面向非极性有机溶剂体系的纳滤膜研究进展

Research Progress of Nanofiltration Membranes for Nonpolar Organic Solvent Systems

摘要

随着全球工业对高效、节能、环保分离技术需求的日益增长，有机溶剂纳滤（OSN）膜技术在溶剂回收、产物纯化等领域展现出巨大潜力。目前，OSN的研究与应用主要集中于极性溶剂体系，而对非极性溶剂（如烷烃、芳香烃等）的分离研究仍较为有限，相关膜材料面临稳定性不足与性能受限的挑战。针对非极性体系中普遍存在的膜溶胀与塑化、界面化学失配及渗透性-选择性权衡等问题，本文首先系统综述了聚合物膜、纳米复合膜及陶瓷膜等OSN膜的制备策略与分离机理；然后重点探讨了上述问题的解决途径，包括耐溶剂聚合物设计、亚纳米孔道精细调控、疏水改性、化学交联以及金属有机框架（MOF）等纳米材料复合等方法；最后，对非极性有机溶剂体系纳滤膜的未来发展方向进行了展望，旨在为其在能源、化工、制药等工业过程中的高效绿色分离应用提供参考。

Abstract

With the growing global industrial demand for efficient, energy-saving and eco-friendly separation technologies, organic solvent nanofiltration (OSN) membrane technology has shown great potential in fields such as solvent recovery and product purification. Currently, the research and application of OSN are mainly focused on polar solvent systems, while studies on the separation of nonpolar solvents (such as alkanes, aromatic hydrocarbons) remain relatively limited. Corresponding membrane materials face the challenges of insufficient stability and limited performance. Addressing common issues in nonpolar systems such as membrane swelling and plasticization, interfacial chemical mismatch, and permeability-selectivity trade-off, this review systematically summarizes the fabrication strategies and separation mechanisms of OSN membranes, including polymer membranes, nanocomposite membranes, and ceramic membranes. It focuses on innovative strategies, including molecular engineering design of new solvent-resistant polymers, construction of precise sub-nanometer pores, incorporation of hydrophobic groups, chemical crosslinking modification, and synergistic optimization of membrane structures and performance using nanofillers such as metal organic-frameworks (MOF). Finally, this review looks forward to the future development directions of nanofiltration membranes for nonpolar organic solvent systems, aiming to provide a reference for their efficient and green separation applications in critical industrial fields such as energy, chemical and pharmaceutical industries.

关键词

有机溶剂纳滤膜 / 非极性溶剂体系 / 膜分离 / 相转化 / 界面聚合 / 涂覆法

Key words

organic solvent nanofiltration membrane / nonpolar solvent system / membrane separation / phase inversion / interfacial polymerization / coating method

参考文献

[1] MARCHETTI P, JIMENEZ—SOLOMON M F, SZEKELY G, LIVINGSTON A G . Molecular separation with organic solvent nanofiltration: A critical review [J]. Chemical Reviews, 2014, 114(21): 10735-10806.

[2] MERLET R, WINNUBST L, NIJMEIJER A, AMIRILARGANI M, SUDHÖLTER E J R, DE SMET L C P M, SALVADOR—COB S, VANDEZANDE P, DORBEC M, SLUIJTER S, VAN VEEK H, VANDELFT Y, WIENK I, CUPERUS P, BEHERA S, HARTANTO Y, VANKELECOM I F J, DE WIT P . Comparing the performance of organic solvent nanofiltration membranes in non—polar solvents [J]. Chemie Ingenieur Technik, 2021, 93(9): 1389-1395.

[3] WANG Z, LUO X, ZHANG J, ZHANG F, FANG W, JIN J . Polymer membranes for organic solvent nanofiltration: Recent progress, challenges and perspectives [J]. Advanced Membranes, 2023, 3: 100063.

[4] SZEKELY G, JIMENEZ—SOLOMON M F, MARCHETTI P, KIM J F, LIVINGSTON A G . Sustainability assessment of organic solvent nanofiltration: From fabrication to application [J]. Green Chem, 2014, 16(10): 4440-4473.

[5] VANDEZANDE P, GEVERS L E M, VANKELECOM I F J . Solvent resistant nanofiltration: Separating on a molecular level [J]. Chem Soc Rev, 2008, 37(2): 365-405.

[6] TAO M, XUE L, LIU F, JIANG L . An intelligent superwetting PVDF membrane showing switchable transport performance for oil/water separation [J]. Advanced Materials, 2014, 26(18): 2943-2948.

[7] DING Y, WANG J, WU J, WANG J, LIU F . Binary nanofibrous membranes with independent oil/water transport channels for durable emulsion separation [J]. Journal of Membrane Science, 2023, 673: 121484.

[8] GAO A, LIU F, XIONG Z, YANG Q . Tunable adhesion of superoleophilic/superhydrophobic poly(lactic acid) membrane for controlled—release of oil soluble drugs [J]. Journal of Colloid and Interface Science, 2017, 505: 49-58.

[9] SUN H, WANG N, XU Y, WANG F, LU J, WANG H, AN Q F . Aromatic—aliphatic hydrocarbon separation with oriented monolayer polyhedral membrane [J]. Science, 2024, 386(6725): 1037-1042.

[10] KUSHIDA W, GONZALES R R, SHINTANI T, MATSUOKA A, NAKAGAWA K, YOSHIOKA T, MATSUYAMA H . Organic solvent mixture separation using fluorine—incorporated thin film composite reverse osmosis membrane [J]. Journal of Materials Chemistry A, 2022, 10(8): 4146-4156.

[11] YOSHIWAKA Y, KITAGAWA T, SHINTANI T, NAKAGAWA K, YOSHIOKA T, MATSUYAMA H . AF2400/polyketone composite OSRO membrane for organic solvent mixture separation [J]. Separation and Purification Technology, 2023, 320: 124150.

[12] 王晨洋, 徐浪, 成世杰, 帅旗, 左丹英 . 表面喷雾N, N—二甲基乙酰胺/水—浸没沉淀相转化法制备PVDF多孔膜的结构和性能 [J]. 功能高分子学报, 2022, 35(3): 292-298.

[13] WANG C Y, XU L, CHENG S J, SHUAI Q, ZUO D Y . Structure and performance of PVDF porous membrane prepared by surface spraying DMAc/H₂O—immersion precipitation phase inversion method [J]. Journal of Functional Polymers, 2022, 35(3): 292-298.

[14] TANG Y, LIU J, ZHOU B, WANG L, LIN Y, ZHANG C, WANG X . A criterion of diluent selection for the polymeric membrane formation via thermally induced phase separation process based on Hansen solubility parameter theory [J]. Advanced Membranes, 2022, 2: 100033.

[15] GU S, LI S, XU Z . Organic solvent nanofiltration membranes for separation in non—polar solvent system [J]. Green Energy & Environment, 2025, 10(2): 244-267.

[16] GORGOJO P, KARAN S, WONG H C, JIMENEZ—SOLOMON M F, CABRAL J T, LIVINGSTON A G . Ultrathin polymer films with intrinsic microporosity: Anomalous solvent permeation and high flux membranes [J]. Advanced Functional Materials, 2014, 24(30): 4729-4737.

[17] LASSEUGUETTE E, MALPASS—EVANS R, CARTA M, MCKEOWN N B, FERRARI M C . Temperature and pressure dependence of gas permeation in a microporous Tröger’s base polymer [J]. Membranes, 2018, 8(4): 132.

[18] JIN Y, ZHANG A, DONG G, HOU J, ZHU J, ZHANG Y . Ultrathin membranes comprising polymers of intrinsic microporosity oligomers for high—performance organic solvent nanofiltration [J]. Journal of Membrane Science, 2025, 714: 123436.

[19] XU L, LI S, MAO H, LI Y, ZHANG A, WANG S, LIU W, LV J, WANG T, CAI W, SANG L, XIE W, PEI C, LI Z, FENG Y, ZHAO Z . Highly flexible and superhydrophobic MOF nanosheet membrane for ultrafast alcohol—water separation [J]. Science, 2022, 378(6617): 308-313.

[20] MA Z, LIAN P, LI J, REN Y, SHI Y, MA H, GUO Y, PAN Q, YUAN S, WANG Y, LIU H, LIU L, DONG Y, SU Y, ZHAO J, AN Q, HE G, JIANG Z . Mixed matrix membranes by incorporating methyl—functionalized covalent organic framework into PDMS for high flux ethanol/water separation [J]. Advanced Membranes, 2025, 5: 100150.

[21] WANG L, SUN B, ZHANG W, ZHOU X, LUO H, WU L . Covalent organic framework incorporated PDMS mixed matrix membrane for enhanced pervaporation performance in n—butanol/water separation [J]. Chemical Engineering Journal, 2026, 530: 173697.

[22] TANG S, WU Z, FENG G, WEI L, WENG J, RUIZ—HITZKY E, WANG X . Multifunctional sandwich—like composite film based on superhydrophobic MXene for self—cleaning, photodynamic and antimicrobial applications [J]. Chemical Engineering Journal, 2023, 454: 140457.

[23] LU Y, CHAN J Y, ZHANG H, LI X, NOLVACHAI Y, MARRIOTT P J, ZHANG X, SIMON G P, BANASZAK HOLL M M, WANG H . Cyclodextrin metal—organic framework—polymer composite membranes towards ultimate and stable enantioselectivity [J]. Journal of Membrane Science, 2021, 620: 118956.

[24] WANG W, BATOOL N, MODERNE M, QUINTANA GONZÁLEZ J J, PETIT E, FLAUD V, CHÈVREMONT W, LAJAUNIE L, AUBERT T, VOIRY D . Single—layer silica nanosheets with in—plane porosity enable high—performance nanolaminate membranes for organic solvent nanofiltration [J]. Journal of the American Chemical Society, 2026, 148(2): 2229-2238.

[25] LIN R, ZHAO Q, CHU H, FENG F, ZHOU X, JIANG X, SHAO L, ZHANG Y . Nanofiller—confined spatial fluctuation in monomer diffusion synthesizing ultrafast reverse osmosis membranes driven by hydrogen—bonding networks [J]. Nature Communications, 2025, 16(1): 9978.

[26] HE Y, LI G, LIN H, HAN Q, YE Y, WANG J, LIU F . Enhanced Mg²⁺/Li⁺ separation by amino crown ether composite nanofiltration membrane with Mg²⁺ transport barrier [J]. Journal of Membrane Science, 2024, 709: 123137.

[27] SHEN T, ZHENG Y, NAN Y, YUE Z, GAO S, JIN J . Sub—1 Å precision tuning interlayer spacing of robust graphene oxide membranes for high—selectivity molecular sieving [J]. Advanced Functional Materials, 2025, 36(8): e16359.

[28] ZEIDLER S, PUHLFÜRSS P, KÄTZEL U, VOIGT I . Preparation and characterization of new low MWCO ceramic nanofiltration membranes for organic solvents [J]. Journal of Membrane Science, 2014, 470: 421-430.

[29] ISHAK N F, HASHIM N A, OTHMAN M H D, MONASH P, ZUKI F M . Recent progress in the hydrophilic modification of alumina membranes for protein separation and purification [J]. Ceramics International, 2017, 43(1): 915-925.

[30] SHI D, HUANG F, XUE K, SHI X, ZHU N, YU K, ZHANG Z, DUAN Y, CHEN T, YUAN H, YANG H, ZHAO W, IMBROGNO J, ZHAO D . Scalable metal—organic framework membranes through nonclassical crystallization for molecular separation [J]. Science Advances, 11(49): eadz5237.

[31] WU H, XU Y, TANG Q, WU B, WU P . Microstructure engineering of polyamide membranes for ultrafast polar and non—polar solvent transport [J]. Nature Communications, 2025, 16(1): 8414.

[32] THOMPSON K A, MATHIAS R, KIM D, KIM J, RANGNEKAR N, JOHNSON J R, HOY S J, BECHIS I, TARZIA A, JELFS K E, MCCOOL B A, LIVINGSTON A G, LIVELY R P, FINN M G . N—Aryl—linked spirocyclic polymers for membrane separations of complex hydrocarbon mixtures [J]. Science, 2020, 369(6501): 310-315.

[33] JANG H Y, JOHNSON J R, MA Y, MATHIAS R, BHANDARI D A, LIVELY R P . Torlon® hollow fiber membranes for organic solvent reverse osmosis separation of complex aromatic hydrocarbon mixtures [J]. AIChE Journal, 2019, 65(12): e16757.

[34] GUGLIUZZA A, DRIOLI E . PVDF and HYFLON AD membranes: Ideal interfaces for contactor applications [J]. Journal of Membrane Science, 2007, 300(1—2): 51-62.

[35] CHISCA S, MUSTEATA V E, ZHANG W, VASYLEVSKYI S, FALCA G, ABOU—HAMAD E, EMWAS A H, ALTUNKAYA M, NUNES S P . Polytriazole membranes with ultrathin tunable selective layer for crude oil fractionation [J]. Science, 2022, 376(6597): 1105-1110.

[36] REN Y, MA H, KIM J, AL OTMI M, LIN P, DAI C, LEE Y J, ZHAI Z, JANG W J, YANG S, SARSWAT A, FELIACHI Y, SAMPATH J, REALFF M J, LIVELY R P, GUO S . Fluorine—rich poly(arylene amine) membranes for the separation of liquid aliphatic compounds [J]. Science, 2025, 387(6730): 208-214.

[37] LEE T H, BALCIK M, ALI Z, JOO T, RIVERA M P, PINNAU I, SMITH Z P . Microporous polyimine membranes for efficient separation of liquid hydrocarbon mixtures [J]. Science, 2025, 388(6749): 839-844.

[38] 韩蔚瑶, 张彩丽, 翁云宣 . 抗溶胀型聚酰亚胺气体分离膜的制备及其研究进展 [J]. 中国科学: 化学, 2020, 50(6): 655-668.

[39] HAN W Y, ZHANG C L, WENG Y X . Preparation and research progress of polyimide membranes in gas separation with anti—plasticization property [J]. Scientia Sinica Chimica, 2020, 50(6): 655-668.

[40] LIU W, JIANG X, YANG Y, GUO L, WANG H, SHAO L . Mixed matrix membranes containing exceptional Bi—HHTP MOF for highly—efficient CO₂/N₂ separation [J]. Journal of Membrane Science, 2025, 735: 124576.

[41] WANG T, HU J, OUYANG R, WANG Y, HUANG Y, HU S, LI W X . Nature of metal—support interaction for metal catalysts on oxide supports [J]. Science, 2024, 386(6724): 915-920.

[42] 刘佳欢, 王建强, 刘富 . 单体扩散控制界面聚合制备聚酰胺薄层复合纳滤膜研究进展 [J]. 膜科学与技术, 2025, 45(4): 194-205.

[43] LIU J H, WANG J Q, LIU F . Research progress in preparation of polyamide nanofiltration membranes by monomer diffusion controlled interfacial polymerization [J]. Membrane Science and Technology(Chinese), 2025, 45(4): 194-205.

[44] LI G, LIU Y, HE Z, SHI K, LIU F . Retrievable ultrafast covalent triazine framework membranes for organic solvent nanofiltration [J]. Chemical Engineering Journal, 2024, 484: 149488.

[45] KARAN S, JIANG Z, LIVINGSTON A G . Sub—10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation [J]. Science, 2015, 348(6241): 1347-1351.

[46] ZHENG F, PAN Z, LIAO Y, ZHAN J, FANG S, PANG J, ZHANG T, HAN G . Polyamide nanofilms with Janus microporous framework for sustainable solvent filtration [J]. Nature Communications, 2025, 17(1): 1288.

[47] LEE T H, BALCIK M, WU W N, PINNAU I, SMITH Z P . Dual—phase microporous polymer nanofilms by interfacial polymerization for ultrafast molecular separation [J]. Science Advances, 10(33): eadp6666.

[48] JIANG Z, DONG R, EVANS A M, BIERE N, EBRAHIM M A, LI S, ANSELMETTI D, DICHEL W R, LIVINGSTON A G . Aligned macrocycle pores in ultrathin films for accurate molecular sieving [J]. Nature, 2022, 609(7925): 58-64.

[49] XU J, JIANG R, QIU Z, CHEN C, LIU B, HU X, WANG B, ZHANG M, SHEN L, LIN H . Conjugated microporous polymer for membrane separation: A review [J]. Separation and Purification Technology, 2025, 362: 131795.

[50] XU Z, CHEN Z, ZHONG X, YANG S, CHEN Y, FENG Y, ZHANG P, LI Y, XUE M, CHEN X . Microenvironment engineering of conjugated microporous polymer membranes enabling ultrahigh solvent permeability and molecular sieving [J]. Journal of the American Chemical Society, 2026, 148(2): 2719-2727.

[51] 李兴祥, 阎明政, 王宪实, 马军, 周宗尧 . 有机溶剂纳滤薄层纳米复合膜的最新研究进展 [J]. 膜科学与技术, 2025, 45(3): 189-200.

[52] LI X X, YAN M Z, WANG X S, MA J, ZHOU Z Y . The development of thin—film nanocomposite membranes for organic solvent nanofiltration [J]. Membrane Science and Technology(Chinese), 2025, 45(3): 189-200.

[53] CHEN Z, LI B, LIU Y, XU Z M, ZHONG X F, ZHANG P P, LIU L M, LI Y, XUE M, CHEN X M . Multivariate MOF hollow fiber membranes with precision—tuned subnanometer channels toward aromatic hydrocarbon separation [J]. Angewandte Chemie International Edition, 2025, 64(32): e202508510.

[54] LI S, DONG R, MUSTEATA V E, KIM J, RANGNEKAR N D, JOHNSON J R, MARSHALL B D, CHISCA S, XU J, HOY S, MCCOOL B A, NUNES S P, JIANG Z, LIVINGSTON A G . Hydrophobic polyamide nanofilms provide rapid transport for crude oil separation [J]. Science, 2022, 377(6614): 1555-1561.

[55] BRUNO N C, MATHIAS R, LEE Y J, ZHU G, AHN Y H, RANGNEKAR N D, JOHNSON J R, HOY S, BECHIS I, TARZIA A, JELFS K E, MCCOOL B A, LIVELY R, FINN M G . Solution—processable polytriazoles from spirocyclic monomers for membrane—based hydrocarbon separations [J]. Nature Materials, 2023, 22(12): 1540-1547.

[56] LI J, FANG Y, XIONG R, FENG W, GUO H, LI F, ZHANG M, WANG S, FANG C, ZHU B, LEE Y M, ZHU L . Spirocyclic poly(vinylene ether ketone) membranes with enhanced microporosity for energy—efficient alcohol—hydrocarbon azeotrope separation [J]. Nature Communications, 2025, 16(1): 10000.

[57] PARK S H, ALAMMAR A, FULOP Z, PULIDO B A, NUNES S P, SZEKELY G . Hydrophobic thin film composite nanofiltration membranes derived solely from sustainable sources [J]. Green Chemistry, 2021, 23(3): 1175-1184.

[58] ALDURAIEI F, ABDULHAMID M A, GEBREYOHANNES A Y, PEEVA L, LIVINGSTON A, NUNES S P, SZEKELY G . Thin—film composite membranes with contorted monomer for high—flux isothermal refining [J]. Journal of Membrane Science, 2024, 700: 122712.

[59] FENG W, LI F, LI J, LI Z, XU L, GUO H, LI N, CAO X, FANG C, ZHU B, ZHU L . Asymmetrical polyimide membranes with programmable polymer chain architectures for liquid hydrocarbon fractionation [J]. Science Advances, 11(37): eady3674.

[60] LI J, LIU C, ZHU C, XIN J, WANG Z, LIU Y, ZHANG C, LIANG H, YANG H, WU J, XU Z . Fully aromatic fluorinated polyamide nanofilms with molecular gating for ultrafast crude oil fractionation [J]. Angewandte Chemie International Edition, 2025, 65(1): e202512620.

基金资助

浙江省领雁研发计划(2024C03284(SD2))

浙江省自然科学基金杰出青年基金(延续项目)(LRG25E030002)