含有MCM-41分子筛的混合基质复合膜用于CO2分离

doi:10.11949/j.issn.0438-1157.20150257

化工学报 ›› 2015, Vol. 66 ›› Issue (10): 3979-3990.DOI: 10.11949/j.issn.0438-1157.20150257

含有MCM-41分子筛的混合基质复合膜用于CO₂分离

何玉鹏¹, 王志¹, 乔志华¹, 远双杰², 王纪孝¹

1 天津大学化工学院化学工程研究所, 天津化学化工协同创新中心, 化学工程联合国家重点实验室天津大学, 天津市膜科学与海水淡化技术重点实验室, 天津 300072;
2 中国石油天然气管道工程有限公司, 河北廊坊 065000

收稿日期:2015-03-03 修回日期:2015-04-27 出版日期:2015-10-05 发布日期:2015-10-05
通讯作者: 王志
基金资助:
国家自然科学基金项目(21436009);国家高技术研究发展计划项目(2012AA03A611)。

Novel mixed matrix composite membranes containing MCM-41 for CO₂ separation

HE Yupeng¹, WANG Zhi¹, QIAO Zhihua¹, YUAN Shuangjie², WANG Jixiao¹

1 Chemical Engineering Research Center, School of Chemical Engineering and Technology, Tianjin University, Tianjin Key Laboratory of Membrane Science and Desalination Technology, State Key Laboratory of Chemical Engineering, Collaborative Innovation Center of Chemical Science and Engineering Tianjin, Tianjin 300072, China;
2 China Petroleum Pipeline Engineering Corporation, Langfang 065000, Hebei, China

Received:2015-03-03 Revised:2015-04-27 Online:2015-10-05 Published:2015-10-05
Supported by:
supported by the National Natural Science Foundation of China (21436009) and the National High technology Research and Development Program of China (2012AA03A611).

摘要/Abstract

摘要：

为了提高CO₂分离膜的性能,将接枝了氨基的MCM-41分子筛(MCM-NH₂)添加到聚乙烯基胺(PVAm)水溶液中配制涂膜液,并将PVAm-MCM-NH₂涂膜液涂覆到聚砜(PSf)超滤膜上制备PVAm-MCM-NH₂/PSf混合基质复合膜。复合膜分离层较薄,有利于CO₂渗透速率的提高。接枝的胺基提高了分子筛与聚合物的相容性和膜内胺基含量,有利于膜渗透选择性能的提高。使用CO₂/N₂混合气(15% CO₂ + 85% N₂,体积分数)考察了不同MCM-NH₂添加量的PVAm-MCM-NH₂/PSf膜的渗透选择性能。当涂膜液中m_MCM-NH2/m_PVAm为0.2、湿涂层厚度为50 μm,测试温度为22℃、进料气压力为0.11 MPa时,膜的CO₂渗透速率可达4.66×10^-7 mol·m^-2·s^-1·Pa^-1,CO₂/N₂分离因子可达150。较高的CO₂/N₂分离性能表明PVAm-MCM-NH₂/PSf膜在烟道气碳捕集领域具有良好的应用前景。此外,考察了湿涂层厚度、热处理、添加小分子胺等条件对膜渗透选择性能的影响。

关键词: 混合基质膜, 复合膜, 分子筛, MCM-41, 烟道气, 二氧化碳捕集

Abstract:

To improve the performance of CO₂ separation membrane, MCM-41 modified by amines (MCM-NH₂) was filled into polyvinylamine (PVAm) aqueous solution to fabricate PVAm-MCM-NH₂ coating solutions. PVAm-MCM-NH₂/polysulfone (PSf) mixed matrix composite membranes were prepared by coating PVAm-MCM-NH₂ solutions on PSf ultrafiltration membranes. The separation layer of the composite membrane was very thin, which benefited the improvement of CO₂ permeance. The amine groups grafted to MCM-41 facilitated the transport of CO₂ through reversible reaction and simultaneously improved the filler-polymer interface compatibility. The separation performance of PVAm-MCM-NH₂/PSf membranes with different MCM-NH₂ content was tested using CO₂/N₂ mixed gas (15% (vol) CO₂ + 85%(vol) N₂). When m_MCM-NH2/m_PVAm in the coating solution was 0.2 at testing temperature of 22℃ and feed gas pressure of 0.11 MPa, the composite membrane exhibited a CO₂ permeance of 4.66×10^-⁷ mol·m^-²·s^-¹·Pa^-¹ and a CO₂/N₂ selectivity of 150. The high-performance PVAm-MCM-NH₂/PSf membrane showed promising applications in CO₂ capture from flue gas. Moreover, the effects of the wet coating thickness, the heat treatment and the introduction of the small molecule amines on the separation performance of PVAm-MCM-NH₂/PSf membrane were investigated. The results indicated that the increase of wet coating thickness (from 50 μm to 100 μm) with heat treatment under 80℃ or the introduction of ethanediamine would lead to the improvement of the pressure stability, but the loss of CO₂/N₂ separation performance under low pressures.

Key words: mix matrix membranes, composite membranes, molecular sieves, MCM-41, flue gas, CO₂ capture

中图分类号:

TQ028.8

何玉鹏, 王志, 乔志华, 远双杰, 王纪孝. 含有MCM-41分子筛的混合基质复合膜用于CO₂分离[J]. 化工学报, 2015, 66(10): 3979-3990.

HE Yupeng, WANG Zhi, QIAO Zhihua, YUAN Shuangjie, WANG Jixiao. Novel mixed matrix composite membranes containing MCM-41 for CO₂ separation[J]. CIESC Journal, 2015, 66(10): 3979-3990.

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含有MCM-41分子筛的混合基质复合膜用于CO₂分离

Novel mixed matrix composite membranes containing MCM-41 for CO₂ separation

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