Asymmetric copolyimide membranes fabricated by nonsolvent-induced phase separation for He/CH₄ and He/N₂ separation

Abstract

Membrane gas separation is considered an energy-saving technique to extract He from natural gas due to no phase change and room temperature operation. However, the membrane performance was strongly limited by the trade-off between permeance and selectivity. Herein, novel 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)-2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (APAF)-5-amino-2-(4-aminobenzene)benzimidazole (BIA) asymmetric membranes with a thickness of 300 nm were successfully prepared by the non-solvent induced phase separation method. The membrane performance was modulated by regulating dope solution compositions (e.g., tetrahydrofuran and polymer concentration). The ideal He/CH₄ selectivity was 124 and the optimized He permeance reached 87 GPU, beyond the current upper bound. He/CH₄ selectivity was 75 and He permeance was 73 GPU for the binary mixture feed containing 0.2 mol % He. The membrane showed good resistance to CO₂ and C₂H₆, which are the typical impurities in natural gas. The 6FDA-APAF-BIA membranes have good stability (> 160 h), which can provide great potential in He extraction from natural gas.

Graphical abstract

Keywords

He separation / membrane / natural gas / copolyimide

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was sponsored by the National Key Research and Development Program of China (Grant No. 2021YFC2101203), the National Natural Science Foundation of China (Grant Nos. 22178164 and U22B20148), the Jiangsu Provincial Carbon Peak Carbon Neutral Science and Technology Innovation Special Fund (Grant No. BE2022033), the Jiangsu Specially-Appointed Professors Program, and the State Key Laboratory of Materials-Oriented Chemical Engineering (Grant No. ZK202002). We thank the support given by Liming Pu and Miao Yang from China Petroleum Engineering Construction Co., Ltd.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2405-5 and is accessible for authorized users.

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