王 青^1，2 ，陈慧媛¹ ，吴涵钰¹ ，刘 峤¹ ，徐 农^1，2 ，范 茏¹ ，牛鑫蒲^{3 ，}胡坤宏¹ 

1. 合肥大学 能源材料与化工学院，安徽 合肥 230601；2. 南京工业大学 材料化学工程国家重点实验室，江苏 南京 211816；3. 广岛大 学 化学工程系，日本 广岛 739-8527

引用格式： 

王青，陈慧媛，吴涵钰，等. FAU沸石分子筛膜的制备及渗透汽化研究进展［J］. 中国粉体技术，2024，30（5）：21-34. 

WANG Q， CHEN H Y， WU H Y， et al. Progress in preparation and pervaporation of FAU zeolite membranes［J］. China Powder Science and Technology，2024，30（5）：21−34.

DOI：10.13732/j.issn.1008-5548.2024.05.003

收稿日期：2024-05-22，修回日期：2024-06-13，上线日期：2024-07-04。

基金项目：国家自然科学基金项目，编号：22308076；安徽省自然科学基金项目，编号：2308085QB65；安徽省重点研究和开发计划项目， 编号：2022a05020041；安徽省高校自然科学研究项目，编号：2023AH040305；安徽省高校优秀青年科研项目，项目名称：碳化 硅膜可控构筑及其 CO2捕集与甲烷重整制氢集成过程研究；安徽省高校优秀科研创新团队项目，编号：2022AH010096， 2023AH010050；材料化学工程国家重点实验室开放课题项目，编号：KL21-04；南京共鸿科技有限公司技术开发项目，编号： 902/22050123153。

第一作者简介：王青（1990—），男，研究员，博士，安徽省优青，硕士生导师，研究方向为无机陶瓷膜的制备与应用。E-mail：qing‐ wang@hfuu. edu. cn。

摘要：【目的】 FAU（faujasite）沸石分子筛膜作为重要的亲水性、大孔径（0.74 nm）的膜材料，在渗透汽化（pervaporation， PV）液体分离领域具有广阔的应用前景。为了促进FAU沸石分子筛膜的开发及应用，揭示其在PV领域的发展现状。【研究现状】综述近年来FAU沸石分子筛膜的制备方法，包括原位合成法、干凝胶法、二次生长法、微波加热法等，分析各种方 法的特点；探讨如何通过制备参数调控实现 FAU 沸石分子筛膜性能提升的策略；总结 FAU 沸石分子筛膜的 PV 分离机 制，在PV领域的应用进展和所面临的挑战。【展望】为了有效制备无缺陷的FAU沸石分子筛膜，提高分离性能，应进一步 聚焦于FAU沸石分子筛膜的制备方法创新、制备工艺优化和膜结构精密调控；FAU沸石分子筛膜有望在工业分离过程中 发挥更大的应用价值。

关键词：FAU分子筛膜；沸石；渗透汽化；分离机制；膜分离

Abstract

Significance FAU zeolite membranes have garnered substantial scientific and technological interest due to their potential in various separation processes， especially pervaporation. These membranes are notable for their high thermal stability， chemical resistance， and exceptional selectivity， making them promising candidates for applications in chemical processing， biomolecular sensing， and environmental protection. Specifically， the large pore size （0. 74 nm） and high hydrophilicity of FAU zeolites enable effective separation of liquid mixtures， making them highly valuable for industrial applications such as the dehydration of organic solvents and wastewater treatment. The development of FAU zeolite membranes not only enhances separation efficiency but also offers a sustainable and energy-efficient alternative to traditional separation methods.

Progress Over recent decades， significant advancements have been made in synthesizing and applying FAU zeolite membranes for pervaporation. Various synthesis methods， including in-situ synthesis， dry gel conversion， secondary growth， and microwave-assisted synthesis， have been explored to enhance membrane quality and performance. Optimization of synthesis parameters such as temperature， time， and gel composition has shown promising results in achieving defect-free membranes with high selectivity and flux. Techniques like ion exchange and 3-aminopropyltriethoxysilane （APTES） modification of tubular supports have further enhanced membrane properties. Furthermore， a deep understanding of the pervaporation separation mechanism of FAU zeolite membranes is crucial for elucidating the relationship between membrane structure and pervaporation performance， predicting suitable application systems， and achieving high separation efficiency. Most recently， researchers have investigated the pervaporation separation mechanism of FAU membranes through the relationship between single gas permeance， pervaporation permeance， and polarity index （affinity）. The results indicated that within a similar range of permeate molecule sizes， gas permeation exhibited Knudsen selectivity. However， the PV permeance showed a good correlation with the polarity index， suggesting that the PV separation process through FAU membranes is governed by an adsorption-diffusion mechanism. This strong correlation provides a novel， convenient， and environmentally friendly tool for predicting PV performance. Additionally， researchers have explored the application of FAU membranes in the pervaporation of various mixtures， demonstrating their potential for the efficient separation of water and organic solvents. Despite these advancements， the synthesis of defect-free， reproducible， industrially scalable， and cost-effective FAU membranes with high separation performance remains a crucial challenge to be addressed.

Conclusions and Prospects Significant progress has been achieved in developing FAU zeolite membranes for pervaporation. However， challenges persist in achieving reproducibility， scalability， and minimal defects. Future research should focus on optimizing synthesis conditions， exploring advanced characterization techniques， and validating membrane performance in industrial settings. Innovative synthesis methods tailored for FAU zeolite membranes， such as vacuum-seeding and microwave heating， warrant further exploration. Detailed studies on pervaporation mechanisms are essential for better understanding and controlling the separation process. Industrial application studies are crucial for validating laboratory-scale successes and adapting membranes for practical use. Improving mechanical stability and reducing defects are key to successful implementation in real-world applications. Addressing these challenges through systematic research and technological innovation could establish FAU zeolite membranes as pioneers in membrane separation， particularly in pervaporation and other separation processes.

Keywords：FAU molecular sieve membrane； zeolite； pervaporation； separation mechanism； membrane separation

参考文献（References）

［1］ WEE S-L， TYE C-T， BHATIA S. Membrane separation process-pervaporation through zeolite membrane ［J］. Separation and Purification Technology，2008，63（3）：500-516.

［2］ KAYVANI FARD A， MCKAY G， BUEKENHOUDT A， et al. Inorganic membranes： Preparation and application for water treatment and desalination ［J］. Materials，2018，11（1）：74.

［3］ NARAYANAN S， TAMIZHDURAI P， MANGESH V L， et al. Recent advances in the synthesis and applications of mordenite zeolite–review ［J］. RSC Advances，2021，11（1）：250-267. ［4］ XU H， WU P. New progress in zeolite synthesis and catalysis ［J］. National science review，2022，9（9）： nwac045.

［5］ SONG W， LI G， GRASSIAN V H， et al. Development of improved materials for environmental applications： Nanocrystalline NaY zeolites ［J］. Environmental science & technology，2005，39（5）：1214-1220.

［6］ MA N， WANG R， HE G， et al. Preparation of high‐performance zeolite NaA membranes in clear solution by adding SiO₂ into Al₂O₃ hollow‐fiber precursor ［J］. AIChE Journal，2018，64（7）：2679-2688.

［7］ YAN Z， WU X， ZHU B， et al. Improvement of esterification conversion by rapid pervaporation dehydration using a highflux and acid-resistant MOR zeolite membrane ［J］. Separation and Purification Technology，2022，286：120415.

［8］ PENG L， WU Z， WANG B， et al. Fabrication of high-stability W-MFI zeolite membranes for ethanol/water mixture sepa‐ ration ［J］. Journal of Membrane Science，2022，659：120729.

［9］ WANG Q， WU A， ZHONG S， et al. Highly （h0h）-oriented silicalite-1 membranes for butane isomer separation ［J］. Journal of Membrane Science，2017，540：50-59.

［10］ZHOU J， ZHOU C， XU K， et al. Seeding-free synthesis of large tubular zeolite FAU membranes for dewatering of dimethyl carbonate by pervaporation ［J］. Microporous and Mesoporous Materials，2020，292：109713.

［11］YANG S， NAVROTSKY A， PHILLIPS B L. An in situ calorimetric study of the synthesis of FAU zeolite ［J］. Microporous and Mesoporous Materials，2001，46（2-3）：137-151.

［12］THANG H V， GRAJCIAR L， NACHTIGALL P， et al. Adsorption of CO₂ in FAU zeolites： Effect of zeolite composition ［J］. Catalysis Today，2014，227：50-56.

［13］GUEUDRe L， QUOINEAUD A A， PIRNGRUBER G， et al. Evidence of multiple cation site occupation in zeolite NaY with high Si/Al ratio ［J］. The Journal of Physical Chemistry C，2008，112（29）：10899-10908.

［14］ZHU M， AN X， GUI T， et al. Effects of ion-exchange on the pervaporation performance and microstructure of NaY zeolite membrane ［J］. Chinese Journal of Chemical Engineering，2023，59：176-181.

［15］LI Y， LI L， YU J. Applications of zeolites in sustainable chemistry ［J］. Chem，2017，3（6）：928-949.

［16］LIU Y， WANG N， PAN J H， et al. In situ synthesis of MOF membranes on ZnAl-CO₃ LDH buffer layer-modified substrates ［J］. Journal of the American Chemical Society，2014，136（41）：14353-14356.

［17］YANG K， ZHANG X， CHAO C， et al. In-situ preparation of NaA zeolite/chitosan porous hybrid beads for removal of ammonium from aqueous solution ［J］. Carbohydrate polymers，2014，107：103-109.

［18］FENG H， LI C， SHAN H. In-situ synthesis and catalytic activity of ZSM-5 zeolite ［J］. Applied Clay Science，2009，42 （3-4）：439-445.

［19］NAZIR L S M， YEONG Y F， CHEW T L. Methods and synthesis parameters affecting the formation of FAU type zeolite membrane and its separation performance： a review ［J］. Journal of Asian Ceramic Societies，2020，8（3）：553-571.

［20］YU L， ZENG C， WANG C， et al. In situ impregnation− gelation− hydrothermal crystallization synthesis of hollow fiber zeolite NaA membrane［J］. Microporous and Mesoporous Materials，2017，244：278-283.

［21］ZHU G， QIU S， YU J， et al. Synthesis and characterization of high-quality zeolite LTA and FAU single nanocrystals ［J］. Chemistry of materials，1998，10（6）：1483-1486.

［22］冒进，王艺频，刘菁，等 . 地质聚合物原位合成八面沸石膜及其渗透汽化性能［J］. 硅酸盐学报，2013，41（9）： 1244-1250. MAO J， WANG Y， LIU J， et al. In-situ synthesis of faujasite zeolite membrane from geopolymer and its pervaporation properties ［J］. Journal of the Chinese Ceramic Society，2013，41（9）：1244-1250.

［23］UENO K， YAMADA S， NEGISHI H， et al. Fabrication of pure-silica* BEA-type zeolite membranes on tubular silica sup‐ ports coated with dilute synthesis gel via steam-assisted conversion ［J］. Separation and Purification Technology，2020， 247：116934.

［24］MATSUKATA M， SEKINE Y， KIKUCHI E， et al. Synthesis of FAU-Zeolite Membrane by a Secondary Growth Method： Influence of Seeding on Membrane Growth and Its Performance in the Dehydration of Isopropyl Alcohol–Water Mixture ［J］. ACS Omega，2021，6（14）：9834-9842.

［25］KOSINOV N， GASCON J， KAPTEIJN F， et al. Recent developments in zeolite membranes for gas separation ［J］. Journal of Membrane Science，2016，499：65-79.

［26］WANG Q， CHEN H， HE F， et al. High-Performance FAU Zeolite Membranes Derived from Nano-Seeds for Gas Separation ［J］. Membranes，2023，13（11）：858.

［27］ZHU G， LI Y， ZHOU H， et al. Microwave synthesis of high performance FAU-type zeolite membranes： Optimization， characterization and pervaporation dehydration of alcohols ［J］. Journal of Membrane Science，2009，337（1-2）：47-54.

［28］LI Y， YANG W. Microwave synthesis of zeolite membranes： A review ［J］. Journal of Membrane Science，2008，316（1- 2）：3-17.

［29］XU X， YANG W， LIU J， et al. Fast formation of NaA zeolite membrane in the microwave field ［J］. Chinese Science Bulletin，2000，45：1179-1181.

［30］NAZIR L S M， YEONG Y F， CHEW T L. Study on the effect of seed particle size toward the formation of NaX zeolite membranes via vacuum-assisted seeding technique ［J］. Journal of Asian Ceramic Societies，2021，9（2）：586-597.

［31］XIAO W， CHEN Z， ZHOU L， et al. A simple seeding method for MFI zeolite membrane synthesis on macroporous support by microwave heating ［J］. Microporous and Mesoporous Materials，2011，142（1）：154-160.

［32］李子祎，潘恩泽，王佳轩，等 . ZSM-5 沸石分子筛膜的制备及脱盐性能研究［J］. 化工学报，2021，72（10）：5247- 5256. LI Z， PAN E， WANG J， et al. Preparation of ZSM-5 zeolite membrane and its application in desalination ［J］. CIESC Journal，2021，72（10）：5247-5256.

［33］ZHANG X， LIU H， YEUNG K L. Influence of seed size on the formation and microstructure of zeolite silicalite-1 membranes by seeded growth ［J］. Materials Chemistry and Physics，2006，96（1）：42-50.

［34］ZHU G， LI Y， CHEN H， et al. An in situ approach to synthesize pure phase FAU-type zeolite membranes： effect of aging and formation mechanism ［J］. Journal of Materials Science，2008，43：3279-3288.

［35］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.

［36］GUO W F， CHUNG T-S， MATSUURA T. Pervaporation study on the dehydration of aqueous butanol solutions： a comparison of flux vs. permeance， separation factor vs. selectivity ［J］. Journal of Membrane Science，2004，245（1-2）： 199-210.

［37］WANG Q， QIAN C， XU N， et al. Synthesis optimization and separation mechanism of ZSM-5 zeolite membranes for pervaporation dehydration of organic solvents ［J］. Science of The Total Environment，2024，929：172641.

［38］WANG Q， GUO Y， XU N， et al. FAU zeolite membranes synthesized using nanoseeds—Separation mechanism and optimization for the pervaporation dehydration of various organic solvents ［J］. Journal of Membrane Science，2024，696： 122522.

［39］WANG Q， XU N， LIU Q， et al. Low-temperature cross-linking fabrication of sub-nanoporous SiC-based membranes for application to the pervaporation removal of methanol ［J］. Journal of Membrane Science，2022，662：121008.

［40］DONG G， NAGASAWA H， YU L， et al. Pervaporation removal of methanol from methanol/organic azeotropes using organosilica membranes： Experimental and modeling ［J］. Journal of Membrane Science，2020，610：118284.

［41］WANG Q， YOKOJI M， NAGASAWA H， et al. Microstructure evolution and enhanced permeation of SiC membranes derived from allylhydridopolycarbosilane ［J］. Journal of Membrane Science，2020，612：118392.

［42］CHENG X， PAN F， WANG M， et al. Hybrid membranes for pervaporation separations ［J］. Journal of Membrane Science，2017，541：329-346.

［43］LIU G， JIN W. Pervaporation membrane materials： Recent trends and perspectives ［J］. Journal of Membrane Science， 2021，636：119557.

［44］RAZA W， YANG J， WANG J， et al. HCl modification and pervaporation performance of BTESE membrane for the dehydration of acetic acid/water mixture ［J］. Separation and Purification Technology，2020，235：116102.

［45］SONG Y， PAN F， LI Y， et al. Mass transport mechanisms within pervaporation membranes ［J］. Frontiers of Chemical Science and Engineering，2019，13：458-474.

［46］XIA B， WANG S， LI B， et al. Seeding-free synthesis of FAU-type membrane with dry gel modified α-alumina support ［J］. Microporous and Mesoporous Materials，2021，323：111219.

［47］DAOU T J， DOS SANTOS T， NOUALI H， et al. Synthesis of FAU-type zeolite membranes with antimicrobial activity ［J］. Molecules，2020，25（15）：3414.

［48］BETTENS B， DEKEYZER S， VAN DER BRUGGEN B， et al. Transport of pure components in pervaporation through a microporous silica membrane ［J］. The Journal of Physical Chemistry B，2005，109（11）：5216-5222.

［49］WANG Q， KAWANO Y， YU L， et al. Development of high-performance sub-nanoporous SiC-based membranes derived from polytitanocarbosilane ［J］. Journal of Membrane Science，2020，598：117688.

［50］DOBRAK A， VERRECHT B， VAN DEN DUNGEN H， et al. Solvent flux behavior and rejection characteristics of hydrophilic and hydrophobic mesoporous and microporous TiO2 and ZrO2 membranes ［J］. Journal of Membrane Science，2010， 346（2）：344-352.

［51］CASTRO-MUnOZ R， GONZáLEZ-VALDEZ J， AHMAD M Z. High-performance pervaporation chitosan-based membranes： New insights and perspectives ［J］. Reviews in Chemical Engineering，2021，37（8）：959-974.

［52］ZHU M， HUANG S， GONG Y， et al. Effect of flouride on preparation and pervaporation performance of NaY zeolite membrane for EtOH/ETBE mixture ［J］. Microporous and Mesoporous Materials，2019，282：48-52.

［53］NAZIR L S M， YEONG Y F， CHEW T L. Controlled growth of Faujasite zeolite with NaX topology by manipulating solution aging and Na₂O/Al₂O₃ ratios ［J］. Colloids and Surfaces A： Physicochemical and Engineering Aspects，2020，600： 124803.

［54］IKEDA A， HASEGAWA Y. Efficient transesterification of methyl acetate with 2-propanol by the selective removal of methanol using zeolite membranes ［J］. Chemistry Letters，2021，50（1）：113-115.

［55］ZHANG F， XU L， HU N， et al. Preparation of NaY zeolite membranes in fluoride media and their application in dehydration of bio-alcohols ［J］. Separation and Purification Technology，2014，129：9-17.

［56］WANG Z， KUMAKIRI I， TANAKA K， et al. NaY zeolite membranes with high performance prepared by a variabletemperature synthesis ［J］. Microporous and Mesoporous Materials，2013，182：250-258.

［57］KWON Y， CHAUDHARI S， KIM C， et al. Ag-exchanged NaY zeolite introduced polyvinyl alcohol/polyacrylic acid mixed matrix membrane for pervaporation separation of water/isopropanol mixture ［J］. RSC Advances，2018，8（37）：20669- 20678.

［58］KULKARNI S S， KITTUR A A， KARIDURAGANAVAR M Y， et al. Pervaporation dehydration of isopropyl alcohol with NaY zeolite incorvorated hybrid membranes ［J］. Journal of Applied Polymer Science，2008，109（3）：2043-2053.

［59］SEKULIC J， LUITEN M W J， TEN ELSHOF J E， et al. Microporous silica and doped silica membrane for alcohol dehydration by pervaporation ［J］. Desalination，2002，148（1-3）：19-23.

［60］LIN X， KIKUCHI E， MATSUKATA M J C C. Preparation of mordenite membranes on α-alumina tubular supports for pervaporation of waterisopropyl alcohol mixtures ［J］. 2000，（11）：957-958.

［61］NAGASAWA H， MATSUDA N， KANEZASHI M， et al. Pervaporation and vapor permeation characteristics of BTESE-derived organosilica membranes and their long-term stability in a high-water-content IPA/water mixture ［J］. 2016，498： 336-344.

［62］GONG G， WANG J， NAGASAWA H， et al. Fabrication of a layered hybrid membrane using an organosilica separation layer on a porous polysulfone support， and the application to vapor permeation ［J］. 2014，464：140-148.