功能化Zr-MOF强化混合基质膜CO2分离

doi:10.16085/j.issn.1000-6613.2022-0462

化工进展 ›› 2022, Vol. 41 ›› Issue (9): 4954-4962.DOI: 10.16085/j.issn.1000-6613.2022-0462

功能化Zr-MOF强化混合基质膜CO₂分离

方龙龙¹(), 郑文姬¹, 宁梦佳²^,³, 张明扬¹, 杨雨晴¹, 代岩²^,³(), 贺高红¹^,²()

^1.大连理工大学化工学院盘锦分院，辽宁盘锦 124221
^2.大连理工大学盘锦产业技术研究院，辽宁省化学助剂合成与分离重点实验室，辽宁盘锦 124221
^3.沈阳工业大学石油化工学院，辽宁辽阳 111003

收稿日期:2022-03-24 修回日期:2022-04-28 出版日期:2022-09-25 发布日期:2022-09-27
通讯作者: 代岩,贺高红
作者简介:方龙龙（1996—），男，硕士研究生，研究方向为气体分离膜。E-mail：fll@mail.dlut.edu.cn。
基金资助:
国家自然科学基金创新研究群体(22021005);辽宁省“兴辽英才”计划青年拔尖人才(XLYC2007040);辽宁省化学助剂与合成重点实验室开放课题(ZJKF2002);辽宁“百千万人才工程”培养经费项目

Enhanced CO₂ separation of mixed matrix membranes by functionalized Zr-MOF

FANG Longlong¹(), ZHENG Wenji¹, NING Mengjia²^,³, ZHANG Mingyang¹, YANG Yuqing¹, DAI Yan²^,³(), HE Gaohong¹^,²()

^1.School of Chemical Engineering at Panjin, Dalian University of Technology, Panjin 124221, Liaoning, China
^2.Panjin Institute of Industrial Technology, Liaoning Key Laboratory of Chemical Additive Synthesis and Separation, Dalian University of Technology, Panjin 124221, Liaoning, China
^3.School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, Liaoning, China

Received:2022-03-24 Revised:2022-04-28 Online:2022-09-25 Published:2022-09-27
Contact: DAI Yan, HE Gaohong

摘要/Abstract

摘要：

混合基质膜（MMMs）在气体分离领域具有良好的应用前景，金属有机框架（MOFs）由于具有高孔隙率和有机连接基团，常被用作填料制备MMMs。但由于MOFs与聚合物的界面相容性问题，MMMs的气体分离性能提升受到限制。本文合成了功能化的Zr-MOF（UiO-66-AC），并利用其与聚醚共聚酰胺（Pebax）共同制备了混合基质膜。填料中引入的羰基和羧基等基团提供了MOFs与聚合物基质之间较强的界面相互作用。与纯Pebax膜相比，UiO-66-AC/Pebax MMMs的气体渗透性能得到了显著提高。当填料质量分数为6%时，膜的CO₂渗透系数为102.4 Barrer，CO₂/N₂和CO₂/CH₄选择性分别为90.6和26.0，CO₂/N₂分离性能突破了Robeson上限(2008)，表明该混合基质膜在CO₂的分离应用上具有潜力。

关键词: 金属有机框架, 混合基质膜, CO₂捕集, 聚醚共聚酰胺

Abstract:

Mixed matrix membranes (MMMs) have promising applications in the field of gas separation, and metal-organic frameworks (MOFs) are often used as fillers to prepare MMMs due to their high porosity and organic linking groups. However, the improvement of gas separation performance of MMMs is limited due to the interfacial compatibility between MOFs and polymers. Herein, a functionalized Zr-MOF (UiO-66-AC) was synthesized to prepare mixed matrix membranes with poly(ether-b-amide) (Pebax). The introduction of groups such as carbonyl and carboxyl groups in the filler provided strong interfacial interactions between MOFs and the polymer matrix. Compared with pristine Pebax membranes, the gas permeability of UiO-66-AC/Pebax MMMs was significantly improved. When the filler content was 6%, the CO₂ permeability coefficient of the membrane was 102.4 Barrer, the CO₂/N₂ and CO₂/CH₄ selectivities were 90.6 and 26.0, respectively, and the CO₂/N₂ separation performance exceeded the Robeson upper bond (2008), indicating that the UiO-66-AC/Pebax MMMs had potential for CO₂ separation applications.

Key words: metal organic framework, mixed matrix membranes, CO₂ capture, Pebax

中图分类号:

TQ028.8

方龙龙, 郑文姬, 宁梦佳, 张明扬, 杨雨晴, 代岩, 贺高红. 功能化Zr-MOF强化混合基质膜CO₂分离[J]. 化工进展, 2022, 41(9): 4954-4962.

FANG Longlong, ZHENG Wenji, NING Mengjia, ZHANG Mingyang, YANG Yuqing, DAI Yan, HE Gaohong. Enhanced CO₂ separation of mixed matrix membranes by functionalized Zr-MOF[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4954-4962.

图/表 11

图1 UiO-66-AC的合成方案

图2 填料的表征

图3 UiO-66-NH2和UiO-66-AC混合基质膜的表面和横截面SEM图像

图4 UiO-66-NH2和UiO-66-AC混合基质膜的EDS映射图像

图5 UiO-66-NH2和UiO-66-AC混合基质膜的FTIR表征

图6 UiO-66-NH2和UiO-66-AC混合基质膜的XRD表征

图7 Pebax/UiO-66-NH2和Pebax/UiO-66-AC膜的DSC表征

图8 填料含量对混合基质膜的CO2渗透性和选择性的影响

图9 进料压力对UiO-66-NH2和UiO-66-AC混合基质膜气体渗透性的影响

图10 Robeson上限图及长期稳定性测试

表1 所报道的Pebax基混合基质膜的气体分离性能与本研究的对比

膜（Pebax基）	$p C O 2$ /Barrer	CO₂/N₂选择性	压力/bar	参考文献
GO	108	48.5	7	［38］
MWNTs-NH₂	298	52	7	［39］
ZnO@ZIF-8HNTs	140	67	7	［40］
NH₂-MIL-53（Al）	149	55.5	10	［41］
ZIF-8@GO	136.2	77.9	3	［42］
原始Pebax	89.5	81.3	8	本工作
UiO-66-NH₂-6%	91.0	86.2	8	本工作
UiO-66-AC-6%	102.4	90.6	8	本工作

表1 所报道的Pebax基混合基质膜的气体分离性能与本研究的对比

膜（Pebax基）	$p C O 2$ /Barrer	CO₂/N₂选择性	压力/bar	参考文献
GO	108	48.5	7	［38］
MWNTs-NH₂	298	52	7	［39］
ZnO@ZIF-8HNTs	140	67	7	［40］
NH₂-MIL-53（Al）	149	55.5	10	［41］
ZIF-8@GO	136.2	77.9	3	［42］
原始Pebax	89.5	81.3	8	本工作
UiO-66-NH₂-6%	91.0	86.2	8	本工作
UiO-66-AC-6%	102.4	90.6	8	本工作

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功能化Zr-MOF强化混合基质膜CO₂分离

Enhanced CO₂ separation of mixed matrix membranes by functionalized Zr-MOF

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