高性能NaA沸石膜的制备及渗透蒸发应用研究
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摘要
渗透蒸发作为一种新型的膜分离技术,相对于传统的分离方法而言,具有分离效率高、能耗低、操作简便、设备简单等优点,近年来得到广泛的关注。NaA沸石分子筛膜由于其强的亲水性和介于大多数有机溶剂与水分子之间小的孔径,使其成为渗透蒸发过程脱除有机溶剂中微量水最理想的沸石膜。对于乙醇/水体系,NaA沸石分子筛膜具有非常好的的分离性能,将其与精馏过程耦合用于生物质燃料乙醇的制备,具有广阔的应用前景。
本论文利用SEM、XRD以及渗透蒸发等表征手段寻求在大孔载体管上制备出高性能的NaA沸石膜。首先分别采用二次修补法和两步涂晶法在长度为25 cm的载体管上制备出高性能的NaA沸石膜,并在两种制备方法的基础上对NaA沸石膜进行放大制备,通过渗透蒸发性能测试,制备的长度为80 cm的NaA沸石分子筛膜具有较好的分离效果,已达到工业化应用的要求。本论文取得的具体成果如下：
(1)采用高浓度合成液配方1Al2O3：2SiO2：2Na2O：120H2O对于低浓度合成液配方1Al2O3：5SiO2：50Na2O：1000H2O合成一次存在小缺陷的膜能够给以很好的修补,对于乙醇含量为90wt.%的乙醇/水体系,在温度为70℃和真空度为200～300 Pa的条件下,其分离系数大于5000,渗透通量最高可达到1.9210 kg·m-2·h-1,而且具有很高重复性。
(2)采用合成液摩尔配比1Al2O3：5SiO2：50Na2O：1000H2O,对于采用两步涂晶后的载体管进行动态水热合成一次就可以获得高性能的NaA沸石分子筛膜。通过渗透蒸发性能测试,在温度为70℃和真空度为200～300 Pa的条件下,对90wt.%水/乙醇混合物进行分离,其分离系数大于10000,渗透通量最高可以达到1.8510 kg·m-2·h-1,且具有很高的重复性。
(3)在大孔a-Al2O3载体管上成功制备出长度为80 cm的NaA沸石分子筛膜,通过渗透蒸发性能测试,对于乙醇浓度为90 wt.%的乙醇/水体系,保持进料流量为200L·h-1,当料液温度升高到120℃,其渗透通量最高可达到8.6781 kg·m-2·h-1,而且分离系数大于1000,已能够满足工业化应用要求。
Pervaporation has received widely attention as a new type membrane separation in recent years, because it is an effective and energy-efficient technology compared with conventional separation process.NaA zeolite membranes have become ideal materials on dehydration of organic by pervaporation due to its high hydrophilicity and small pore size which range between most organic solvents and water molecules.NaA zeolite membrane has good ethanol/water separation performance, which is expected to be utilized in a hybrid distillation/pervaporation system for bio-ethanol dehydration.
In this thesis, the characterization methods of SEM、XRD and pervaporation were utilized to seek preparation methods of high performance NaA zeolite membrane on macro-porous support. First of all, high performance NaA zeolite membranes with the length of 25 cm were prepared by second repair method and two-step seeding method. NaA zeolite membranes were enlarged preparation on the basis of the previous two methods, which had good pervaporation performance and met the requirements of industrial application. The main conclusions obtained in this thesis were as follows:
(1)NaA zeolite membrane with the defects was repaired well by another high concentration formulation 1Al2O3:2SiO2:2Na2O:120H2O,which was dynamic hydrothermally synthesized one time with the formulation 1Al2O3:5SiO2= 50Na2O: 1000H2O.Pervaporation (PV) experiments were carried out at 70℃and 200～300 Pa using a 90 wt.% water/ethanol mixture with a laboratory scale apparatus to test the performance of as-synthesized membranes. They showed the high performance with the water flux up to 1.9210 kg·m-2·h-1 and the separation factor more than 5000.
(2) High performance NaA zeolite membrane was prepared by two-step seeding method, which was dynamic hydrotherrmally synthesized just one time with the formulation 1Al2O3:5SiO2:50Na2O:1000H2O.Pervaporation (PV) experiments were carried out at 70℃and 200～300 Pa using a 90 wt.% water/ethanol mixture with a laboratory scale apparatus to test the performance of as-synthesized membranes.They showed the high performance with the water flux up to 1.8510 kg·m-2·h-1 and the separation factor more than 10000.
(3)NaA zeolite membranes with the length of 80 cm were successfully prepared on the macro-porousα-Al2O3 support. Pervaporation (PV) experiments were carried out using a 90 wt. % water/ethanol mixture with a pilot scale apparatus to test the performance of as-synthesized membranes, maintain the feed flow rate was 200 L·h-1,when the feed temperature was increased to 120℃,the permeation flux could reach 8.6781 kg·m-2·h-1 and the separation factor>1000, which had met the requirements of industrial application.
本论文利用SEM、XRD以及渗透蒸发等表征手段寻求在大孔载体管上制备出高性能的NaA沸石膜。首先分别采用二次修补法和两步涂晶法在长度为25 cm的载体管上制备出高性能的NaA沸石膜,并在两种制备方法的基础上对NaA沸石膜进行放大制备,通过渗透蒸发性能测试,制备的长度为80 cm的NaA沸石分子筛膜具有较好的分离效果,已达到工业化应用的要求。本论文取得的具体成果如下：
(1)采用高浓度合成液配方1Al2O3：2SiO2：2Na2O：120H2O对于低浓度合成液配方1Al2O3：5SiO2：50Na2O：1000H2O合成一次存在小缺陷的膜能够给以很好的修补,对于乙醇含量为90wt.%的乙醇/水体系,在温度为70℃和真空度为200～300 Pa的条件下,其分离系数大于5000,渗透通量最高可达到1.9210 kg·m-2·h-1,而且具有很高重复性。
(2)采用合成液摩尔配比1Al2O3：5SiO2：50Na2O：1000H2O,对于采用两步涂晶后的载体管进行动态水热合成一次就可以获得高性能的NaA沸石分子筛膜。通过渗透蒸发性能测试,在温度为70℃和真空度为200～300 Pa的条件下,对90wt.%水/乙醇混合物进行分离,其分离系数大于10000,渗透通量最高可以达到1.8510 kg·m-2·h-1,且具有很高的重复性。
(3)在大孔a-Al2O3载体管上成功制备出长度为80 cm的NaA沸石分子筛膜,通过渗透蒸发性能测试,对于乙醇浓度为90 wt.%的乙醇/水体系,保持进料流量为200L·h-1,当料液温度升高到120℃,其渗透通量最高可达到8.6781 kg·m-2·h-1,而且分离系数大于1000,已能够满足工业化应用要求。
Pervaporation has received widely attention as a new type membrane separation in recent years, because it is an effective and energy-efficient technology compared with conventional separation process.NaA zeolite membranes have become ideal materials on dehydration of organic by pervaporation due to its high hydrophilicity and small pore size which range between most organic solvents and water molecules.NaA zeolite membrane has good ethanol/water separation performance, which is expected to be utilized in a hybrid distillation/pervaporation system for bio-ethanol dehydration.
In this thesis, the characterization methods of SEM、XRD and pervaporation were utilized to seek preparation methods of high performance NaA zeolite membrane on macro-porous support. First of all, high performance NaA zeolite membranes with the length of 25 cm were prepared by second repair method and two-step seeding method. NaA zeolite membranes were enlarged preparation on the basis of the previous two methods, which had good pervaporation performance and met the requirements of industrial application. The main conclusions obtained in this thesis were as follows:
(1)NaA zeolite membrane with the defects was repaired well by another high concentration formulation 1Al2O3:2SiO2:2Na2O:120H2O,which was dynamic hydrothermally synthesized one time with the formulation 1Al2O3:5SiO2= 50Na2O: 1000H2O.Pervaporation (PV) experiments were carried out at 70℃and 200～300 Pa using a 90 wt.% water/ethanol mixture with a laboratory scale apparatus to test the performance of as-synthesized membranes. They showed the high performance with the water flux up to 1.9210 kg·m-2·h-1 and the separation factor more than 5000.
(2) High performance NaA zeolite membrane was prepared by two-step seeding method, which was dynamic hydrotherrmally synthesized just one time with the formulation 1Al2O3:5SiO2:50Na2O:1000H2O.Pervaporation (PV) experiments were carried out at 70℃and 200～300 Pa using a 90 wt.% water/ethanol mixture with a laboratory scale apparatus to test the performance of as-synthesized membranes.They showed the high performance with the water flux up to 1.8510 kg·m-2·h-1 and the separation factor more than 10000.
(3)NaA zeolite membranes with the length of 80 cm were successfully prepared on the macro-porousα-Al2O3 support. Pervaporation (PV) experiments were carried out using a 90 wt. % water/ethanol mixture with a pilot scale apparatus to test the performance of as-synthesized membranes, maintain the feed flow rate was 200 L·h-1,when the feed temperature was increased to 120℃,the permeation flux could reach 8.6781 kg·m-2·h-1 and the separation factor>1000, which had met the requirements of industrial application.
引文
[1]LIN J, KUMAKIRI I, NAIR B, et al. Microporous Inorganic Membranes [J]. Separation & Purification Methods,2002,31(2):229-379.
[2]张雄福,王金渠,殷德宏,等.用喷涂晶种法合成ZSM-5沸石膜及其影响因素考察[J].催化学报,2000,21(5)：451-455.
[3]黄仲涛,曾昭槐,钟邦克,等.无机膜技术及其应用[M].北京：中国石化出版社,1999.
[4]HSIEH H P. Inorganic Membranes. AIChE Symp.Ser. New York.1988.84(261):1.
[5]徐南平,邢卫红,赵宜江.无机膜技术及应用[M].北京：化学工业出版社,2003.
[6]BURGGRAAF A J, COT L. Fundamentals of Inorganic Membrane Science and Technology. Netherland:Elsevier Science B.V.;1996.
[7]BHAVE R R. Inorganic Membrane:Synthesis, Characteristics and Application. New York:Van Nostrand Reinhold,1991:155-157.
[8]王强兵,汤惠萍,奚正平.多孔金属膜研究进展[J].材料学报,2004,18(6)：26-35.
[9]CASTRICUM H L, SAH A, MITTELMEIJER-HAZELEGER M C, et al. Microporous structure and enhanced hydrophobicity in methylated SiO2 for molecular separation [J]. Journal of Materials Chemistry,2007,17(15):1509-1517.
[10]DE VOS R M, MAIER W F, VERWEIJ H. Hydrophobic silica membranes for gas separation [J]. Journal of Membrane Science,1999,158(1-2):277-288.
[11]LI J, WANG X, WANG L, et al. Preparation of alumina membrane from aluminium chloride [J]. Journal of Membrane Science,2006,275(1-2):6-11.
[12]PETERS T A, FONTALVO J, VORSTMAN M A G, et al. Hollow fibre microporous silica membranes for gas separation and pervaporation:Synthesis, performance and stability [J]. Journal of Membrane Science,2005,248(1-2):73-80.
[13]TAVOLARO A, DRIOLI E. Zeolite Membranes [J]. Advanced Materials,1999,11(12):975-996.
[14]BEIN T. Synthesis and Applications of Molecular Sieve Layers and Membranes [J]. Chemistry of Materials,1996,8(8):1636-1653.
[15]BU X, FENG P, STUCKY G D. Large-Cage Zeolite Structures with Multidimensional 12-Ring Channels [J]. Science,1997,278(5346):2080-2085.
[16]PERSSON A E, SCHOEMAN B J, STERTE J, et al. The synthesis of discrete colloidal particles of TPA-silicalite-1 [J]. Zeolites,14(7):557-567.
[17]TOSHEVA L, VALTCHEV V P. Nanozeolites:Synthesis, Crystallization Mechanism, and Applications [J]. Chemistry of Materials,2005,17(10):2494-2513.
[18]DUVAL J M, FOLKERS B, MULDER M H V, et al. Adsorbent filled membranes for gas separation. Part 1. Improvement of the gas separation properties of polymeric membranes by incorporation of microporous adsorbents [J]. Journal of Membrane Science, 1993,80(1):189-198.
[19]WERNICK D L, OSTERHUBER E J. Permeation through a single crystal of Zeolite NaX [J]. Journal of Membrane Science,1985,22(1):137-146.
[20]TANTEKIN-ERSOLMAZ S B, ATALAY-ORAL C, TATLIER M, et al. Effect of zeolite particle size on the performance of polymer-zeolite mixed matrix membranes [J]. Journal of Membrane Science,2000,175(2):285-288.
[21]WRIGHT C T, PAUL D R. Gas sorption and transport in UV-irradiated polyarylate opolymers based on tetramethyl bisphenol-A and dihydroxybenzophenone [J]. Journal of Membrane Science,1997,124(2):161-174.
[22]FRIBOULET A, DAVID A, THOMAS D. Excitability, memory and oscillations in artificial acetylcholinesterase membranes [J]. Journal of Membrane Science,1981,8(1):33-39.
[23]JIA M, PEINEMANN K-V, BEHLING R-D. Molecular sieving effect of the zeolite-filled silicone rubber membranes in gas permeation [J]. Journal of Membrane Science, 1991,57(2-3):289-292.
[24]JIA M-D, PLEINEMANN K-V, BEHLING R-D. Preparation and characterization of thin-film zeolite-PDMS composite membranes [J]. Journal of Membrane Science,1992,73(2-3):119-128.
[25]HAYHURST D T, PARAVAR A R. Diffusion of Cl to C5 normal paraffins in silicalite [J]. Zeolites,1988,8(1):27-29.
[26]Haag W O, Tsikoyiannis J G; Catalytic conversion over membrane composed of a pure molecular sieve:US,5110478[P/OL].1992. http://www.patentstorm.us/patents/5110478/fulltext.html.
[27]ISHIKAWA A, CHIANG T H, TODA F. Separation of water-alcohol mixtures by permeation through a zeolite membrane on porous glass [J]. Journal of the Chemical Society, Chemical Communications,1989(12):764-765.
[28]BAKKER W J W, VAN DEN BROEKE L J P, KAPTEIJN F, et al. Temperature dependence of one-component permeation through a silicalite-1 membrane [J]. AIChE Journal, 1997,43(9):2203-2214.
[29]BOWEN T C, NOBLE R D, FALCONER J L. Fundamentals and applications of pervaporation through zeolite membranes [J]. Journal of Membrane Science,2004,245(1-2):1-33.
[30]LIN X, CHEN X, KITA H, et al. Synthesis of silicalite tubular membranes by in situ crystallization [J]. AIChE Journal,2003,49(1):237-247.
[31]KUSAKABE K, KURODA T, MOROOKA S. Separation of carbon dioxide from nitrogen using ion-exchanged faujasite-type zeolite membranes formed on porous support tubes [J]. Journal of Membrane Science,1998,148(1):13-23.
[32]王金渠,王国强,江志东,等.ZSM-5沸石膜合成中几个影响因素[J].大连理工大学学报,1998,38(6)：654-658.
[33]BERNAL M P, XOMERITAKIS G, TSAPATSIS M. Tubular MFI zeolite membranes made by secondary (seeded) growth [J]. Catalysis Today,2001,67(1-3):101-107.
[34]LAI R, GAVALAS G R. Surface Seeding in ZSM-5 Membrane Preparation [J]. Industrial & Engineering Chemistry Research,1998,37(11):4275-4283.
[35]MINTOVA S, BEIN T. Microporous Films Prepared by Spin-Coating Stable Colloidal Suspensions of Zeolites [J]. Advanced Materials,2001,13(24):1880-1883.
[36]HUANG A, LIN Y S, YANG W. Synthesis and properties of A-type zeolite membranes by secondary growth method with vacuum seeding [J]. Journal of Membrane Science, 2004,245(1-2):41-51.
[37]CHEN H, LI Y, YANG W. Preparation of silicalite-1 membrane by solution-filling method and its alcohol extraction properties [J]. Journal of Membrane Science,2007,296(1-2):122-130.
[38]张雄福,王金渠,殷德宏,等.用喷涂晶种法合成ZSM-5沸石膜及其影响因素考察[J].催化学报,2000,21(5)：451-454.
[39]杨国辉,张雄福,刘海鸥,等.一种简单组装纳米沸石粒子层的方法及其二次法成膜研究[J].高等学校化学学报,2006,27(9)：1593-1598.
[40]BERENGUER-MURCIA A, MORALLON E, CAZORLA-AMOROS D, et al. Preparation of thin silicalite-1 layers on carbon materials by electrochemical methods [J]. Microporous and Mesoporous Materials,2003,66(2-3):331-340.
[41]LOVALLO M C, TSAPATSIS M, OKUBO T. Preparation of an Asymmetric Zeolite L Film [J]. Chemistry of Materials,1996,8(8):1579-1583.
[42]KONDO M, KOMORI M, KITA H, et al. Tubular-type pervaporation module with zeolite NaA membrane [J]. Journal of Membrane Science,1997,133(1):133-141.
[43]AOKI K, KUSAKABE K, MOROOKA S. Gas permeation properties of A-type zeolite membrane formed on porous substrate by hydrothermal synthesis [J]. Journal of Membrane Science,1998,141(2):197-205.
[44]XU X, YANG W, LIU J, et al. Synthesis of a High-Permeance NaA Zeolite Membrane by Microwave Heating [J]. Advanced Materials,2000,12(3):195-198.
[45]MOTUZAS J, HENG S, ZE LAU P P S, et al. Ultra-rapid production of MFI membranes by coupling microwave-assisted synthesis with either ozone or calcination treatment [J]. Microporous and Mesoporous Materials,2007,99(1-2):197-205.
[46]CASANAVE D, CIAVARELLA P, FIATY K, et al. Zeolite membrane reactor for isobutane dehydrogenation:Experimental results and theoretical modelling [J]. Chemical Engineering Science,1999,54(13-14):2807-2815.
[47]BARBIERI G, MARIGLIANO G, GOLEMME G, et al. Simulation of CO2 hydrogenation with CH3OH removal in a zeolite membrane reactor [J]. Chemical Engineering Journal, 2002,85(1):53-59.
[48]HASEGAWA Y, KUSAKABE K, MOROOKA S. Selective oxidation of carbon monoxide in hydrogen-rich mixtures by permeation through a platinum-loaded Y-type zeolite membrane [J]. Journal of Membrane Science,2001,190(1):1-8.
[49]JAFAR J J, BUDD P M, HUGHES R. Enhancement of esterification reaction yield using zeolite A vapour permeation membrane [J]. Journal of Membrane Science,2002,199(1-2):117-123.
[50]OKAMOTO K-I, KITA H, HORII K. Zeolite NaA Membrane:Preparation, Single-Gas Permeation, and Pervaporation and Vapor Permeation of Water/Organic Liquid Mixtures [J]. Industrial & Engineering Chemistry Research,2000,40(1):163-175.
[51]JAFAR J J, BUDD P M. Separation of alcohol/water mixtures by pervaporation through zeolite A membranes [J]. Microporous Materials,1997,12(4-6):305-311.
[52]徐如人,庞文琴,于吉红,等.分子筛与多孔材料化学[M].北京：科学出版社,2004.
[53]KITA H, FUCHIDA K, HORITA T, et al. Preparation of Faujasite membranes and their permeation properties [J]. Separation and Purification Technology,2001,25(1-3):261-268.
[54]VAN DEN BERG A W C, GORA L, JANSEN J C, et al. Zeolite A membranes synthesized on a UV-irradiated TiO2 coated metal support:the high pervaporation performance [J]. Journal of Membrane Science,2003,224(1-2):29-37.
[55]MORIGAMI Y, KONDO M, ABE J, et al. The first large-scale pervaporation plant using tubular-type module with zeolite NaA membrane [J]. Separation and Purification Technology, 2001,25(1-3):251-260.
[56]PERA-TITUS M, MALLADA R, LLORENS J, et al. Preparation of inner-side tubular zeolite NaA membranes in a semi-continuous synthesis system [J]. Journal of Membrane Science, 2006,278(1-2):401-409.
[57]KONDO M, YAMAMURA T, YUKITAKE T, et al. IPA purification for lens cleaning by vapor permeation using zeolite membrane [J]. Separation and Purification Technology, 2003,32(1-3):191-198.
[58]HAN Y, MA H, QIU S, et al. Preparation of zeolite A membranes by microwave heating [J]. Microporous and Mesoporous Materials,1999,30(2-3):321-326.
[59]CHEN X, YANG W, LIU J, et al. Synthesis of zeolite NaA membranes with high permeance under microwave radiation on mesoporous-layer-modified macroporous substrates for gas separation [J].Journal of Membrane Science,2005,255(1-2):201-211.
[60]LI Y, CHEN H, LIU J, et al. Microwave synthesis of LTA zeolite membranes without seeding [J]. Journal of Membrane Science,2006,277(1-2):230-239.
[61]LI Y, LIU J, YANG W. Formation mechanism of microwave synthesized LTA zeolite membranes [J]. Journal of Membrane Science,2006,281(1-2):646-657.
[62]XU X, YANG W, LIU J, et al. Synthesis of NaA zeolite membrane by microwave heating [J]. Separation and Purification Technology,2001,25(1-3):241-249.
[63]HUANG A, YANG W. Hydrothermal synthesis of NaA zeolite membrane together with microwave heating and conventional heating [J].Materials Letters,2007,61(29):5129-5132.
[64]VANE L M. A review of pervaporation for product recovery from biomass fermentation processes [J]. Journal of Chemical Technology and Biotechnology,2005,80(6):603-629.
[65]张艳艳,熊兴耀,谭兴和,等.燃料乙醇渗透蒸发脱水研究进展[J].酿酒科技,2009,4(178)：87-90.
[66]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.
[67]KAPTEIJN F, BAKKER W J W, ZHENG G, et al. Permeation and separation of light hydrocarbons through a silicalite-1 membrane:Application of the generalized Maxwell-Stefan equations [J]. The Chemical Engineering Journal and the Biochemical Engineering Journal, 1995,57(2):145-153.
[68]KRISHNA R,VAN DEN BROEKE L J P. The Maxwell-Stefan description of mass transport across zeolite membranes [J].The Chemical Engineering Journal and the Biochemical Engineering Journal,1995,57(2):155-162.
[69]VAN DE GRAAF J M, KAPTEIJN F, MOULIJN J A. Modeling permeation of binary mixtures through zeolite membranes [J]. AIChE Journal,1999,45(3):497-511.
[70]VAN DEN BROEKE L J P. Simulation of diffusion in zeolitic structures [J]. AIChE Journal, 1995,41(11):2399-2414.
[71]VAN DEN BROEKE L J P, BAKKER W J W, KAPTEIJN F, et al. Binary permeation through a silicalite-1 membrane [J]. AIChE Journal,1999,45(5):976-985.
[72]NOMURA M, YAMAGUCHI T, NAKAO S I. Ethanol/water transport through silicalite membranes [J]. Journal of Membrane Science,1998,144(1-2):161-171.
[73]NISHIYAMA N, UEYAMA K, MATSUKATA M. Gas permeation through zeolite-alumina composite membranes [J]. AIChE Journal,1997,43(S11):2724-2730.
[74]NOMURA M, YAMAGUCHI T, NAKAO S I. Transport phenomena through intercrystalline and intracrystalline pathways of silicalite zeolite membranes [J]. Journal of Membrane Science, 2001,187(1-2):203-212.
[75]SHAH D, KISSICK K, GHORPADE A, et al. Pervaporation of alcohol-water and dimethylformamide-water mixtures using hydrophilic zeolite NaA membranes:mechanisms and experimental results [J]. Journal of Membrane Science,2000,179(1-2):1.85-205.
[76]SOMMER S, MELIN T. Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1:Dehydration of solvents [J]. Chemical Engineering Science,2005,60(16):4509-4523.
[77]KONDO M, KITA H. Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents [J]. Journal of Membrane Science,361(1-2):223-231.
[78]BECK J S, VARTULI J C, ROTH W J, et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates [J]. Journal of the American Chemical Society, 1992,114(27):10834-10843.
[79]KRESGE C T, LEONOWICZ M E, ROTH W J, et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature,1992,359(6397):710-712.
[80]姜文选,刘炳泗.分子筛复合膜的研究进展与评述[J].抚顺石油学院学报,2000,20(1)：28-33.
[81]http://www.iza-structure.org
[82]黄淼球,程守田,高广立.“偏高岭石-碱-水”体系中4A沸石晶体生长规律及其机理探讨[J].矿物岩石,1997,17(1)：31-32.
[83]周志辉.NaA分子筛膜及分子筛／炭复合膜的制备与应用[D].大连：大连理工大学化工学院,2008.
[84]SATO K, NAKANE T. A high reproducible fabrication method for industrial production of high flux NaA zeolite membrane [J].Journal of Membrane Science,2007,301(1-2):151-161.
[85]张雄福,王金渠.沸石分子筛膜的合成与应用研究进展[J].石油化工,1999,28(4)：266-270.
[86]罗彦,仲盛来,徐南平.NaA型分子筛膜的合成及应用进展[J].化工进展,2004,23(7)：701-704.
[2]张雄福,王金渠,殷德宏,等.用喷涂晶种法合成ZSM-5沸石膜及其影响因素考察[J].催化学报,2000,21(5)：451-455.
[3]黄仲涛,曾昭槐,钟邦克,等.无机膜技术及其应用[M].北京：中国石化出版社,1999.
[4]HSIEH H P. Inorganic Membranes. AIChE Symp.Ser. New York.1988.84(261):1.
[5]徐南平,邢卫红,赵宜江.无机膜技术及应用[M].北京：化学工业出版社,2003.
[6]BURGGRAAF A J, COT L. Fundamentals of Inorganic Membrane Science and Technology. Netherland:Elsevier Science B.V.;1996.
[7]BHAVE R R. Inorganic Membrane:Synthesis, Characteristics and Application. New York:Van Nostrand Reinhold,1991:155-157.
[8]王强兵,汤惠萍,奚正平.多孔金属膜研究进展[J].材料学报,2004,18(6)：26-35.
[9]CASTRICUM H L, SAH A, MITTELMEIJER-HAZELEGER M C, et al. Microporous structure and enhanced hydrophobicity in methylated SiO2 for molecular separation [J]. Journal of Materials Chemistry,2007,17(15):1509-1517.
[10]DE VOS R M, MAIER W F, VERWEIJ H. Hydrophobic silica membranes for gas separation [J]. Journal of Membrane Science,1999,158(1-2):277-288.
[11]LI J, WANG X, WANG L, et al. Preparation of alumina membrane from aluminium chloride [J]. Journal of Membrane Science,2006,275(1-2):6-11.
[12]PETERS T A, FONTALVO J, VORSTMAN M A G, et al. Hollow fibre microporous silica membranes for gas separation and pervaporation:Synthesis, performance and stability [J]. Journal of Membrane Science,2005,248(1-2):73-80.
[13]TAVOLARO A, DRIOLI E. Zeolite Membranes [J]. Advanced Materials,1999,11(12):975-996.
[14]BEIN T. Synthesis and Applications of Molecular Sieve Layers and Membranes [J]. Chemistry of Materials,1996,8(8):1636-1653.
[15]BU X, FENG P, STUCKY G D. Large-Cage Zeolite Structures with Multidimensional 12-Ring Channels [J]. Science,1997,278(5346):2080-2085.
[16]PERSSON A E, SCHOEMAN B J, STERTE J, et al. The synthesis of discrete colloidal particles of TPA-silicalite-1 [J]. Zeolites,14(7):557-567.
[17]TOSHEVA L, VALTCHEV V P. Nanozeolites:Synthesis, Crystallization Mechanism, and Applications [J]. Chemistry of Materials,2005,17(10):2494-2513.
[18]DUVAL J M, FOLKERS B, MULDER M H V, et al. Adsorbent filled membranes for gas separation. Part 1. Improvement of the gas separation properties of polymeric membranes by incorporation of microporous adsorbents [J]. Journal of Membrane Science, 1993,80(1):189-198.
[19]WERNICK D L, OSTERHUBER E J. Permeation through a single crystal of Zeolite NaX [J]. Journal of Membrane Science,1985,22(1):137-146.
[20]TANTEKIN-ERSOLMAZ S B, ATALAY-ORAL C, TATLIER M, et al. Effect of zeolite particle size on the performance of polymer-zeolite mixed matrix membranes [J]. Journal of Membrane Science,2000,175(2):285-288.
[21]WRIGHT C T, PAUL D R. Gas sorption and transport in UV-irradiated polyarylate opolymers based on tetramethyl bisphenol-A and dihydroxybenzophenone [J]. Journal of Membrane Science,1997,124(2):161-174.
[22]FRIBOULET A, DAVID A, THOMAS D. Excitability, memory and oscillations in artificial acetylcholinesterase membranes [J]. Journal of Membrane Science,1981,8(1):33-39.
[23]JIA M, PEINEMANN K-V, BEHLING R-D. Molecular sieving effect of the zeolite-filled silicone rubber membranes in gas permeation [J]. Journal of Membrane Science, 1991,57(2-3):289-292.
[24]JIA M-D, PLEINEMANN K-V, BEHLING R-D. Preparation and characterization of thin-film zeolite-PDMS composite membranes [J]. Journal of Membrane Science,1992,73(2-3):119-128.
[25]HAYHURST D T, PARAVAR A R. Diffusion of Cl to C5 normal paraffins in silicalite [J]. Zeolites,1988,8(1):27-29.
[26]Haag W O, Tsikoyiannis J G; Catalytic conversion over membrane composed of a pure molecular sieve:US,5110478[P/OL].1992. http://www.patentstorm.us/patents/5110478/fulltext.html.
[27]ISHIKAWA A, CHIANG T H, TODA F. Separation of water-alcohol mixtures by permeation through a zeolite membrane on porous glass [J]. Journal of the Chemical Society, Chemical Communications,1989(12):764-765.
[28]BAKKER W J W, VAN DEN BROEKE L J P, KAPTEIJN F, et al. Temperature dependence of one-component permeation through a silicalite-1 membrane [J]. AIChE Journal, 1997,43(9):2203-2214.
[29]BOWEN T C, NOBLE R D, FALCONER J L. Fundamentals and applications of pervaporation through zeolite membranes [J]. Journal of Membrane Science,2004,245(1-2):1-33.
[30]LIN X, CHEN X, KITA H, et al. Synthesis of silicalite tubular membranes by in situ crystallization [J]. AIChE Journal,2003,49(1):237-247.
[31]KUSAKABE K, KURODA T, MOROOKA S. Separation of carbon dioxide from nitrogen using ion-exchanged faujasite-type zeolite membranes formed on porous support tubes [J]. Journal of Membrane Science,1998,148(1):13-23.
[32]王金渠,王国强,江志东,等.ZSM-5沸石膜合成中几个影响因素[J].大连理工大学学报,1998,38(6)：654-658.
[33]BERNAL M P, XOMERITAKIS G, TSAPATSIS M. Tubular MFI zeolite membranes made by secondary (seeded) growth [J]. Catalysis Today,2001,67(1-3):101-107.
[34]LAI R, GAVALAS G R. Surface Seeding in ZSM-5 Membrane Preparation [J]. Industrial & Engineering Chemistry Research,1998,37(11):4275-4283.
[35]MINTOVA S, BEIN T. Microporous Films Prepared by Spin-Coating Stable Colloidal Suspensions of Zeolites [J]. Advanced Materials,2001,13(24):1880-1883.
[36]HUANG A, LIN Y S, YANG W. Synthesis and properties of A-type zeolite membranes by secondary growth method with vacuum seeding [J]. Journal of Membrane Science, 2004,245(1-2):41-51.
[37]CHEN H, LI Y, YANG W. Preparation of silicalite-1 membrane by solution-filling method and its alcohol extraction properties [J]. Journal of Membrane Science,2007,296(1-2):122-130.
[38]张雄福,王金渠,殷德宏,等.用喷涂晶种法合成ZSM-5沸石膜及其影响因素考察[J].催化学报,2000,21(5)：451-454.
[39]杨国辉,张雄福,刘海鸥,等.一种简单组装纳米沸石粒子层的方法及其二次法成膜研究[J].高等学校化学学报,2006,27(9)：1593-1598.
[40]BERENGUER-MURCIA A, MORALLON E, CAZORLA-AMOROS D, et al. Preparation of thin silicalite-1 layers on carbon materials by electrochemical methods [J]. Microporous and Mesoporous Materials,2003,66(2-3):331-340.
[41]LOVALLO M C, TSAPATSIS M, OKUBO T. Preparation of an Asymmetric Zeolite L Film [J]. Chemistry of Materials,1996,8(8):1579-1583.
[42]KONDO M, KOMORI M, KITA H, et al. Tubular-type pervaporation module with zeolite NaA membrane [J]. Journal of Membrane Science,1997,133(1):133-141.
[43]AOKI K, KUSAKABE K, MOROOKA S. Gas permeation properties of A-type zeolite membrane formed on porous substrate by hydrothermal synthesis [J]. Journal of Membrane Science,1998,141(2):197-205.
[44]XU X, YANG W, LIU J, et al. Synthesis of a High-Permeance NaA Zeolite Membrane by Microwave Heating [J]. Advanced Materials,2000,12(3):195-198.
[45]MOTUZAS J, HENG S, ZE LAU P P S, et al. Ultra-rapid production of MFI membranes by coupling microwave-assisted synthesis with either ozone or calcination treatment [J]. Microporous and Mesoporous Materials,2007,99(1-2):197-205.
[46]CASANAVE D, CIAVARELLA P, FIATY K, et al. Zeolite membrane reactor for isobutane dehydrogenation:Experimental results and theoretical modelling [J]. Chemical Engineering Science,1999,54(13-14):2807-2815.
[47]BARBIERI G, MARIGLIANO G, GOLEMME G, et al. Simulation of CO2 hydrogenation with CH3OH removal in a zeolite membrane reactor [J]. Chemical Engineering Journal, 2002,85(1):53-59.
[48]HASEGAWA Y, KUSAKABE K, MOROOKA S. Selective oxidation of carbon monoxide in hydrogen-rich mixtures by permeation through a platinum-loaded Y-type zeolite membrane [J]. Journal of Membrane Science,2001,190(1):1-8.
[49]JAFAR J J, BUDD P M, HUGHES R. Enhancement of esterification reaction yield using zeolite A vapour permeation membrane [J]. Journal of Membrane Science,2002,199(1-2):117-123.
[50]OKAMOTO K-I, KITA H, HORII K. Zeolite NaA Membrane:Preparation, Single-Gas Permeation, and Pervaporation and Vapor Permeation of Water/Organic Liquid Mixtures [J]. Industrial & Engineering Chemistry Research,2000,40(1):163-175.
[51]JAFAR J J, BUDD P M. Separation of alcohol/water mixtures by pervaporation through zeolite A membranes [J]. Microporous Materials,1997,12(4-6):305-311.
[52]徐如人,庞文琴,于吉红,等.分子筛与多孔材料化学[M].北京：科学出版社,2004.
[53]KITA H, FUCHIDA K, HORITA T, et al. Preparation of Faujasite membranes and their permeation properties [J]. Separation and Purification Technology,2001,25(1-3):261-268.
[54]VAN DEN BERG A W C, GORA L, JANSEN J C, et al. Zeolite A membranes synthesized on a UV-irradiated TiO2 coated metal support:the high pervaporation performance [J]. Journal of Membrane Science,2003,224(1-2):29-37.
[55]MORIGAMI Y, KONDO M, ABE J, et al. The first large-scale pervaporation plant using tubular-type module with zeolite NaA membrane [J]. Separation and Purification Technology, 2001,25(1-3):251-260.
[56]PERA-TITUS M, MALLADA R, LLORENS J, et al. Preparation of inner-side tubular zeolite NaA membranes in a semi-continuous synthesis system [J]. Journal of Membrane Science, 2006,278(1-2):401-409.
[57]KONDO M, YAMAMURA T, YUKITAKE T, et al. IPA purification for lens cleaning by vapor permeation using zeolite membrane [J]. Separation and Purification Technology, 2003,32(1-3):191-198.
[58]HAN Y, MA H, QIU S, et al. Preparation of zeolite A membranes by microwave heating [J]. Microporous and Mesoporous Materials,1999,30(2-3):321-326.
[59]CHEN X, YANG W, LIU J, et al. Synthesis of zeolite NaA membranes with high permeance under microwave radiation on mesoporous-layer-modified macroporous substrates for gas separation [J].Journal of Membrane Science,2005,255(1-2):201-211.
[60]LI Y, CHEN H, LIU J, et al. Microwave synthesis of LTA zeolite membranes without seeding [J]. Journal of Membrane Science,2006,277(1-2):230-239.
[61]LI Y, LIU J, YANG W. Formation mechanism of microwave synthesized LTA zeolite membranes [J]. Journal of Membrane Science,2006,281(1-2):646-657.
[62]XU X, YANG W, LIU J, et al. Synthesis of NaA zeolite membrane by microwave heating [J]. Separation and Purification Technology,2001,25(1-3):241-249.
[63]HUANG A, YANG W. Hydrothermal synthesis of NaA zeolite membrane together with microwave heating and conventional heating [J].Materials Letters,2007,61(29):5129-5132.
[64]VANE L M. A review of pervaporation for product recovery from biomass fermentation processes [J]. Journal of Chemical Technology and Biotechnology,2005,80(6):603-629.
[65]张艳艳,熊兴耀,谭兴和,等.燃料乙醇渗透蒸发脱水研究进展[J].酿酒科技,2009,4(178)：87-90.
[66]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.
[67]KAPTEIJN F, BAKKER W J W, ZHENG G, et al. Permeation and separation of light hydrocarbons through a silicalite-1 membrane:Application of the generalized Maxwell-Stefan equations [J]. The Chemical Engineering Journal and the Biochemical Engineering Journal, 1995,57(2):145-153.
[68]KRISHNA R,VAN DEN BROEKE L J P. The Maxwell-Stefan description of mass transport across zeolite membranes [J].The Chemical Engineering Journal and the Biochemical Engineering Journal,1995,57(2):155-162.
[69]VAN DE GRAAF J M, KAPTEIJN F, MOULIJN J A. Modeling permeation of binary mixtures through zeolite membranes [J]. AIChE Journal,1999,45(3):497-511.
[70]VAN DEN BROEKE L J P. Simulation of diffusion in zeolitic structures [J]. AIChE Journal, 1995,41(11):2399-2414.
[71]VAN DEN BROEKE L J P, BAKKER W J W, KAPTEIJN F, et al. Binary permeation through a silicalite-1 membrane [J]. AIChE Journal,1999,45(5):976-985.
[72]NOMURA M, YAMAGUCHI T, NAKAO S I. Ethanol/water transport through silicalite membranes [J]. Journal of Membrane Science,1998,144(1-2):161-171.
[73]NISHIYAMA N, UEYAMA K, MATSUKATA M. Gas permeation through zeolite-alumina composite membranes [J]. AIChE Journal,1997,43(S11):2724-2730.
[74]NOMURA M, YAMAGUCHI T, NAKAO S I. Transport phenomena through intercrystalline and intracrystalline pathways of silicalite zeolite membranes [J]. Journal of Membrane Science, 2001,187(1-2):203-212.
[75]SHAH D, KISSICK K, GHORPADE A, et al. Pervaporation of alcohol-water and dimethylformamide-water mixtures using hydrophilic zeolite NaA membranes:mechanisms and experimental results [J]. Journal of Membrane Science,2000,179(1-2):1.85-205.
[76]SOMMER S, MELIN T. Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1:Dehydration of solvents [J]. Chemical Engineering Science,2005,60(16):4509-4523.
[77]KONDO M, KITA H. Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents [J]. Journal of Membrane Science,361(1-2):223-231.
[78]BECK J S, VARTULI J C, ROTH W J, et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates [J]. Journal of the American Chemical Society, 1992,114(27):10834-10843.
[79]KRESGE C T, LEONOWICZ M E, ROTH W J, et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism [J]. Nature,1992,359(6397):710-712.
[80]姜文选,刘炳泗.分子筛复合膜的研究进展与评述[J].抚顺石油学院学报,2000,20(1)：28-33.
[81]http://www.iza-structure.org
[82]黄淼球,程守田,高广立.“偏高岭石-碱-水”体系中4A沸石晶体生长规律及其机理探讨[J].矿物岩石,1997,17(1)：31-32.
[83]周志辉.NaA分子筛膜及分子筛／炭复合膜的制备与应用[D].大连：大连理工大学化工学院,2008.
[84]SATO K, NAKANE T. A high reproducible fabrication method for industrial production of high flux NaA zeolite membrane [J].Journal of Membrane Science,2007,301(1-2):151-161.
[85]张雄福,王金渠.沸石分子筛膜的合成与应用研究进展[J].石油化工,1999,28(4)：266-270.
[86]罗彦,仲盛来,徐南平.NaA型分子筛膜的合成及应用进展[J].化工进展,2004,23(7)：701-704.