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聚乙烯亚胺改性聚酰胺反渗透膜的CO2/N2分离性能

作者：陈方正，崔万祥，庄林家，赵可君，王晋嘉，黄海，俞三传

单位： 1. 浙江浙能燃气股份有限公司，杭州 310008；2. 浙江理工大学化学与化工学院，杭州 310018

关键词：二氧化碳；促进传递；聚乙烯亚胺；膜分离

DOI号：

分类号： TQ051.893

出版年,卷(期):页码： 2024,44(4):130-139

摘要：

传统二氧化碳（CO2）分离膜受“Trade-off”效应制约难以实现渗透性及分离选择性的同步提升，本文将聚乙烯亚胺（PEI）胺基载体分子通过静电作用负载于商业化聚酰胺（PA）复合反渗透膜表面，制备具有CO2促进传递功能的PEI-PA复合膜材料，并系统探究了膜制备与分离工艺对PEI-PA复合膜CO2/N2分离性能的影响规律。膜制备研究表明，复合膜的CO2渗透性能在一定范围内随PEI分子浓度提升而增大，且PEI改性层中胺基在pH中性环境中具有理想的CO2转运活性，在最佳改性条件下（改性溶液中PEI质量分数2.0 %、分子量1800 g/mol、pH值7），复合膜CO2渗透性和CO2/N2分离选择性可达96.9 GPU和90.0，较改性前分别提升37.8%和22.4%。分离实验表明，复合膜CO2渗透速率在一定范围内随压力升高而增大，过高压力下CO2渗透速率趋近饱和且低于N2提升幅度，导致CO2渗透速率和气体分离选择性衰减；而气体温度与流速升高将显著提高N2渗透速率，导致气体分离选择性下降。研究结果验证了将反渗透水处理膜转化为CO2气体分离膜的可行性，为工业化放大实践提供了可靠依据。

Traditional carbon dioxide (CO2) separation membranes are subject to the "Trade-off" effect, which makes it difficult to realize the simultaneous improvement of permeability and separation selectivity. In this study, polyethyleneimine (PEI) was selected as amine-based carrier molecules and loaded onto the surface of commercial polyamide (PA) composite reverse osmosis membrane by electrostatic deposition to prepare composite PEI-PA membrane for the facilitated transport of CO2. The influences of membrane fabrication and separation process conditions on the CO2/N2 separation performance of the obtained PEI-PA membrane were systematically investigated. The study of membrane preparation showed that the CO2 permeability of the composite membrane increased with the concentration of PEI in a certain range. And the amine groups in the PEI modified layer had ideal transport activity of CO2 at the neutral pH. Under the optimal modification conditions (2.0% mass fraction of PEI with molecular mass of 1800 g/mol, pH=7), the CO2 permeability and CO2/N2 selectivity of the composite membrane could reach 96.9 GPU and 90.0, which were 37.8% and 22.4% higher than unmodified membranes, respectively. Separation performance test showed that the CO2 permeation increased with the pressure in a certain range. But it would approach saturation and become lower in growth proportion than N2, resulting in attenuation of the CO2 permeation ratio and CO2/N2 selectivity. Besides, the increase of gas temperature and flow rate significantly increased N2 permeation, resulting in selectivity decline. Above results verify the feasibility of transforming reverse osmosis membranes into CO2 separation membranes, which provides a reliable basis for industrial scale-up practice.

基金项目：

浙江省“领雁计划”研发项目(2022C03048)

作者简介：

陈方正(1974-), 男，浙江嵊州人，高级工程师，主要从事生物质燃气领域技术研究，E-mail: 453724668@qq.com

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