金属-有机框架材料在石化环保领域的应用

doi:10.16085/j.issn.1000-6613.2019-0890

摘要/Abstract

摘要：

石油化工是我国的支柱产业，也是环境污染的主要来源。近年来，随着国家环保形势的日益严峻和相应环保法规的陆续出台，高效处理石化行业所涉及的各类污染问题已成为重中之重。作为一种新型的纳米多孔材料，金属-有机框架（MOF）在石化环保领域展现出了广阔的应用前景。该材料可作为高性能吸附剂、分离膜以及催化材料去除或降解石化行业中的典型污染物。本文系统梳理了MOF材料及其相关工艺在石化环保领域的潜在应用，重点介绍了近年来国内外取得的突破性进展，并在此基础上深入分析了该材料的应用现状、存在问题及未来的研发方向。总体而言，MOF材料具有比传统多孔材料更优异的结构特征和应用性能；展望未来，其能够作为吸附剂、分离膜或是催化材料在石化环保领域得到更大规模的推广与应用。

关键词: 金属-有机框架, 石化环保, 吸附, 膜分离, 催化氧化

Abstract:

Petrochemical industry is one of the core industries in China, whilst it is also a main source of environmental pollutions. Since the nation’s environmental situations become severer together with the fact that more and more environmental regulations have been installed, the effective remediation towards the typical petrochemical-related contaminations is now a priority topic. As a recently-developed class of material, metal-organic frameworks(MOF) have exhibited promising application potentials for environmental remediation in petrochemical industries. The materials could work as effective adsorbents, functional membranes as well as catalytic candidates to remove/separate/degrade petrochemical pollutants. This article reviews the relevant applications in this field, analyzes the most significant work, and finally discusses the future perspectives for the further development of MOF materials. Overall, MOF materials have exhibited better structural features and application performance. It shall work favorably as adsorbents, membranes and catalysts in the environmental areas of petrochemical industries in the future.

Key words: MOF, environmental remediation, petrochemical industry, adsorption, membrane, AOP

中图分类号:

TE99

王成鸿,孟凡宁,魏昕,曹田田,栾金义. 金属-有机框架材料在石化环保领域的应用[J]. 化工进展, 2020, 39(2): 429-438.

Chenghong WANG,Fanning MENG,Xin WEI,Tiantian CAO,Jinyi LUAN. Environmental applications of metal-organic frameworks in petrochemical industries[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 429-438.

图/表 4

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应用领域	具体应用
吸附分离	气体储存，碳捕获，废水处理，燃油净化，萃取吸附剂，色谱固定相等
催化反应	氢化反应，光催化反应，烃类、醇类氧化反应，酯化反应，水解反应等
生物医学	药物负载，药物缓释等
传感	电化学传感器，荧光化学传感器等
电学	电池，超级电容器等

应用领域	具体应用
吸附分离	气体储存，碳捕获，废水处理，燃油净化，萃取吸附剂，色谱固定相等
催化反应	氢化反应，光催化反应，烃类、醇类氧化反应，酯化反应，水解反应等
生物医学	药物负载，药物缓释等
传感	电化学传感器，荧光化学传感器等
电学	电池，超级电容器等

吸附材料	吸附应用	吸附容量/mmol·g^-1	参考文献
MOF-177	CO₂吸附	33.5	[24]
[Cu₂₄(TPBTM^6-)₈(H₂O)₂₄]·xG	CO₂吸附	23.5	[25]
PCN-61	CO₂吸附	21.4	[25]
bio-MOF-11	CO₂吸附	6.0	[26]
1-Eu	CO₂吸附	166.3cm³·g^-1	[27]
MIL-101	VOC（正己烷、甲苯、甲醇、丁酮、二氯甲烷和正丁胺）吸附	12.8（正丁胺）	[28]
UiO-66-NH₂	VOC（甲苯）吸附	2.7	[29]
BUT-66	VOC（苯等芳香性气体）吸附	1.65	[30]
[Zn₄(μ₄-O)(μ₄-4-carboxy-3,5-dimethyl-4-carboxy-pyrazolato)₃]	沙林毒气和芥子气等剧毒气体吸附	—	[31]
沸石13X	CO₂吸附	7.24	[24]
活性炭	VOC（正己烷、甲苯、甲醇、丁酮、二氯甲烷和正丁胺）吸附	0.17（正丁胺）	[28]

吸附材料	吸附应用	吸附容量/mmol·g^-1	参考文献
MOF-177	CO₂吸附	33.5	[24]
[Cu₂₄(TPBTM^6-)₈(H₂O)₂₄]·xG	CO₂吸附	23.5	[25]
PCN-61	CO₂吸附	21.4	[25]
bio-MOF-11	CO₂吸附	6.0	[26]
1-Eu	CO₂吸附	166.3cm³·g^-1	[27]
MIL-101	VOC（正己烷、甲苯、甲醇、丁酮、二氯甲烷和正丁胺）吸附	12.8（正丁胺）	[28]
UiO-66-NH₂	VOC（甲苯）吸附	2.7	[29]
BUT-66	VOC（苯等芳香性气体）吸附	1.65	[30]
[Zn₄(μ₄-O)(μ₄-4-carboxy-3,5-dimethyl-4-carboxy-pyrazolato)₃]	沙林毒气和芥子气等剧毒气体吸附	—	[31]
沸石13X	CO₂吸附	7.24	[24]
活性炭	VOC（正己烷、甲苯、甲醇、丁酮、二氯甲烷和正丁胺）吸附	0.17（正丁胺）	[28]

吸附材料	吸附应用	吸附容量	参考文献
MIL-101	苯吸附	16.7mmol·g^-1	[33]
MIL-101(Cr)	双酚A吸附	156mg·g^-1	[34]
ZIF-8	苯二甲酸吸附	654mg·g^-1	[35]
ZIF-67	苯三唑吸附	308mg·g^-1	[36]
UiO-67	草甘膦吸附	537mg·g^-1	[37]
MIL-53(Al)-NH₂	Pb²⁺吸附	492.4mg·g^-1	[38]
Zr-DMBD	Hg²⁺吸附	—	[39]
Fe-BTC	Pb²⁺、Fe²⁺吸附	394mgPb·g^-1,1634mgHg·g^-1	[40]
UiO-68	U吸附	217mg·g^-1	[41]
UiO-66	As吸附	303mg·g^-1	[42]
介孔氧化硅SBA-15	苯吸附	3.0mmol·g^-1	[33]
商用活性炭	苯二甲酸吸附	249mg·g^-1	[35]
商用活性炭	As吸附	30.5mg·g^-1	[42]