有机功能化α-Al2O3陶瓷中空纤维表面合成高性能分离氢用NaA分子筛膜

通过浸渍3-氨丙基甲基二乙氧基硅烷(ADMS)对α-Al₂O₃中空纤维载体进行有机功能化改性, 使载体表面带正电, 利用NaA分子筛晶种负电性与功能化载体之间的静电吸附机理进行预涂晶种, 采用微波加热-二次生长法于载体表面合成了NaA分子筛膜. 采用X射线衍射(XRD)、zeta 电位、扫描电子显微镜(SEM)等分析手段和气体渗透实验对NaA分子筛膜进行了表征. 考察了未改性NaA分子筛膜与改性NaA分子筛膜的形貌、结构和气体渗透性能差异. XRD结果表明载体表面只有NaA分子筛生成; zeta 电位分析表明NaA分子筛晶种及分子筛前驱体与有机功能化载体电位相反, 存在静电吸附作用; SEM结果显示改性NaA分子筛膜表面颗粒相互联结呈孪生态, 膜厚约5 μm, 膜层致密、均匀、平整; 在不同温度下对H₂、O₂、N₂和C₃H₈进行气体渗透测试,35 °C条件下改性NaA分子筛膜对H₂的渗透率仅为3.6×10^-7 mol·m^-2·s^-1·Pa^-1, 较未改性NaA分子筛膜的渗透率(4.0×10^-7 mol·m^-2·s^-1·Pa^-1)低, 而改性NaA分子筛膜的H₂/C₃H₈理想分离系数则高达11.25, 远大于未改性NaA分子筛膜的H₂/C₃H₈理想分离系数(5.06).     

NaA Zeolite Membrane with High Performance Synthesized by Vapor Phase Transformation Method

IntroductionZeolitemembranes ,asaremarkablebranchofinor ganicmembrane ,havepotentialadvantagesinmanyappli cationssuchascatalysisandseparation ,chemicalsensors ,ascousticwavedevices ,andmicroelectronicdevicesduetotheiruniformporesizeatthemolecularlevelandresis tancetohightemperature .1 5For 10years ,manyre searchershavepaidconsiderableattentiontosynthesisofzeolitemembraneswithhighperformance .Amongthere portedzeolitemembranes ,mostattentionwasfocusedonsynthesisofMFI typezeolitemembranebecausei…     

Effect of sol–gel-based silica buffer layer on the formation of NaA zeolite membrane

The support substrates were modified with sol?Cgel-based silica coating as intermediate buffer layer followed by NaA zeolite seed (prepared hydrothermally at 85?°C for 3?h) coating with 2?wt% aqueous dispersion. The secondary crystallization of NaA zeolite in the silica-seed-coated supports was carried out hydrothermally through crystal growth process at 65?°C for 4 and 8?h (single-stage each), (6?+?4) and (6?+?6)?h (double-stage each), and (6?+?4?+?2) and (6?+?4?+?4)?h (triple-stage each). The crystallization behaviours of the prepared NaA membranes were studied by X-ray diffraction, and the microstructures of the same films were observed by field emission scanning electron microscope. The efficiency of the membranes was tested with gas permeation study. The double-stage secondary crystallization at 65?°C for (6?+?4)?h showed highly interlocked NaA grains in the membrane and it rendered the permeance values of 3.7?×?10^?8?mol?m^?2?s^?1?Pa^?1 and 15.9?×?10^?8 for single gas, nitrogen (N₂) and hydrogen (H₂) respectively with the ideal selectivity of 4.3.     

Facile preparation of compact LTA molecular sieve membranes on polyethyleneimine modified substrates

A facile preparation strategy was proposed for preparation of compact zeolite LTA membranes on polyethyleneimine(PEI) modified substrates without seeding.Through the functionalization of substrates by using PEI,compact LTA membranes can be formed on various kinds of substrates.A well-intergrown and phase-pure LTA membrane with a thickness of about 3.0 μm is successfully prepared on the a-Al_2 O_3 disk after crystallization for 24 h at 60℃.Besides LTA membrane,wellintergrown zeolite FAU membranes can also be formed on PEI-modified a-Al_2 O_3 substrates,suggesting the universality of this strategy.The zeolite LTA membranes synthesized on PEI-modified a-Al_2 O_3 tubes we re evaluated fo r the separation of alcohols/water mixture through pervaporation.The as-synthesized zeolite LTA membranes display high pervaporation performances.For the separation of 10 wt% isopropanol/water solution at 90℃,a high separation factor of44991 and a water flux of 1.73 kg m ~2 h ~1 are achieved.     

Preparation of uniform and nano‐sized NaA zeolite using silatrane and alumatrane precursors

Nano‐sized Na A zeolite was successfully synthesized via the sol–gel process and microwave techniques. The synthesis parameters, such as hydroxide ion concentration, seed amount, as well as heating time and temperature, were studied to obtain the most uniform and very small sized NaA zeolite using the composition of SiO₂:Al₂O₃:xNa₂O:410H₂O; 3 ≤ x ≤ 6. It was found that hydroxide ion concentration affects the crystal size and heating time, whereas a higher amount of seed provides smaller sized NaA zeolite. The zeolite product can be synthesized using a higher temperature for a shorter time or lower temperature for a longer time. The best conditions for synthesizing the smallest size, 0.1–0.2 µm, and the most homogeneous NaA zeolite is to use the composition of SiO₂:Al₂O₃:3Na₂O:410H₂O and 3 wt% crystal seed at 80 °C microwave heating for 6 h. The synthesized NaA zeolite was characterized using XRD and SEM. Copyright © 2006 John Wiley & Sons, Ltd.     

在多孔γ-Al2O3氧化铝载体上微波合成NaA分子筛膜及气体渗透分离性能

The paper presented novel synthesis of NaA zeolite membrane with good performance using microwave heating. The method involved two steps, prior seeding 120 nm of LTA crystals on substrate and then employing a secondary hydrothermal synthesis. Effects of seeding times, synthesis time and synthesis times were investigated in this work. The quality evaluation of membranes respectively used single component gases (HE and N2) and H2/N2 (equivalent volume) mixture. The ideal H2,/N2 selectivity increased from 1.90 of the substrate to 6.37 of the three-stage synthesized membrane, which was distinctly higher than the corresponding Knudsen diffusion selectivity of 3.74. However, the real H2/N2 selectivity of the three-stage synthesis was much lower than the corresponding ideal selectivity and close to the corresponding Knudsen diffusion selectivity of 3.74.     

Preparation and application of zeolite/ceramic microfiltration membranes for treatment of oil contaminated water

NaA zeolite microfiltration (MF) membranes were prepared on α-Al₂O₃ tube by in situ hydrothermal synthesis method and investigated for water separation and recovery from oily water. NaA/α-Al₂O₃ MF membranes with average inter-particle pore sizes of 1.2 μm, 0.4 μm and 0.2 μm were prepared. The membranes were characterized by scanning electron microscope (SEM) and the inter-particle pore size distribution (PSD) was determined by gas bubble pressure method. Membranes with pore sizes of 1.2 μm (NaA1) and 0.4 μm (NaA2) were used to treat an oil-in-water emulsion containing 100 mg/L oil. Better than 99% oil rejection was obtained and water containing less than 1 mg/L oil was produced at 85 L m⁻² h⁻¹ by NaA1 at a membrane pressure of 50 kPa. Consistent membrane performance was maintained by a regeneration regime consisting of frequent backwash with hot water and alkali solution.     

含氟体系中高性能T型分子筛膜的合成

含氟体系中,在负载晶种的大孔莫来石支撑体表面快速合成了高性能且取向生长的T型分子筛膜。采用XRD、SEM和MAS NMR等手段对分子筛膜层和粉末进行表征。讨论了添加物、氟硅比、合成温度和合成时间等条件对膜生长与分离性能的影响,并阐述了含氟体系中T型分子筛膜快速晶化的机理。碱金属氟盐的加入促进了T型分子筛晶体层的晶化速率,并对晶体层形貌产生了一定的影响。膜应用于75℃、水/异丙醇(10∶90,w/w)体系的平均渗透通量和分离因子分别为(4.91±0.18)kg·m-2·h-1和7 060±1 130。     

清液体系中T型分子筛膜的高重复性合成与渗透汽化性能

以自制微米级分子筛为晶种,在清液体系中成功合成出高性能的T型分子筛膜,考察了硅铝比、水硅比、碱度及合成温度与时间等条件对膜的生长和渗透汽化性能的影响.结果表明,在摩尔组成为1SiO₂:0.015Al₂O₃:0.41(Na₂O+K₂O):30H₂O的清液体系中,于423K晶化6h的条件下可较快地形成一层厚度为5μm的连续致密纯相T型分子筛膜,较大缩短了膜合成时间且提高了膜致密性.在优化条件下所合成的膜具有优良的分离性能和高重复性.348K时,在10wt%水-90wt%异丙醇混合物体系中膜的渗透通量和分离因子分别高达4.20kg/(m²·h)和7800.     

含氟体系中高性能T型分子筛膜的合成

含氟体系中,在负载晶种的大孔莫来石支撑体表面快速合成了高性能且取向生长的T型分子筛膜。采用XRD、SEM和MASNMR等手段对分子筛膜层和粉末进行表征。讨论了添加物、氟硅比、合成温度和合成时间等条件对膜生长与分离性能的影响,并阐述了含氟体系中T型分子筛膜快速晶化的机理。碱金属氟盐的加入促进了T型分子筛晶体层的晶化速率,并对晶体层形貌产生了一定的影响。膜应用于75℃、水/异丙醇（10：90,w/w）体系的平均渗透通量和分离因子分别为（4.91±0.18）kg·m^-2·h^-1和7060±1130。     

澄清溶液中NaA型分子筛膜的合成及气体渗透性能

The use of zeolite membranes in separation or combined reaction and separation processes is very attractive. Advantages of using such a type of membranes include their ability to discriminate molecules based on the molecular size and their stability[1]. In the past ten years, most efforts were involved in the synthesis and permeation studies of MFI zeolite membrane[2, 3]. Recently, NaA zeolite membrane has attracted much attention because of its high potential in the dehydration of organic liquids[4]. However, few gas permeation results were reported[5]. Furthermore, most of the NaA zeolite membrane was synthesized from gel[4]. In this letter, the synthesis of NaA zeolite membrane from clear solution and its gas permeation properties are reported.     

A Uniformly Oriented MFI Membrane for Improved CO2 Separation

Membrane separation of CO₂ from natural gas, biogas, synthesis gas, and flu gas is a simple and energy‐efficient alternative to other separation techniques. But results for CO₂‐selective permeance have always been achieved by randomly oriented and thick zeolite membranes. Thin, oriented membranes have great potential to realize high‐flux and high‐selectivity separation of mixtures at low energy cost. We now report a facile method for preparing silica MFI membranes in fluoride media on a graded alumina support. In the resulting membrane straight channels are uniformly vertically aligned and the membrane has a thickness of 0.5 μm. The membrane showed a separation selectivity of 109 for CO₂/H₂ mixtures and a CO₂ permeance of 51×10^?7 mol m^?2 s^?1 Pa^?1 at ?35 °C, making it promising for practical CO₂ separation from mixtures.     

Nanofiltration-like forward osmosis membranes on in-situ mussel-modified polyvinylidene fluoride porous substrate for efficient salt/dye separation

Here, polyvinylidene fluoride (PVDF) membranes were fabricated via non-solvent induced phase separation (NIPS) using dopamine (DA) and polyethyleneimine (PEI) as the hydrophilic additives, which has a loose surface and somewhat improved hydrophilicity. Then nanofiltration (NF)-like thin-film composite forward osmosis (TFC FO) membrane with a loose polyamide (PA) active layer on the blend membrane was synthesized via the interfacial polymerization. The as-prepared NF-like TFC FO membrane exhibited a high water flux (J_w) of 29.98 L m⁻² h⁻¹ and a much low specific salt flux (J_s/J_w) of 0.018 g/L, when 0.6 M NaCl was used as draw solution (DS). It had a superior rejection of malachite green (99.6% ± 0.1%) and a low rejection of NaCl (27.4% ± 4.2%), when filtrated malachite green/NaCl mixture solution in active layer-facing draw solution (AL-FS) mode. The results provide new insights on the design and preparation of FO membranes of selective separation for dyes from salty water.     

Water-alcohol Separation by Pervaporation through Zeolite Modified Poly(amidesulfonamide)s (PASAs)

A series of poly(amidesulfonamide)s (PASAs) which have been synthesized in our laboratory possess good membrane fabrication properties^[1]. The potential use of these membrane materials in RO, UF and PV were demonstrated^[2,3]. Reminiscent to the PV performance of other glassy polymers, most of these materials exhibit a fairly high separation factor albeit a permeation flux below 35 g m^-2 h^-1 in the PV separation of aqueous alcohol mixtures. To have a real application prospect in PV, the permeation flux through the membranes has to e further improved. The present work represents our effort to upgrade the separation characteristics of PASAs by blending with inert hydrophilic zeolites. Three types of PASAs (structure shown in Figure 1) were selected to be fabricated by blending different amount of zeolite NaA or NaX. The zeolite filled membranes were characterized by SEM, IR spectroscopy, sorption measurements and wide-angle X-ray diffraction. By adding proper amount of NaA into the polymer casting solutions, the resultant zeolite filled membranes exhibited improvement in both selectivity and permeability in the separation of 10% aqueous solutions of ethanol, propan-l-ol and propan-2-ol, as compared to the zeolite free membrane (Table 1).     

Pervaporation with chitosan membranes II. Blend membranes of chitosan and polyacrylic acid and comparison of homogeneous and composite membrane based on polyelectrolyte complexes of chitosan and polyacrylic acid for the separation of ethanol-water mixtures

Three different types of blend membranes based on chitosan and polyacrylic acid were prepared from homogeneous polymer solution and their performance on the pervaporation separation of water-ethanol mixtures was investigated. It was found that all membranes are highly water-selective. The temperature dependence of membrane permselectivity for the feed solutions of higher water content (>30 wt%) was unusual in that both permeability and separation factor increased with increase in temperature. This phenomenon might be explained from the aspect of activation energy and suggested that the sorption contribution to activation energy of permeation should not always be ignored when strong interaction occurs in the pervaporation membrane system.A comparison of pervaporation performance between composite and homogeneous membranes was also studied. Typical pervaporation results at 30°C for a 95 wt% ethanol aqueous solution were: for the homogeneous membrane, permeation flux = 33 g/m² h, separation factor = 2216; and for the composite membrane, permeation flux = 132 g/m² h, separation factor = 1008. A transport model consisting of dense layer and porous substrate in series was developed to describe the effect of porous substrate on pervaporation performance.     

Zeolitic Imidazolate Framework/Graphene Oxide Hybrid Nanosheets as Seeds for the Growth of Ultrathin Molecular Sieving Membranes

A defect‐free zeolitic imidazolate framework‐8 (ZIF‐8)/graphene oxide (GO) membrane with a thickness of 100 nm was prepared using two‐dimensional (2D) ZIF‐8/GO hybrid nanosheets as seeds. Hybrid nanosheets with a suitable amount of ZIF‐8 nanocrystals were essential for producing a uniform seeding layer that facilitates fast crystal intergrowth during membrane formation. Moreover, the seeding layer acts as a barrier between two different synthesis solutions, and self‐limits crystal growth and effectively eliminates defects during the contra‐diffusion process. The resulting ultrathin membranes show excellent molecular sieving gas separation properties, such as with a high CO₂/N₂ selectivity of 7.0. This 2D nano‐hybrid seeding strategy can be readily extended to the fabrication of other defect‐free and ultrathin MOF or zeolite molecular sieving membranes for a wide range of separation applications.     

Preparation and catalytic activity of titanium silicalite-1 zeolite membrane with TPABr as template

The preparation of the supported titanium silicalite-1 (TS-1) zeolite membrane with inexpensive tetrapropylammonium bromide (TPABr)/weak base synthesis system was studied by three methods, and the catalytic activity of the obtained TS-1 zeolite membrane was evaluated with the oxidation of 2-propanol (IPA) under pervaporation condition. It was found that TS-1 zeolite membrane could be successfully prepared with “seeding” or “seeding in situ” method, but could not be achieved with “in situ” method. Adding a little amount of promoter ions of PO₄³⁻ into the synthesis gel was of benefit to the catalytic activity of the prepared TS-1 zeolite membrane, but had no obvious effect on the membrane layer formation on the mullite porous support. For “seeding” method, the membrane prepared with the synthesis gel having molar composition of SiO₂:0.1TPABr:0.9Et₂NH:0.03TiO₂:80H₂O:0.06H₃PO₄ at 150 °C for 48 h showed the highest oxidation conversion of IPA of 72% accompanied by a flux of 0.35 kg/m² h. Further more, much higher IPA oxidation conversion of 76% accompanied by a flux of 0.65 kg/m² h was obtained for the TS-1 zeolite membrane prepared with the same synthesis gel by “seeding in situ” method at 150 °C for 72 h.     

MFI纳米片沉积层气相转化制备超薄b轴取向沸石膜

利用乙二胺-水蒸汽进行气相转化（VPT）制备超薄、取向MFI沸石膜,通过将MFI纳米片沉积层转化为致密的沸石膜,实现了膜厚度的有效控制。扫描电子显微镜和X射线衍射表明,制备的沸石膜膜厚度约为280 nm,具有高度b轴取向的致密结构。丁烷异构体双组分分离测试结果表明,在333 K下,等物质的量的正丁烷/异丁烷混合物的正丁烷渗透速率和分离因子分别为1.5×10^-7 mol·m^-2·s^-1·Pa^-1和14.8。Na₂SiO₃作为低聚硅源在MFI沸石纳米片二次生长过程中能够提供硅源和碱度,通过在胺类蒸汽中实现MFI沸石纳米片间的融合生长,进一步提高了膜的取向度和致密性。     

MFI纳米片沉积层气相转化制备超薄b轴取向沸石膜

利用乙二胺-水蒸汽进行气相转化(VPT)制备超薄、取向MFI沸石膜,通过将MFI纳米片沉积层转化为致密的沸石膜,实现了膜厚度的有效控制。扫描电子显微镜和X射线衍射表明,制备的沸石膜膜厚度约为280 nm,具有高度b轴取向的致密结构。丁烷异构体双组分分离测试结果表明,在333 K下,等物质的量的正丁烷/异丁烷混合物的正丁烷渗透速率和分离因子分别为1.5×10^-7 mol·m^-2·s^-1·Pa^-1和14.8。Na₂SiO₃作为低聚硅源在MFI沸石纳米片二次生长过程中能够提供硅源和碱度,通过在胺类蒸汽中实现MFI沸石纳米片间的融合生长,进一步提高了膜的取向度和致密性。