Cu(Qc)2强化Pebax混合基质膜分离CO2

doi:10.16085/j.issn.1000-6613.2021-0963

化工进展 ›› 2021, Vol. 40 ›› Issue (10): 5652-5659.DOI: 10.16085/j.issn.1000-6613.2021-0963

Cu(Qc)₂强化Pebax混合基质膜分离CO₂

宁梦佳¹^,²(), 代岩¹^,²(), 郗元², 章星³, 刘红晶¹(), 贺高红²

^1.沈阳工业大学石油化工学院，辽宁辽阳 111003
^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.中国石油大学(北京)克拉玛依校区，新疆克拉玛依 834000

收稿日期:2021-05-06 修回日期:2021-06-17 出版日期:2021-10-10 发布日期:2021-10-25
通讯作者: 代岩,刘红晶
作者简介:宁梦佳（1994—），女，硕士研究生，研究方向为气体分离膜。E-mail：nmj0924@163.com。
基金资助:
国家自然科学基金青年基金(21706023);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);新疆维吾尔自治区高校科研计划(XJEDU2017S062)

CO₂ separation of Pebax-based mixed matrix membranes promoted by Cu(Qc)₂

NING Mengjia¹^,²(), DAI Yan¹^,²(), XI Yuan², ZHANG Xing³, LIU Hongjing¹(), HE Gaohong²

^1.School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, 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.Department of Petroleum Engineering, Faculty of Petroleum, China University of Petroleum-Beijing at Karamay, Karamay 834000, Xinjiang, China

Received:2021-05-06 Revised:2021-06-17 Online:2021-10-10 Published:2021-10-25
Contact: DAI Yan,LIU Hongjing

摘要/Abstract

摘要：

为了提高Pebax-1657的CO₂分离性能，本文制备了对CO₂有吸附作用的金属有机骨架Cu(Qc)₂，将其加入到Pebax-1657基质中，制备混合基质膜，用于CO₂的气体分离。通过扫描电子显微镜、热重分析、红外光谱和X射线衍射对溶液浇铸法制备的膜进行表征，通过膜的气体渗透性能测试考察填料含量、操作压力和混合气对膜气体渗透性能的影响。结果表明，Cu(Qc)₂在Pebax基质中随机有效地堆叠形成了高选择性的气体传输通道，极大地提高了CO₂/N₂的选择性。随着Cu(Qc)₂填充量的增加，CO₂渗透系数和CO₂/N₂选择性均呈现先上升后下降的趋势。当Cu(Qc)₂的质量分数为3%时，呈现最佳的CO₂/N₂分离性能，CO₂渗透系数和CO₂/N₂选择性分别为102Barrer和84，与Pebax-1657膜相比，分别提高了45.7%和40.0%，突破了Robeson分离上限，表明该混合基质膜在CO₂的分离应用上具有潜力。

关键词: 二氧化碳捕集, 金属有机骨架, 混合基质膜, 渗透性, 选择性

Abstract:

In order to improve the CO₂ separation performance of Pebax-1657, a metal-organic framework Cu(Qc)₂ was prepared which could adsorb CO₂ and be introduced into the Pebax-1657 matrix to prepare Pebax/Cu(Qc)₂ mixed matrix membranes for CO₂ gas separation. The films prepared by the solution casting method were characterized by scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy and X-ray diffraction. Through the gas permeability test of the membrane, the effects of filler content, operating pressure and mixed gas on the gas permeability of the membrane were investigated. The results show that the random and effective stacking of the Cu(Qc)₂ in the mixed matrix membranes create highly selective gas transport channels that dramatically enhance CO₂/N₂ selectivity. Both the CO₂ permeability and CO₂/N₂selectivity show a trend of first increasing and then decreasing with the increase of Cu(Qc)₂ loading. When 3% Cu(Qc)₂ filler is added, the CO₂/N₂ separation performance of the mixed matrix membrane is the best, and the CO₂ permeability coefficient and CO₂/N₂ selectivity are 102 Barrer and 84, respectively. Compared with the pure Pebax-1657 membrane, it has increased by 45.7% and 40.0% respectively, successfully breaking the upper limit of Robeson separation, indicating that the mixed matrix membrane has potential in the application of CO₂ separation.

Key words: carbon dioxide (CO₂) capture, metal-organic framework, mixed matrix membranes, permeability, selectivity

中图分类号:

TQ028.8

宁梦佳, 代岩, 郗元, 章星, 刘红晶, 贺高红. Cu(Qc)₂强化Pebax混合基质膜分离CO₂[J]. 化工进展, 2021, 40(10): 5652-5659.

NING Mengjia, DAI Yan, XI Yuan, ZHANG Xing, LIU Hongjing, HE Gaohong. CO₂ separation of Pebax-based mixed matrix membranes promoted by Cu(Qc)₂[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5652-5659.

图/表 12

图1 Cu(Qc)2的合成原理

图2 Cu(Qc)2的表征图

图3 Pebax/Cu(Qc)2混合基质膜SEM图

图4 Pebax/Cu(Qc)2混合基质膜的红外光图谱

图5 Pebax/Cu(Qc)2混合基质膜的X射线衍射图谱

图6 Cu(Qc)2和Pebax/Cu(Qc)2混合基质膜的热重分析谱图

图7 Pebax/Cu(Qc)2混合基质膜的DSC曲线

图8 Cu(Qc)2含量对Pebax/Cu(Qc)2混合基质膜性能的影响

图9 Pebax/Cu(Qc)2混合基质膜的气体传输通道示意图

图10 进料压力对Pebax/Cu(Qc)2混合基质膜性能的影响

图11 混合气对Pebax/Cu(Qc)2混合基质膜性能的影响

图12 Pebax/Cu(Qc)2混合基质膜的Robeson上限比较图

参考文献 28

29	ZHANG H, GUO R, HOU J, et al. Mixed-matrix membranes containing carbon nanotubes composite with hydrogel for efficient CO₂ separation[J]. ACS Applied Materials & Interfaces, 2016, 8(42): 29044-29051.
30	MOSLEH S, MOZDIANFARD M, HEMMATI M, et al. Mixed matrix membranes of Pebax1657 loaded with iron benzene-1,3,5-tricarboxylate for gas separation[J]. Polymer Composites, 2017, 38(7): 1363-1370.
31	LI X Q, CHENG Y D, ZHANG H Y, et al. Efficient CO₂ capture by functionalized graphene oxide nanosheets as fillers to fabricate multi-permselective mixed matrix membranes[J]. ACS Applied Materials & Interfaces, 2015, 7(9): 5528-5537.
32	WU H, LI X Q, LI Y F, et al. Facilitated transport mixed matrix membranes incorporated with amine functionalized MCM-41 for enhanced gas separation properties[J]. Journal of Membrane Science, 2014, 465: 78-90.
1	高虎. “双碳”目标下中国能源转型路径思考[J]. 国际石油经济, 2021, 29(3): 1-6.
	GAO Hu. China’s energy transformation under the targets of peaking carbon emissions and carbon neutral[J]. International Petroleum Economics, 2021, 29(3): 1-6.
2	WANG L D, AN S L, YU S H, et al. Mass transfer characteristics of CO₂ absorption into a phase-change solvent in a wetted-wall column[J]. International Journal of Greenhouse Gas Control, 2017, 64: 276-283.
3	YOUSEF A M, EL-MAGHLANY W M, ELDRAINY Y A, et al. New approach for biogas purification using cryogenic separation and distillation process for CO₂ capture[J]. Energy, 2018, 156: 328-351.
4	廉玉姣, 王永洪, 张新儒, 等. N₂优先渗透ZIF-8复合膜的制备及其CO₂捕集[J]. 化工学报, 2019, 70(9): 3573-3581.
	LIAN Yujiao, WANG Yonghong, ZHANG Xinru, et al. Preparation of N₂ selective ZIF-8 composite membrane for CO₂ capture[J]. CIESC Journal, 2019, 70(9): 3573-3581.
5	贝鹏志, 刘红晶, 张莹, 等. 离子液体接枝型PI/GO膜的制备及CO₂/N₂分离的应用[J]. 化工进展, 2020, 39(11): 4550-4556.
	BEI Pengzhi, LIU Hongjing, ZHANG Ying, et al. Preparation of ionic liquid grafted-PI/GO membranes and its application in CO₂/N₂ separation[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4550-4556.
6	EBADI AMOOGHIN A, MASHHADIKHAN S, SANAEEPUR H, et al. Substantial breakthroughs on function-led design of advanced materials used in mixed matrix membranes (MMMs): a new horizon for efficient CO₂ separation[J]. Progress in Materials Science, 2019, 102: 222-295.
7	陈丙晨, 徐积斌, 万超, 等. 用于CO₂/CH₄分离的cPIM-1/ZIF-8混合基质膜的制备[J]. 化工进展, 2020, 39(9): 3518-3524.
	CHEN Bingchen, XU Jibin, WAN Chao, et al. ZIF-8 filled carboxylated polymer of intrinsic microporosity membranes for CO₂/CH₄ separation[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3518-3524.
8	PEREZ E, KARUNAWEERA C, MUSSELMAN I, et al. Origins and evolution of inorganic-based and MOF-based mixed-matrix membranes for gas separations[J]. Processes, 2016, 4(3): 32.
9	杨凯, 阮雪华, 代岩, 等. 氨基MIL-101(Cr)强化CO₂分离性能的混合基质膜优化制备[J]. 化工学报, 2020, 71(1): 329-336.
	YANG Kai, RUAN Xuehua, DAI Yan, et al. Optimized fabrication of mixed matrix membranes based on aminoMIL-101(Cr) for highly efficient CO₂ separation [J]. CIESC Journal, 2020, 71(1): 329-336.
10	ZHAO N, LIU T, LIU Z Z, et al. Synthesis and properties of sulfonated biphenyl poly(ether sulfone) and its mixed-matrix membranes containing carbon nanotubes for gas separation[J]. Journal of Applied Polymer Science, 2017, 134(29): 44995.
11	MULDOON P F, VENNA S R, GIDLEY D W, et al. Mixed matrix membranes from a microporous polymer blend and nanosized metal-organic frameworks with exceptional CO₂/N₂ separation performance[J]. ACS Materials Letters, 2020, 2(7): 821-828.
12	LI Y, GUAN H M, CHUNG T S, et al. Effects of novel silane modification of zeolite surface on polymer chain rigidification and partial pore blockage in polyethersulfone (PES)-zeolite A mixed matrix membranes[J]. Journal of Membrane Science, 2006, 275(1/2): 17-28.
13	JAPIP S, XIAO Y, T-S CHUNG. Particle-size effects on gas transport properties of 6FDA-durene/ZIF-71 mixed matrix membranes[J]. Industrial & Engineering Chemistry Research,2016, 55 (35): 9507-9517.
14	SEOANE B, CORONAS J, GASCON I, et al. Metal-organic framework based mixed matrix membranes: a solution for highly efficient CO₂ capture? [J]. Chemical Society Reviews, 2015, 44(8): 2421-2454.
15	VINOBA M, BHAGIYALAKSHMI M, ALQAHEEM Y, et al. Recent progress of fillers in mixed matrix membranes for CO₂ separation: a review[J]. Separation and Purification Technology, 2017, 188: 431-450.
16	ZHENG W J, DING R, YANG K, et al. ZIF-8 nanoparticles with tunable size for enhanced CO₂ capture of Pebax based MMMs[J]. Separation and Purification Technology, 2019, 214: 111-119.
17	MESHKAT S, KALIAGUINE S, RODRIGUE D. Mixed matrix membranes based on amine and non-amine MIL-53(Al) in Pebax^® MH-1657 for CO₂ separation[J]. Separation and Purification Technology, 2018, 200: 177-190.
18	GE B S, XU Y Y, ZHAO H R, et al. High performance gas separation mixed matrix membrane fabricated by incorporation of functionalized submicrometer-sized metal-organic framework[J]. Materials, 2018, 11(8): 1421.
19	HE T J, XIAO Y H, ZHAO Q D, et al. Ultramicroporous metal-organic framework Qc-5-Cu for highly selective adsorption of CO₂ from C₂H₄ stream[J]. Industrial & Engineering Chemistry Research, 2020, 59(7): 3153-3161.
20	TANG Y N, WANG S, ZHOU X, et al. Room temperature synthesis of Cu(Qc)₂ and its application for ethane capture from light hydrocarbons[J]. Chemical Engineering Science, 2020, 213: 115355.
21	CHEN K J, MADDEN D G, PHAM T, et al. Tuning pore size in square-lattice coordination networks for size-selective sieving of CO₂[J]. Angewandte Chemie, 2016, 128(35): 10424-10428.
22	NUGENT P, RHODUS V, PHAM T, et al. Enhancement of CO₂ selectivity in a pillared pcu MOM platform through pillar substitution[J]. Chemical Communications, 2013, 49(16): 1606.
23	LI B Y, ZHANG Z J, LI Y, et al. Enhanced binding affinity, remarkable selectivity, and high capacity of CO₂ by dual functionalization of a rht-type metal-organic framework[J]. Angewandte Chemie International Edition, 2012, 51(6): 1412-1415.
24	PATEL H A, JE S H, PARK J, et al. Unprecedented high-temperature CO₂ selectivity in N₂-phobic nanoporous covalent organic polymers[J]. Nature Communications, 2013, 4: 1357.
25	GUAN W X, YANG X C, DONG C Y, et al. Prestructured MXene fillers with uniform channels to enhance CO₂ selective permeation in mixed matrix membranes[J]. Journal of Applied Polymer Science, 2021, 138(8): 49895.
26	GUAN W X, DAI Y, DONG C Y, et al. Zeolite imidazolate framework (ZIF)-based mixed matrix membranes for CO₂ separation: a review[J]. Journal of Applied Polymer Science, 2020, 137(33): 48968.
27	YANG X C, ZHENG W J, XI Y, et al. Constructing low-resistance and high-selectivity transport multi-channels in mixed matrix membranes for efficient CO₂ separation[J]. Journal of Membrane Science, 2021, 624: 119046.
28	HABIB N, SHAMAIR Z, TARA N, et al. Development of highly permeable and selective mixed matrix membranes based on Pebax^®1657 and NOTT-300 for CO₂ capture[J]. Separation and Purification Technology, 2020, 234: 116101.

[1]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[2]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[3]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[4]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[5]	李化全, 王明华, 邱贵宝. 硫酸酸解钙钛矿相精矿的行为[J]. 化工进展, 2023, 42(S1): 536-541.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[8]	朱传强, 茹晋波, 孙亭亭, 谢兴旺, 李长明, 高士秋. 固体高分子脱硝剂选择性非催化还原NO _x 特性[J]. 化工进展, 2023, 42(9): 4939-4946.
[9]	潘宜昌, 周荣飞, 邢卫红. 高效分离同碳数烃的先进微孔膜：现状与挑战[J]. 化工进展, 2023, 42(8): 3926-3942.
[10]	毛善俊, 王哲, 王勇. 基团辨识加氢：从概念到应用[J]. 化工进展, 2023, 42(8): 3917-3922.
[11]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.
[12]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[13]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[14]	王晓晗, 周亚松, 于志庆, 魏强, 孙劲晓, 姜鹏. 不同晶粒尺寸Y分子筛的合成及其加氢裂化反应性能[J]. 化工进展, 2023, 42(8): 4283-4295.
[15]	李佳, 樊星, 陈莉, 李坚. 硝酸生产尾气中NO _x 和N₂O联合脱除技术研究进展[J]. 化工进展, 2023, 42(7): 3770-3779.

Cu(Qc)₂强化Pebax混合基质膜分离CO₂

CO₂ separation of Pebax-based mixed matrix membranes promoted by Cu(Qc)₂

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价