced. All of them needed to be taken into account in future research.

Key words: porous materials, metal-organic frameworks, adsorptive separation, aromatics, cycloalkanes

中图分类号:

金彬浩, 朱小倩, 柯天, 张治国, 鲍宗必, 任其龙, 苏宝根, 杨启炜. 芳香烃/环烷烃吸附分离材料研究进展[J]. 化工进展, 2024, 43(4): 1863-1881.

JIN Binhao, ZHU Xiaoqian, KE Tian, ZHANG Zhiguo, BAO Zongbi, REN Qilong, SU Baogen, YANG Qiwei. Advances in adsorbents for aromatics/cycloalkanes separation[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1863-1881.

图/表 22

参考文献 81

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名称	分子结构	分子尺寸/Å			动力学直径/Å	沸点/K	极化率/10^-24cm³
名称	分子结构	X	Y	Z	动力学直径/Å	沸点/K	极化率/10^-24cm³
苯		7.3	6.6	3.3	5.35~5.85	353.3	10.0~10.7
环己烷		7.2	6.6	5.0	6.0	353.9	10.8~11.7
甲苯		8.3	6.6	4.0	5.25	383	12.32
甲基环己烷		8.3	6.6	5.1	6.49	374	12.83

名称	分子结构	分子尺寸/Å			动力学直径/Å	沸点/K	极化率/10^-24cm³
名称	分子结构	X	Y	Z	动力学直径/Å	沸点/K	极化率/10^-24cm³
苯		7.3	6.6	3.3	5.35~5.85	353.3	10.0~10.7
环己烷		7.2	6.6	5.0	6.0	353.9	10.8~11.7
甲苯		8.3	6.6	4.0	5.25	383	12.32
甲基环己烷		8.3	6.6	5.1	6.49	374	12.83

吸附剂		优先吸附芳香烃
吸附剂		温度/K		静态吸附容量/mmol·g^-1		静态吸附组分压力/kPa		吸附分离机理
Cu₂I₂(BTTP₄)^[54]		—		Bz(2.60), Cy(1.43)		p₀^①		热力学
Ni₃(OH)(Ina)₃(BDC)_1.5^[55]		298		Bz(3.83), Cy(0.17)		p₀^①		热力学
ZnL^[56]		298		Bz(1.47), Cy(0.45)		p₀^①		热力学
DAT-MOF-1^[57]		298		Bz(1.50), Cy(0.20)		100		热力学
Mn-MOF-74^[61]		298		Bz(9.38), Cy(0.25)		12.5		热力学
MAF-24β^[65]		298		Bz(2.57), Cy(0.20)		p₀^①		刚性排阻
MAF-stu-13^[66]		298		Bz(2.59), Cy(0.21)		p₀^①		刚性排阻
Li₂Zn₂(NO₂-bdc)₃(bpy)^[67]		293		Bz(2.90), Cy(0.18)		p₀^①		刚性排阻
Zn(μ₄-TCNQ-TCNQ)bpy^[68]		298		Bz(3.57), Cy(0.89)		p₀^①		柔性排阻
CID-23^[69]		298		Bz(1.20), Cy(0.09)		10		柔性排阻
Cu(bpp)₂(BF₄)₂^[70]		283		Bz(3.18), Cy(trace)^②		p₀^①		柔性排阻
CTF-IP10^[73]		298		Bz(12.43), Cy(trace)^②		p₀^①		热力学
TBICOF^[74]		298		Bz(28.66), Cy(8.31)		p₀^①		热力学
CMP-S-1^[75]		298		Bz(8.30), Cy(4.50)		p₀^①		热力学
杂化[3]芳烃^[78]		298		Bz(1.30), Cy(trace)^②		p₀^①		热力学
TAPM-1^[38]		298		Bz(3.71), Cy(0.17), TOL(2.28), MCH(0.31)		12		热力学
[2]Cage^③[81]		—		—		—		热力学
EtP5α^[79]		298		TOL:MCH = 98.8:1.2(liquid)^④		P₀^①		柔性排阻
吸附剂	优先吸附环烷烃
吸附剂	温度/K		模拟穿透时间/min·g^-1		模拟穿透条件（分压，载气流速）		等摩尔混合气（液）吸附比		吸附分离机理
MUF-77^[62]	293		苯(100),环己烷(180)		0.5kPa, 100mL_N/min		—		热力学
CUB-30^[62]	293		苯(30),环己烷(400)		0.5kPa, 100mL_N/min		—		热力学
[Zn₁₂(tdc)₆(glycolate)₆(dabco)₃] (glycolate = 1,2-戊二醇)^[64]	—		—		—		Bz∶Cy = 0.2∶1(气) Bz∶Cy = 0.4∶1(液)		热力学
EtP6β^[79]	298						TOL∶MCH = 0.8∶99.2(液)		柔性排阻
1α^[80]	298		—		—		Bz∶Cy = 0.17∶0.83(气) TOL∶MCH = 0.14∶0.86(气)		热力学

吸附剂		优先吸附芳香烃
吸附剂		温度/K		静态吸附容量/mmol·g^-1		静态吸附组分压力/kPa		吸附分离机理
Cu₂I₂(BTTP₄)^[54]		—		Bz(2.60), Cy(1.43)		p₀^①		热力学
Ni₃(OH)(Ina)₃(BDC)_1.5^[55]		298		Bz(3.83), Cy(0.17)		p₀^①		热力学
ZnL^[56]		298		Bz(1.47), Cy(0.45)		p₀^①		热力学
DAT-MOF-1^[57]		298		Bz(1.50), Cy(0.20)		100		热力学
Mn-MOF-74^[61]		298		Bz(9.38), Cy(0.25)		12.5		热力学
MAF-24β^[65]		298		Bz(2.57), Cy(0.20)		p₀^①		刚性排阻
MAF-stu-13^[66]		298		Bz(2.59), Cy(0.21)		p₀^①		刚性排阻
Li₂Zn₂(NO₂-bdc)₃(bpy)^[67]		293		Bz(2.90), Cy(0.18)		p₀^①		刚性排阻
Zn(μ₄-TCNQ-TCNQ)bpy^[68]		298		Bz(3.57), Cy(0.89)		p₀^①		柔性排阻
CID-23^[69]		298		Bz(1.20), Cy(0.09)		10		柔性排阻
Cu(bpp)₂(BF₄)₂^[70]		283		Bz(3.18), Cy(trace)^②		p₀^①		柔性排阻
CTF-IP10^[73]		298		Bz(12.43), Cy(trace)^②		p₀^①		热力学
TBICOF^[74]		298		Bz(28.66), Cy(8.31)		p₀^①		热力学
CMP-S-1^[75]		298		Bz(8.30), Cy(4.50)		p₀^①		热力学
杂化[3]芳烃^[78]		298		Bz(1.30), Cy(trace)^②		p₀^①		热力学
TAPM-1^[38]		298		Bz(3.71), Cy(0.17), TOL(2.28), MCH(0.31)		12		热力学
[2]Cage^③[81]		—		—		—		热力学
EtP5α^[79]		298		TOL:MCH = 98.8:1.2(liquid)^④		P₀^①		柔性排阻
吸附剂	优先吸附环烷烃
吸附剂	温度/K		模拟穿透时间/min·g^-1		模拟穿透条件（分压，载气流速）		等摩尔混合气（液）吸附比		吸附分离机理
MUF-77^[62]	293		苯(100),环己烷(180)		0.5kPa, 100mL_N/min		—		热力学
CUB-30^[62]	293		苯(30),环己烷(400)		0.5kPa, 100mL_N/min		—		热力学
[Zn₁₂(tdc)₆(glycolate)₆(dabco)₃] (glycolate = 1,2-戊二醇)^[64]	—		—		—		Bz∶Cy = 0.2∶1(气) Bz∶Cy = 0.4∶1(液)		热力学
EtP6β^[79]	298						TOL∶MCH = 0.8∶99.2(液)		柔性排阻
1α^[80]	298		—		—		Bz∶Cy = 0.17∶0.83(气) TOL∶MCH = 0.14∶0.86(气)		热力学

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