膜科学与技术

氨基聚芳醚的合成及其CO2/N2分离性能

作者：赵思雨，宗立率，邹宇阳，李战胜，张守海，蹇锡高

单位：大连理工大学化工学院，辽宁省高性能树脂材料专业技术创新中心，大连116024

关键词：氨基聚芳醚；CO2分离；烟道气；碳捕集

出版年,卷(期):页码： 2022,42(6):110-117

摘要：

烟道气碳捕集对于减缓温室效应和实现“双碳”目标具有重要意义。作为第二代碳捕集技术，高性能膜材料研发是膜法碳捕集（CO2/N2分离）技术大规模应用的基础。引入与CO2具有亲和性的氨基基团，提高CO2渗透选择性，是获得高性能CO2/N2分离膜材料的有效途径之一。本文采用溶液缩聚法，利用具有CO2亲和性的9,9-双-（4-氨苯基）-2,7-二羟基芴（BADHF）单体，通过调整BADHF和DHPZ单体的摩尔比，合成了一系列不同氨基含量的氨基聚芳醚，并对其化学结构、分子量和热性能进行分析表征。采用溶剂蒸发法制备氨基聚芳醚均质膜，探究氨基含量和温度对CO2、N2气体渗透行为的影响。结果表明，CO2和N2在氨基聚芳醚中的渗透系数都可由Arrhenius方程描述。随氨基含量增大，CO2和N2的渗透系数下降，CO2/N2选择性则先增大后降低，BADHF和DHPZ摩尔比为8:2的氨基聚芳醚的分离性能最佳，CO2/N2选择性达到20.25。

The post-combustion carbon dioxide capture is essential for the mitigation of the global greenhouse effect and achieving 'carbon emission peak’ and ‘carbon neutrality’. As the second-generation carbon capture technology, the development of high-performance membrane materials is the basis for the large-scale application of membrane-based carbon capture (CO2/N2 separation). The CO2 permselectivity could be improved by the addition of CO2-philic groups, which is one of the most promising methods for the developments of high performance membrane materials for CO2/N2 separation. In this work, 9,9'-bis-(4-aminophenyl)-2,7-dihydroxyfluorene (BADHF) of CO2-philicity was used as monomer to synthesize the amino poly(arylene ether) with various molar ratio of BADHF and DHPZ. The chemical structure and thermal properties of amino poly(arylene ether) were characterized. The homogeneous amino poly(arylene ether) membranes were prepared by the solvent evaporation method. The effects of amino content and temperature on the gas permselcetivity were investigated. The CO2 and N2 permeability of amino poly(arylene ether) could be correlated by the Arrhenius equation. With the increase of amino content, the CO2 and N2 permeability reduced, CO2/N2 selectivity increased first and then decreased. When the molar ratio of BADHF and DHPZ was 8:2, the amino poly(arylene ether) had the best CO2/N2 separation performance with CO2/N2 selectivity of 20.25.

赵思雨（1997-），女，辽宁锦州人，硕士研究生，主要从事聚合物气体分离膜材料的研究

参考文献：

[1] 徐南平, 赵静, 刘公平. “双碳”目标下膜技术发展的思考 [J]. 化工进展, 2022, 41(03): 1091-1096.
[2] 王志, 原野, 生梦龙, 等. 膜法碳捕集技术——研究现状及展望 [J]. 化工进展, 2022, 41(03): 1097-1101.
[3] MERKEL T C, LIN H, WEI X, et al. Power plant post-combustion carbon dioxide capture: An opportunity for membranes [J]. Journal of Membrane Science, 2010, 359(1): 126-139.
[4] XIE K, FU Q, QIAO G G, et al. Recent progress on fabrication methods of polymeric thin film gas separation membranes for CO2 capture [J]. Journal of Membrane Science, 2019, 572: 38-60.
[5] TONG Z, HO W S W. Facilitated transport membranes for CO2 separation and capture [J]. Separation Science and Technology, 2017, 52(2): 156-167.
[6] HAN S H, LEE J E, LEE K-J, et al. Highly gas permeable and microporous polybenzimidazole membrane by thermal rearrangement [J]. Journal of Membrane Science, 2010, 357(1): 143-151.
[7] HOUDE A Y, KRISHNAKUMAR B, CHARATI S G, et al. Permeability of dense (homogeneous) cellulose acetate membranes to methane, carbon dioxide, and their mixtures at elevated pressures [J]. Journal of Applied Polymer Science, 1996, 62(13): 2181-92.
[8] 伍勇东, 赵丹, 任吉中, 等. Pebax/TPP共混膜的制备及CO2分离性能研究 [J]. 膜科学与技术, 2020, 40(1): 37-44.
[9] 闫海龙, 高缨佳, 胡爱军, 等. 分离CO2的纳米材料/ Pebax混合基质膜研究进展 [J]. 膜科学与技术, 2021, 41(5): 174-182.
[10] 谢亚芳, 金花, 李砚硕. ZIF-93/Pebax 2533混合基质膜的制备及其CO2/N2分离性能研究 [J]. 膜科学与技术, 2021, 41(5): 79-86+96.
[11] CHEN K K, HAN Y, ZHANG Z, et al. Enhancing membrane performance for CO2 capture from flue gas with ultrahigh MW polyvinylamine [J]. Journal of Membrane Science, 2021, 628: 119215.
[12] LIAO J, WANG Z, WANG M, et al. Adjusting carrier microenvironment in CO2 separation fixed carrier membrane [J]. Journal of Membrane Science, 2016, 511: 9-19.
[13] WU D, SUN C, DUTTA P K, et al. SO2 interference on separation performance of amine-containing facilitated transport membranes for CO2 capture from flue gas [J]. Journal of Membrane Science, 2017, 534: 33-45.
[14] 张守海, 蹇锡高. 杂萘联苯聚芳醚功能膜的研究进展 [J]. 高分子通报, 2011, 9: 1-12.
[15] LIN H, FREEMAN B D. Materials selection guidelines for membranes that remove CO2 from gas mixtures [J]. Journal of Molecular Structure, 2005, 739(1): 57-74.
[16] CHEN Z, WANG Z, HOU L, et al. A simple self-regulating permeability and selectivity of poly (arylene ether ketone) with amino groups for gas separation membrane [J]. Journal of Polymer Research, 2019, 26(12): 267.
[17] CHEN Y-P, HE X-Y, DAYO A Q, et al. Synthesis and characterization of cardanol containing tetra-functional fluorene-based benzoxazine resin having two different oxazine ring structures [J]. Polymer, 2019, 179: 121620.
[18] SUN H. COMPASS: An ab Initio Force-Field Optimized for Condensed-Phase ApplicationsOverview with Details on Alkane and Benzene Compounds [J]. The Journal of Physical Chemistry B, 1998, 102(38): 7338-7364.
[19] GOLZAR K, AMJAD-IRANAGH S, AMANI M, et al. Molecular simulation study of penetrant gas transport properties into the pure and nanosized silica particles filled polysulfone membranes [J]. Journal of Membrane Science, 2014, 451: 117-134.
[20] 李战胜, 高波, 张守海, 等. 渗透汽化分离芳烃/烷烃的聚芳醚腈酮复合膜的制备 [J]. 膜科学与技术, 2019, 39(5): 18-22.
[21] RIZZUTO C, CARAVELLA A, BRUNETTI A, et al. Sorption and Diffusion of CO2/N2 in gas mixture in thermally-rearranged polymeric membranes: A molecular investigation [J]. Journal of Membrane Science, 2017, 528: 135-146.
[22] AKKERMANS R L C, SPENLEY N A, ROBERTSON S H. Monte Carlo methods in Materials Studio [J]. Mol Simul, 2013, 39(14-15): 1153-1164.
[23] 邹修洋, 王杰, 李梅生, 等. 渗透汽化膜传递机理分子动力学模拟研究进展 [J]. 膜科学与技术, 2019, 39(1): 136-142.
[24] CHENG S-X, CHUNG T-S, WANG R, et al. Gas-sorption properties of 6FDA–durene/1,4-phenylenediamine (pPDA) and 6FDA–durene/1,3-phenylenediamine (mPDA) copolyimides [J]. Journal of Applied Polymer Science, 2003, 90(8): 2187-2193.
[25] LI Z, JIANG C. Investigation of the dynamics of poly(ether sulfone) membrane formation by immersion precipitation [J]. Journal of Polymer Science Part B: Polymer Physics, 2005, 43(5): 498-510.
[26] LIN H, FREEMAN B D. Gas solubility, diffusivity and permeability in poly(ethylene oxide) [J]. Journal of Membrane Science, 2004, 239(1): 105-117.

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