聚乙烯胺/埃洛石纳米管混合基质膜的制备及其CO2/N2分离

doi:10.11949/j.issn.0438-1157.20180420

化工学报 ›› 2018, Vol. 69 ›› Issue (9): 4106-4113.DOI: 10.11949/j.issn.0438-1157.20180420

• 材料化学工程与纳米技术 • 上一篇下一篇

聚乙烯胺/埃洛石纳米管混合基质膜的制备及其CO₂/N₂分离

侯蒙杰¹, 张新儒^1,2, 王永洪^1,2, 李晋平^1,2, 刘成岑¹, 凌军³

1. 太原理工大学化学化工学院, 山西太原 030024;
2. 气体能源高效清洁利用山西省重点实验室, 山西太原 030024;
3. 云南中烟工业有限责任公司技术中心, 云南昆明 650231

收稿日期:2018-04-23 修回日期:2018-06-16 出版日期:2018-09-05 发布日期:2018-09-05
通讯作者: 王永洪
基金资助:
国家自然科学基金青年基金（21506140）；山西省煤层气联合基金（2015012009）；中国博士后基金（2016M601289）；山西省留学人员科技活动项目择优资助经费。

Preparation of PVAm mixed matrix membranes by incorporating halloysite nanotubes for CO₂/N₂ separation

HOU Mengjie¹, ZHANG Xinru^1,2, WANG Yonghong^1,2, LI Jinping^1,2, LIU Chengcen¹, LING Jun³

1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China;
2. Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, Shanxi, China;
3. Technology Centre, China Tobacco Yunnan Industrial Co., Ltd., Kunming 650231, Yunnan, China

Received:2018-04-23 Revised:2018-06-16 Online:2018-09-05 Published:2018-09-05
Supported by:
supported by the National Natural Science Foundation of China (21506140), the Joint Fund of Shanxi Provincial Coal Seam Gas(2015012009), the China Postdoctoral Science Foundation (2016M601289) and the Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province.

摘要/Abstract

摘要：

制备高性能的气体分离膜，是实现CO₂高效回收的关键。为了提高CO₂分离膜的性能，将中空管状结构的埃洛石纳米管（HNTs）添加到聚乙烯胺（PVAm）中配制涂膜液，并将PVAm-HNTs涂膜液涂覆到聚砜（PSf）超滤膜上制备PVAm-HNTs/PSf混合基质膜。其中PSf超滤膜作为支撑层，PVAm-HNTs致密涂层作为功能层，功能层结构与形态对CO₂分离具有关键作用。采用XRD、SEM对HNTs的结构与形态进行表征，并借助FTIR和SEM对膜的形态与结构进行分析。在进料气为纯气条件下，系统地研究了HNTs添加量、进料压力、PVAm-HNTs涂层厚度对PVAm-HNTs/PSf膜的CO₂分离性能影响，并考察了混合基质膜的CO₂/N₂混合气分离性能。结果显示：在水溶液中显示正电性的PVAm与负电性的HNTs具有较好的界面相容性。HNTs添加量为1%（质量）、PVAm-HNTs湿涂层厚度为50 μm的混合基质膜，表现出最优的CO₂分离性能。在进料气压力为0.1 MPa、测试温度为25℃、CO₂/N₂（15/85，体积比）混合气进料的条件下，膜的CO₂渗透速率为178 GPU，CO₂/N₂选择性为83；该膜具有较好的稳定性，经过120 h运行后，渗透性和选择性仍能保持稳定。

关键词: 埃洛石纳米管, 聚乙烯胺, 膜, 烟道气, CO₂捕集

Abstract:

The preparation of gas separation membranes with high permselectivity is the key for CO₂ efficient recovery. To improve the CO₂ separation performance of membrane, halloysite nanotubes (HNTs) with hollow and tubular structure were incorporated into polyvinylamine (PVAm) aqueous solution to fabricate PVAm-HNTs coating solutions. PVAm-HNTs/polysulfone (PSf) mixed matrix membranes (MMMs) were prepared by coating PVAm-HNTs solutions on PSf ultrafiltration membranes. The PSf membrane is the supporting layer, and PVAm-HNTs coating layer is the functional layer, which is the key for CO₂ separation. The structure and morphology of HNTs were characterized by XRD and SEM. The morphology and structure of the membranes were analyzed by FTIR and SEM. The effects of HNTs content, feed pressure, and the thickness of PVAm-HNTs coating layer were systematically investigated by using pure CO₂ and N₂ pure gas. The CO₂/N₂[15/85(volume)] mixed gas separation performance also were investigated. The good interfacial interaction is attributed to the electrostatic attraction between PVAm and negatively charged HNTs. At testing temperature of 25℃ and feed gas pressure of 0.1 MPa, PVAm-HNTs/PSf-1%(mass) MMMs with wet coating thickness of 50 μm exhibited long-term performance stability, and the CO₂separation performance maintained high CO₂ permeability of 178 GPU with CO₂/N₂ selectivity of 83 for CO₂/N₂ mixed gas over 120 h.

Key words: halloysite nanotube, polyvinylamine, membranes, flue gas, CO₂ capture

中图分类号:

TQ028.8

侯蒙杰, 张新儒, 王永洪, 李晋平, 刘成岑, 凌军. 聚乙烯胺/埃洛石纳米管混合基质膜的制备及其CO₂/N₂分离[J]. 化工学报, 2018, 69(9): 4106-4113.

HOU Mengjie, ZHANG Xinru, WANG Yonghong, LI Jinping, LIU Chengcen, LING Jun. Preparation of PVAm mixed matrix membranes by incorporating halloysite nanotubes for CO₂/N₂ separation[J]. CIESC Journal, 2018, 69(9): 4106-4113.

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聚乙烯胺/埃洛石纳米管混合基质膜的制备及其CO₂/N₂分离

Preparation of PVAm mixed matrix membranes by incorporating halloysite nanotubes for CO₂/N₂ separation

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