Effect of substrate curvature on microstructure and gas permeability of hollow fiber MFI zeolite membranes

Literature data show that gas permeability of MFI zeolite membrane varies depending on the geometry of supports. The present work investigates the effects of the surface curvature of substrates on the microstructure and the gas permeation property of supported zeolite membranes. MFI zeolite membranes were grown on porous alumina hollow fibers with different diameters (surface curvature) by the secondary growth method. Single gas permeation and H₂/CO₂ binary gas separation from 25 to 300 were conducted to study the membrane quality. The zeolite membranes on supports of larger surface curvature have higher permeability and lower selectivity due to the presence of more inter‐crystalline gaps in the zeolite layer formed during the template removal step. The effects of the support surface curvature (and geometry) on zeolite membrane microstructure and gas permeation characteristics are semi‐quantitatively analyzed by a transport model considering both structural change and gas diffusion in micropores. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3419–3428, 2018     

Ethanol/water mixture pervaporation performance of b‐oriented silicalite‐1 membranes made by gel‐free secondary growth

b‐oriented silicalite‐1 membranes on porous silica supports were synthesized using gel‐free secondary growth. The porous silica supports were made by pressing crushed quartz fibers followed by sintering and polishing, and further modified by slip‐coating three layers of Stöber silica particles (1000, 350, and 50 nm). The b‐oriented seed layers were prepared by rubbing silicalite‐1 particles (2 μm × 0.8 μm × 3 μm along a‐, b‐, and c‐axis, respectively) after depositing a polymeric layer on the support. After silicalite‐1 seed deposition, a final coating of spherical silica particles was applied. Well‐intergrown, μm‐thick, b‐oriented membranes were obtained, which, after calcination, exhibited ethanol permselectivity in ethanol/water mixture pervaporation. At 60°C and for ～5 wt % ethanol/water mixtures, the best membrane exhibited overall pervaporation separation factor of 85 (corresponding to membrane intrinsic selectivity of 7.7) and total flux of 2.1 kg/(m²·h). This performance is comparable to the best performing MFI membranes reported in the literature. © 2015 American Institute of Chemical Engineers AIChE J, 62: 556–563, 2016     

动态水热法制备Silicalite-1分子筛膜包覆多孔缺陷Al2O3微球

采用晶种涂覆-预晶化-晶化成膜的动态水热法成功在具有多孔缺陷的氧化铝微球上合成Silicalite-1分子筛膜。以乙醇作为润湿试剂在氧化铝表面涂覆一层晶种,将涂覆过晶种的载体加入到分子筛合成液中预晶化,一层分子筛完全覆盖载体并与载体结合牢固。预晶化后的载体在动态水热条件下处理3天,得到致密分子筛膜包覆的Al₂O₃微球。运用X射线衍射（XRD）和扫描电镜（SEM）对所得材料进行表征。结果表明,包覆的分子筛膜具有典型的MFI结构,晶粒交互生长,厚度约为3μm。考察了TPAOH用量和水量对分子筛膜微观结构的影响,结果发现TPAOH用量主要影响Silicalite-1分子筛膜的形貌,当TPAOH用量为0.17时,合成的Silicalite-1分子筛膜连续致密,而水量对分子筛膜微观结构的影响较小。这种晶种涂覆-预晶化-晶化成膜的方法有助于在多孔缺陷的Al₂O₃微球上制备高质量的分子筛膜。     

ZrO2 和Al2O3支撑的MFI 型沸石分子筛膜:支撑体材料对膜性能的影响

采用水热合成法，以纯SiO2为源物质，在介孔Y2O3掺杂的ZrO2(YZ)及大孔α-Al2O3支撑体上制备出高质量的MFI型沸石分子筛膜，通过H2／n-C4H10气体混合物的渗透分离和p-xylene的蒸发研究了不同支撑体上MFI型沸石分子筛膜分离性能，在较低温度范围，YZ支撑的MFI型沸石分子筛膜中n-C4H10的渗透率比Al2O3支撑的膜高很多，最大n-C4H10与H2的分离率达到500，Al2O3支撑的膜中py-xylene的蒸发流量随时间下降很快，而YZ支撑的膜中的蒸发流量则变化缓慢，用XRD对膜的晶体结构进行分析，通过多种温度下热处理不同支撑体上的膜样品研究了其热稳定性与支持体材料的关系，YZ支撑的MFI型沸石分子筛膜的MFI结构在1000摄氏度后仍能保持，而Al2O3支撑的膜950摄氏度时已完全转变为石英相，研究结果表明，YZ支撑的MFI型沸石分子筛膜比Al2O3支撑的膜表现出更好的厌不性，热稳定性以及抗阻塞性。     

纳米片Ga-MFI分子筛合成及其对航空燃油催化裂解反应中低碳烯烃选择性的影响

在纳米片Al-MFI分子筛合成的基础上,以镓源[Ga(NO₃)₃·xH₂O]替换铝源[Al₂(SO₄)₃·18H₂O],合成出类质同象纳米片Ga-MFI分子筛,采用X射线衍射、扫描电镜、BET比表面积分析和NH₃程序升温脱附法等技术对其进行了表征,并考察了普通ZSM-5分子筛、纳米片Al-MFI分子筛和纳米片Ga-MFI分子筛对航空燃油裂解反应的催化性能。结果表明,合成的分子筛是具有MFI骨架拓扑结构的纳米片状分子筛,具有较大的比表面积（482m²/g）和中孔孔容;与铝原子相比,镓原子与硅、氧原子形成的酸性位点的酸性减弱。在高温下（600℃）,它抑制了氢转移反应的进行,减少了低碳烯烃的二次反应和结焦前体（芳香烃）在酸性位点上的吸附,使其具有更高催化活性和低碳烯烃选择性,从而获得了比纳米片Al-MFI分子筛高14.47%的热沉。该研究为高超音速飞行器的主动热防护提供了技术支撑。     

On the effect of morphological features on the properties of MFI zeolite membranes

MFI type zeolite membranes were prepared on alumina and stainless steel tubular supports by different synthesis procedures, giving rise to different zeolite layer structures and distributions of zeolite material with respect to the support. This was used as a base to establish a classification of zeolite membranes. SEM and EPMA analysis showed clear differences among different types of MFI zeolite membranes, concerning the morphology and location of the zeolite deposits. Three types of membranes were identified, namely: type-A membranes, in which the zeolitic material was located mainly inside the support pores; type-B membranes, with a thin layer of randomly oriented crystals on top of the support; and type-C corresponding to MFI c-oriented membranes. These morphological differences translated into diverse qualitative and quantitative behavior of the corresponding membranes, as shown by the evolution of single-gas permeances and separation selectivity with temperature, and by adsorption and temperature-programmed desorption experiments.     

Modification of pillared MFI zeolite nanosheets by nitridation with tailored activity in benzylation of mesitylene and benzyl alcohol

The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH₃ atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), pyridine-IR spectroscopy and N₂ adsorption–desorption isotherms. The analyses showed that the nitridation didn't destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Brønsted-to-Lewis (B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Brønsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Brønsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.     

Preparation of high‐performance zeolite NaA membranes in clear solution by adding SiO2 into Al2O3 hollow‐fiber precursor

Zeolite NaA membranes were prepared in a clear synthesis solution without the aid of nanoseeds. To improve the properties of the membranes formed in a clear solution, alumina hollow fibers were fabricated by adding silica powder to the conventional spinning slurry, resulting in hollow fibers with a mullite phase. Prior to the membrane synthesis, the hollow fibers were pretreated by dipping in an aged synthesis solution diluted with isopropanol. Dense zeolite NaA membranes on mullite‐containing alumina hollow fibers were successfully obtained at 100°C for 2 h without the aid of nanoseeds. The membranes have a good pervaporation performance with a high flux of 10.8 kg m^?2 h^?1 and a separation factor of over 10,000. The abundant mullite‐phase hydroxyl groups on the support surface promote the nucleation and growth of zeolite crystals on the support, resulting in dense membranes. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2679–2688, 2018     

含氟体系中MFI型分子筛膜的制备及其乙醇/水分离性能

以氟化铵为矿化剂、四丙基溴化铵为模板剂,在负载晶种的钇稳定氧化锆(YSZ)中空纤维支撑体表面合成了MFI型分子筛膜,并用于乙醇/水的分离;系统考察了氟硅比(n_NH4F/n_SiO2)、合成时间等条件对膜分离性能的影响,在n_NH4F/n_SiO2为0.8、合成时间为8 h下合成出高性能膜,其通量达8.2 kg·m^-2·h^-1、乙醇/水分离因子为47;同时研究了MFI型分子筛膜在乙醇/水体系中的分离稳定性,揭示出该方法所合成膜表面无Si-OH,从而避免了Si-OH与乙醇反应而带来膜分离性能的下降.     

Enhanced compactness of oriented MFI zeolite films by heat treatment of seed layer

The achievement of compact and defect-free film structure is crucial for the application of b-oriented MFI zeolite film. In this work, a novel heat treatment technique was used to treat zeolite seeded substrates prior to secondary growth. The influence of the heat treatment parameters such as treat temperature and time on the final film morphology were systematically investigated. The relationship between film compactness and the parameters was established. Under the optimized treat temperature of 120?°C and treat time of 1?h, compact and uniform b-oriented MFI zeolite film was achieved. The applicability of the optimum heat treatment condition was validated by employing various film substrates.     

Efficient separation of N2 and he at low temperature using MFI membranes

Ultra‐thin MFI membranes were evaluated for N₂/He separation over the temperature range of 85–260 K for the first time. The membranes were rather nitrogen selective at all the conditions investigated. A highest N₂/He selectivity of 75.7 with a high N₂ flux of 83 kg/m²/h was observed at 124 K. The separation was attributed to adsorption selectivity to N₂, effectively hindering the transport of He in the zeolite pores. The exceedingly high permeance even at low temperatures was ascribed to the ultrathin (<1μm) membrane used. As the pressure ratios increased, a better separation performance was obtained. A mathematical model showed the largest difference of adsorbed loading over the film at ca. 120 K was the main reason for the observed maximum selectivity. Further, the modelling indicated the selectivity would increase 2–3 times by reducing the influence of defects, concentration polarization, and pressure drop over the support. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2833–2842, 2016     

Effect of metal‐support interface on hydrogen permeation through palladium membranes

Thin palladium membranes of different thicknesses were prepared on sol‐gel derived mesoporous γ‐alumina/α‐alumina and yttria‐stabilized zirconia/α‐alumina supports by a method combining sputter deposition and electroless plating. The effect of metal‐support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes are significantly smaller than those for the Pd/YSZ/α‐Al₂O₃ membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd‐Al alloy, than the Pd/YSZ/α‐Al₂O₃ membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Performance of zeolite powder and tubular membrane having different Si/Al ratio for removing As(III) in aqueous phase

Three different types of zeolite having pore sizes in the range 0.26‐0.74 nm, (NaP, NaA, and NaY) powders and membranes are synthesized with different Si:Al ratio on low cost clay alumina tubular support. The results of the permeation and separation studies showed that the NaP zeolite powder and membrane removes maximum As(III) from the water solution (more than 80%) compared to other zeolites. The removal of As(III) to achieve drinking water standard, by zeolite membrane, in a single step process does not seem to have been reported before the present investigation. These are the novelty achieved.     

Pure H2 production through hollow fiber hydrogen‐selective MFI zeolite membranes using steam as sweep gas

Hollow fiber MFI zeolite membranes were modified by catalytic cracking deposition of methyldiethoxysilane to enhance their H₂/CO₂ separation performance and further used in high temperature water gas shift membrane reactor. Steam was used as the sweep gas in the MR for the production of pure H₂. Extensive investigations were conducted on MR performance by variations of temperature, feed pressure, sweep steam flow rate, and steam‐to‐CO ratio. CO conversion was obviously enhanced in the MR as compared with conventional packed‐bed reactor (PBR) due to the coupled effects of H₂ removal as well as counter‐diffusion of sweep steam. Significant increment in CO conversion for MR vs. PBR was obtained at relatively low temperature and steam‐to‐CO ratio. A high H₂ permeate purity of 98.2% could be achieved in the MR swept by steam. Moreover, the MR exhibited an excellent long‐term operating stability for 100 h in despite of the membrane quality. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3459–3469, 2015     

A transient method for mass‐transfer characterization through supported zeolite membranes: Extension to two components

In a previous work (Courthial et al.) a transient state characterization method for zeolite supported membranes has been proposed and tested for single components in the Henry domain. An extension of the method to single components beyond the Henry domain and to binary mixtures is described. Since the method is based on experiments performed within the linear domain, the dynamic model previously developed for single components in the Henry domain is extended. The parameter estimation procedure that is described is based on a deep analysis of the model structure with respect to its structural identifiability properties. Some experimental results concerning pure n‐butane as well as isobutane/n‐butane mixtures transport through mordenite framework inverted (MFI)‐supported membranes are finally shown to illustrate the technique. © 2012 American Institute of Chemical Engineers AIChE J, 59: 959–970, 2013     

Krypton‐xenon separation properties of SAPO‐34 zeolite materials and membranes

Separation of the radioisotope ⁸⁵Kr from ¹³⁶Xe is an important target during used nuclear fuel recycling. We report a detailed study on the Kr and Xe adsorption, diffusion, and membrane permeation properties of the silicoaluminophosphate zeolite SAPO‐34. Adsorption and diffusion measurements on SAPO‐34 crystals indicate their potential for use in Kr‐Xe separation membranes, but also highlight competing effects of adsorption and diffusion selectivity. SAPO‐34 membranes are synthesized on α?alumina disk and tubular substrates via steam assisted conversion seeding and hydrothermal growth, and are characterized in detail. Membrane transport measurements reveal that SAPO‐34 membranes can separate Kr from Xe by molecular sieving, with Kr permeabilities around 50 Barrer and mixture selectivity of 25–30 for Kr at ambient or slight sub‐ambient conditions. The membrane transport characteristics are modeled by the Maxwell‐Stefan equations, whose predictions are in very good agreement with experiment and confirm the minimal competing effects of adsorption and diffusion. © 2016 American Institute of Chemical Engineers AIChE J, 63: 761–769, 2017     

b轴取向MFI分子筛膜的制备及应用研究进展

分子筛膜是一种新型的无机膜,具有孔道结构规整、化学和热稳定性好、机械强度高、抗污染性能好、易于改性等优点。b轴取向MFI分子筛膜因可以缩短传质路径、降低传质阻力、提高扩散效率,在膜分离和膜反应器领域有着广泛的应用前景,受到国内外学者的普遍关注。综述了b轴取向分子筛膜的制备方法及应用研究进展。详细介绍了原位水热合成法、二次生长法、微波辅助合成法、无凝胶法、固相转化法及纳米片法等。二次生长法可以控制分子筛膜的微观结构,且受载体表面性质的影响较小;微波辅助法可以缩短结晶时间,降低能耗,对工业化生产具有重要意义;无凝胶法具有制备工艺简单、环境友好等优点。在上述方法的基础上,将纳米片作为晶种可以降低膜厚。最后,展望了b轴取向MFI分子筛膜的发展前景,在制备b轴取向连续无缺陷MFI分子筛膜方面仍面临许多挑战,包括提高膜的机械强度和长期运行稳定性、实现粗糙或弯曲以及大尺寸载体表面取向膜层的制备等。     

MFI型分子筛膜的制备及表征

采用无模板剂的二次生长合成方法,在-αA l2O3基膜上合成了MFI型分子筛膜,用XRD,SEM和气体渗透实验等方法进行表征,表明合成在-αA l2O3基膜的物质为MFI型分子筛。二次生长分子筛膜的正/异丁烷理想分离系数在298 K和473 K时分别为77和70,气体分离数据表明,2种分子筛膜对气体分离是由分子筛分占主导,同时分子筛膜完整无裂缺。不同温度,通过MFI分子筛膜渗透汽化分离质量分数分别为5%、50%和95%的乙醇/水的渗透通量和分离因子,结果表明渗透通量随温度的升高而升高,而分离因子随温度的升高却降低;渗透通量随乙醇质量分数的升高而降低,分离因子却随质量分数的升高而升高。     

Enhanced gas separation properties by using nanostructured PES‐Zeolite 4A mixed matrix membranes

The polymer–zeolite mixed matrix membranes were fabricated by incorporating nanosized or microsized zeolite 4A into polyethersulfone. A comparison of zeolite 4A nanocrystals and microcrystals was made by using SEM, XRD, N₂ adsorption–desorption measurements. Zeolite particles were well‐distributed in the polymer phase, as reflected by the SEM images. The effects of the zeolite 4A particle size on the gas permeation performance were studied. Experimental results demonstrate that mixed matrix membranes exhibit decreased gas permeabilities due to the barrier effect of zeolite particles. The obtained permselectivity is greatly enhanced for He/N₂, H₂/N₂, He/CO₂, and H₂/CO₂ gas pairs, especially for nanosized zeolite 4A mixed matrix membranes. The gas permeation performance difference is observed between the nanostructured and microstructured membranes, which is attributed to a combined effect of different zeolite composition and different particle size. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3800–3805, 2006     

Factors affecting the formation of zeolite seed layers and the effects of seed layers on the growth of zeolite silicalite-1 membranes

The present study investigates the formation of silicalite-1 seed layers on a porous carbon support of 0.5 μm pore size and α-A1₂O₃ supports with different pore sizes (0.1 μm and 4 μm) via the slip-casting technique. The effects of support property, seed size and solvent on the formation of seed layers were investigated in detail. The growth of silicalite-1 membranes on different seeded supports by hydrothermal synthesis was also evaluated. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) characterizations indicate that a continuous seed layer can be obtained on the smooth support of 0.1 μm pore size by using any seed of 100 nm, 600 nm or 2.2 μm in size, whereas, on the coarse supports with either 0.5 μm or 4 μm pore size, a continuous seed layer cannot be formed using the above seed sizes and the same seeding time. At a longer contact time, a seed layer can also be formed using 100 nm seed on the supports with larger pore size. However, the layer is not uniform and smooth. For a hydrophobic porous carbon support, seeding ethanol suspension, which has weak polarity, favors the formation of a continuous seed layer. The seed layers and membranes grown from the smaller seed are more uniform and continuous and possess smoother surfaces than those from the larger seed. The seed layer and respective grown membrane formed from nanosized seed (100 nm) are the most uniform and compact. With this method of seeded secondary synthesis of zeolite membranes, the quality of a membrane mainly depends on the quality of the seed layer. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(4): 520–526 [译自: 高校化学工程学报]