The influence of membrane formation parameters on structural morphology and performance of PES/PDMS composite membrane for gas separation

In this study, influence of membrane preparation parameters on structural morphology and performance of polyethersulfone/polydimethylsiloxane (PES/PDMS) composite membrane was investigated for gas separation. Asymmetric PES flat sheet membranes were composed by phase inversion method and used as supports. PES composite membranes were fabricated by coating silicone rubber as selective layer on the top surface of support. Effects of different concentrations of PES and PDMS, solvent type, and support thickness on membrane performance were investigated for separation of oxygen from nitrogen. The optimized superior membrane was further modified using polyvinylidenfluoride, methanol and ethanol as additives in PES solutions and/or in water coagulation bath to promote the membrane capability. The results showed that addition of ethanol and methanol in cast solution and coagulation bath can greatly affect the morphology and hence the performance of the prepared membranes. The permeance changes have the contrary trend with solubility parameter difference between solvent and nonsolvent mixture, for instance when this parameter difference was lowest, higher permeance was obtained. Support and coating polymer concentration can control the permeance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reliable production of highly concentrated bioethanol by a conjunction of pervaporation using a silicone rubber sheet‐covered silicalite membrane with adsorption process

For the production of highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, pervaporation performance was investigated using a silicalite membrane entirely covered with a silicone rubber sheet to prevent direct contact with acidic compounds. By using a resistance model for membrane permeation, the separation factor of the covered silicalite membrane towards ethanol can be estimated from the individual pervaporation performances of the silicalite membrane and the silicone rubber sheet. No decrease in the ethanol concentration through the silicone rubber sheet‐covered membrane was caused when ethanol solutions containing succinic acid were supplied. By directly passing the permeate‐enriched ethanol vapor mixed with water vapor through a dehydration column packed with a molecular sieve of pore size 0.3 nm, highly concentrated bioethanol up to 97% (w/w), greater than the azeotropic point in the ethanol/water binary systems, can be obtained from 9% (w/w) fermentation broth. Copyright © 2004 Society of Chemical Industry     

烧结温度对TiO2/不锈钢中空纤维复合膜结构和性能的影响

不锈钢中空纤维膜基膜孔径大,直接涂覆分离层容易产生表面缺陷。在二氧化钛悬浮液中加入聚乙烯醇作为黏结剂,通过真空辅助抽滤法在不锈钢中空纤维基膜表面形成一层均匀的分离层。通过高温烧结得到了TiO₂/不锈钢中空纤维复合膜,考察了烧结温度对于TiO₂/不锈钢中空纤维复合膜表面分离层形貌和结构的影响。不同烧结温度时,TiO₂/不锈钢中空纤维复合膜的表面形貌有所差异;随着烧结温度的升高,不锈钢复合膜的孔径和纯水通量均先升高再下降。当烧结温度为500℃时,表面涂层均匀,孔径分布集中,水通量较高。最后,以SPT-500膜测试了水包油乳液分离效果,分离效率达到99%以上,且具有良好的抗污染性能。     

Preparation and properties of PVDF-fabric composite membrane for membrane distillation

The flat sheet PVDF-fabric composite membrane used for membrane distillation was prepared by coating and wet phase inversion process. The composite membrane consisted of a PVDF porous membrane layer and a fabric layer. The thin polyester filament woven fabric with water-and-oil repellent finish was used as the support of composite membrane. The effects of fabric texture, PVDF concentration in casting solution and functional finishing of fabric on the preparation and properties of the composite membrane were investigated. The experimental results showed that fabric texture, PVDF concentration and functional finishing of fabric had great influence on the preparation and properties of the composite membrane. When the PVDF concentration in casting solution was 10-12% and the support fabric, with 435 warps/10 cm and 273 wefts/10 cm and the area weight of 79 g/m², was finished with 2 g/L water-and-oil repellent agent FK-501, the prepared composite membrane exhibited better performance in tensile strength, peeling strength and water vapor permeability, with mean pore size of 0.63 μm and overall porosity of 57.6%.     

Effect of coating procedure on composite gas separation membrane performance

The influence of different coating procedures on the transport and separation properties of composite gas separation membranes was studied. The composite membrane (CM) comprises a coating material (silicone rubber) in occluding contact with an asymmetric polysulfone flat membrane (AM). Permeabilities, ideal separation factors and structure of the CM were found to depend strongly on the evaporation time, volume and concentration of the coating solutions. Gas permeation experiments (H₂, N₂, CO₂, CH₄) indicated that gas permeabilities decreased rapidly with an increasing amount of coating. A maximum in the H₂/N₂, H₂/CH₄ ideal separation factor was reached as the amount of coating was increased. Scanning electron microscopy (SEM) studies revealed the presence of a dense isotropic layer of coating material above an anisotropic layer comprised of a mixture of polysulfone nodules and silicone material. The results showed that the CM prepared with a concentration of 6% silicone solution and contact time of 1 min has the best gas separation performance.     

PDMS/ZIF-8 coating polymeric hollow fiber substrate for alcohol permselective pervaporation membranes

In order to develop high performance composite membranes for alcohol permselective pervaporation (PV), poly (dimethylsiloxane)/ZIF-8 (PDMS/ZIF-8) coated polymeric hollow fiber membranes were studied in this research. First, PDMS was used for the active layer, and Torlon®, PVDF, Ultem®, and Matrimid® with different porosity were used as support layer for fabrication of hollow fiber composite membranes. The performance of the membranes varied with different hollow fiber substrates was investigated. Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers. The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated. The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect. Based on the result, ZIF-8 was introduced to prepare more selective separation layer, in order to improve the PV performance. The PDMS/ZIF-8/Torlon® membrane had a separation factor of 8.9 and a total flux of 847 g·m^-2·h^-1. This hollow fiber PDMS/ZIF-8/Torlon® composite membrane has a great potential in the industrial application.     

Innovative hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride (PVDF) composite membrane for vacuum membrane distillation

Though membrane distillation (MD) has gained more and more attention in the field of desalination, the wetting phenomenon was still a non-negligible problem. In this work, a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride composite membranes. This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane. In terms of anti-wetting properties, contact angle and liquid entry pressure of all composite membranes (except for those based on 0.45 μm) exceeded 160° and 0.3 MPa, respectively. In particular, the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5% (mass) saline solution (NaCl) at 60 ℃. The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux. And for stability tests (testing the 0.22 μm membrane coated by 5% (mass) PFPE), the highest MD flux 29.08 kg·m^-2·h^-1 and stable salt rejection (over 99.99%) during the period. Except that, the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography, porosity, mechanical strength and pore size characteristics. This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.     

CNT-MF/硅橡胶泡沫复合材料的制备及介电性能

以碳纳米管(CNT)作为核,密胺树脂(MF)作为壳,苯乙烯马来酸酐共聚物(SMA)为乳化剂,原位聚合制备微胶囊化碳纳米管(CNT-MF),并将包覆后的碳纳米管作为填料添加到硅橡胶泡沫中,制备了CNT-MF/硅橡胶泡沫复合材料。探讨了核/壳质量比对微胶囊化碳纳米管的包覆效果的影响,同时研究了微胶囊化碳纳米管用量对硅橡胶泡沫泡孔结构和介电性能的影响。结果表明,微胶囊化碳纳米管的加入有利于提高复合材料的泡孔结构,大泡孔的存在和泡孔面积有利于材料介电性能的提高。当核/壳质量比为1∶10的微胶囊化碳纳米管添加量为15 phr时,复合材料介电性能表现最佳,此时复合材料在1 kHz的介电常数为26.34,介电损耗仅为0.013 6。     

Support surface pore structures matter: Effects of support surface pore structures on the TFC gas separation membrane performance over a wide pressure range

In this work, the effects of support surface pore structures(including surface pore size, surface pore density and surface porosity) on the performance of thin film composite(TFC) gas separation membrane over a wide pressure range(from 0.3 to 2.0 MPa) were studied. To fulfill it, the polysulfone(PSf) supports with different surface pore structures were prepared. Two kinds of wide-accepted polymeric membrane materials, i.e., polyvinylamine(PVAm) and Pebax 1657 copolymer, were used as skin layer materials. We pointed out for the first time that the support surface average pore size and pore density could affect the chain mobility of polymer of skin layer at the support surface pore entrance, then, can affect the TFC membrane performance. Besides, we also discussed the effects of support on the TFC membrane performance when the feed pressure changes for the first time. This work can provide guidance for choosing a suitable support for TFC gas separation membrane.     

Fabrication and characterization of PDMS coated PES membranes for separation of ethylene from nitrogen

Composite membranes were prepared for separation of ethylene from nitrogen using polyethersulfone (PES) as support and polydimethylsiloxane (PDMS-a grade of silicone rubber) as active layer at various concentrations. Permeance and ideal selectivity were measured for all membranes under the transmembrane pressure of 2 to 6 bars. Influences of affecting parameters on membrane performance (i.e. permeance and selectivity) were investigated. The studied parameters include: PES concentration in casting solution, solvent type, PDMS concentration in coating layer, support thickness, coating thickness and coagulation atmosphere. For all coated membranes, the ethylene permeance was higher compared to the nitrogen permeance except for 5% coated air coagulated membrane. This membrane was more permeable for N₂ in comparison with ethylene under the pressures higher than 2 bars. The nitrogen permeance exhibited a rather constant value. There was no significant change in nitrogen permeance with respect to the coating layer, whereas ethylene permeance was highly influenced by coating layer composition and support thickness. The governing mechanism for the separation is solution-diffusion of ethylene in PDMS layer (solution-diffusion model). The SEM study was carried out for investigation of membrane morphology. In a run ethylene was passed through the membrane after the passage of nitrogen. In the second run ethylene was passed through the membrane before nitrogen. The nitrogen selectivity was reduced in the later test. This is due to the ethylene high solubility in membrane matrix.     

碳分子筛填充硅橡胶膜用于渗透蒸发分离稀醋酸-水溶液

From the reference[1] it is known that the addition of silicalite-1 in silicone rubber membranes results in an increase of both flux and selectivity for alcohol in the separation of alcohol/water by pervaporation.In order to enhance performance of pervaporation toward the aqueous solution of acetic acid,incorporation of carbon molecular sieve(CMS)into a PDMS membrane was investigated. CMS is widely used in adsorption processes because of its high selectivity toward certain compounds[2]. It was assumed that the flux and selectivity of pure PDMS membrane could be enhanced owing to the preferential adsorption of CMS to organics.CMS content in the membrane and several important pervaporation operation parameters, including feed concentration of acetic acid, and feed temperature, were investigated.     

分子筛膜晶种涂敷机的研制

研制了基于800~1000 mm长工业规格不锈钢或陶瓷管状支撑体的晶种涂敷设备。采用先喷涂后摩擦工艺,结合自动化控制技术,实现了分子筛膜大规模制备中晶种的快速涂敷。详细介绍了涂敷机工作原理和主要结构,分析研究了影响设备涂敷性能的主要因素。对不锈钢支撑体进行晶种涂敷制备NaA透水膜实验,在温度为75℃、原料液中乙醇质量分数为90%的条件下,膜渗透通量为4.2~5.8 kg·m^-2·h^-1;渗透液中水质量分数为99.2%~99.8%;生产率为30根/小时,成品率大于98%。     

微胶囊化石墨烯/硅橡胶泡沫电介质材料的制备及介电行为

以苯乙烯马来酸酐共聚物(SMA)为乳化剂、三聚氰胺甲醛树脂(密胺树脂,MF)为壁材、片状石墨烯(GE)为芯材,通过原位聚合法制备了包覆的石墨烯“微胶囊”,并以微胶囊作为填料,双组分室温硫化泡沫硅橡胶(RTVSR)作为基体,通过室温硫化(RTV)硅橡胶制备具有泡孔结构的电介质复合材料。提出了对石墨烯进行微胶囊化包覆的制备新工艺,讨论了超声分散功率、石墨烯与壁材的用量比例对微胶囊形貌和包覆效果的影响,并比较了包覆前后、发泡前后电介质复合材料的介电性能。研究结果表明,石墨烯与壁材质量比为1∶100、超声功率为840 W时制备的分散液较稳定、石墨烯的表面附着物较多;同时包覆(微胶囊化)能减少石墨烯发生团聚,0.3 g微胶囊填量下,包覆后的微胶囊石墨烯/泡沫电介质材料的介电常数是包覆前石墨烯/硅橡胶电介质材料的2.45倍,而介电损耗比石墨烯/硅橡胶复合材料还低,只有0.002,同时泡孔的存在有利于提升复合材料的介电性能。     

Selective separation of n‐butanol from aqueous solutions by pervaporation using silicone rubber‐coated silicalite membranes

BACKGROUND: To use butanol as a liquid fuel and feedstock, it is necessary to establish processes for refining low‐concentration butanol solutions. Pervaporation (PV) employing hydrophobic silicalite membranes for selective recovery of butanol is a promising approach. In this study, the adsorption behavior of components present in clostridia fermentation broths on membrane material (silicalite powder) was investigated. The potential of PV using silicone rubber‐coated silicalite membranes for the selective separation of butanol from model acetone–butanol–ethanol (ABE) solutions was investigated. RESULTS: The equilibrium adsorbed amounts of ABE per gram of silicalite from aqueous solutions of binary mixtures at 30 °C increased as follows: ethanol (95 mg) < acetone (100 mg) < n‐butanol (120 mg). The amount of butanol adsorbed is decreased by the adsorption of acetone and butyric acid. In the separation of ternary butanol/water/acetone mixtures, the enrichment factor for acetone decreased, compared with that in binary acetone/water mixtures. In the separation of a model acetone–butanol–ethanol (ABE) fermentation broth containing butyric acid by PV using a silicone rubber‐coated silicalite membrane, the permeate butanol concentration was comparable with that obtained in the separation of a model ABE broth without butyric acid. The total flux decreased with decreasing feed solution pH. CONCLUSION: A silicone rubber‐coated silicalite membrane exhibited highly selective PV performance in the separation of a model ABE solution. It is very important to demonstrate the effectiveness of PV in the separation of actual clostridia fermentation broths, and to identify the factors affecting PV performance. Copyright © 2011 Society of Chemical Industry     

支撑层对硅橡胶复合膜渗透汽化分离性能的影响

引言 为了扩大渗透汽化技术的应用领域,科研工作者需要进一步增强渗透汽化膜的分离性能.从工业化的观点而言,用于实际应用的渗透汽化膜大多是复合膜,它由选择层(或分离层)和支撑层组成.一般认为,选择层决定着复合膜的选择性和通量,支撑层起支撑和机械稳定作用.Nijhuis[1]在从甲苯-水体系中分离甲苯的过程中对均质膜和以聚砜为支撑层的复合膜的分离性能进行了比较;Sturken[2]分别用聚醚酰亚胺和聚偏氟乙烯为支撑层的硅橡胶膜从二氯乙烷-水体系中提取二氯乙烷,他们得到了相同的结论:支撑层的影响可以忽略.然而Scholz[3],Heinzelmann[4],Rautenbach[5],Borges[6],Vankelecom[7],Farooq[8],Lipnizki[9]等均在各自研究中发现,由于基膜和分离层的物理化学性质以及制膜方法等众多因素的存在使得支撑层在一定程度上影响复合膜的分离性能;Feng[10]对均质硅橡胶膜和有微孔支撑层的硅橡胶复合膜的分离性能进行了比较,发现均质硅橡胶膜优先透过异丙醇,而有微孔亲水性支撑层的硅橡胶复合膜则优先透过水,这表明在一定的情况下,支撑层甚至起主导作用并能够决定复合膜的分离性能.因此,通过系统研究以不同多孔材料为支撑层的复合膜对有机物-水溶液的分离性能的影响,能够找到最优的复合膜支撑层,从而能够提高复合膜的分离性能.然而,至今关于支撑层对渗透汽化膜分离性能影响的系统研究仍相当少.     

Separation properties of alcohol–water mixture through silicalite-I-filled silicone rubber membranes by pervaporation

The structure and the adsorption–desorption properties of zeolite silicalite-I by different treatments after synthesis were studied. The pervaporation properties of the alcohol–water mixture through silicone rubber filled with zeolite silicalite-I by different treatments were also investigated. Treating silicalite-I by acid or/and under steam was found to eliminate the metallic impurities in the zeolite and to perfect the crystalline structure of the zeolite. After treatment, silicalite-I is more selective to alcohol and the desorption of the alcohol from the zeolite is also easier. The silicone rubber membrane filled with treated silicalite-I shows a high performance for alcohol extraction from the dilute aqueous solution by pervaporation. The separation factor of the poly(dimethyl siloxane) (PDMS) membrane filled with silicalite-I treated successively by acid and steam is about 30 when the ethanol content in the feed is 5 wt % at 50°C. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 629–636, 1998     

Synthesis and characterization of silicalite-1 membrane prepared on a novel support by the pore plugging method

The effect of the support pore size on the membrane morphology was investigated for zeolite silicalite-1 membranes synthesized by pore plugging method on supports with zirconium oxide and/or titanium oxide active layer. Parameters including surface coverage, zeolite layer thickness, crystal size and shape, zeolite penetration depth were used to quantify the membrane morphology. Five supports with different pore sizes for their active layer in the range of 0.14–1.4 μm were investigated. The X-ray diffraction (XRD) analysis showed a typical silicalite-1 zeolite structure with a high internal crystalline order grown inside the pores as well as on top of all supports. The XRD results also showed that the silicalite-1 crystals in the synthesized membranes are not randomly oriented. The crystallographic preferred orientation (CPO) analysis revealed that the degree of orientation toward either the a-axis or b-axis perpendicular to the support surface, increased by decreasing the pore size of the support. The 0.45 μm support had the most preferably oriented zeolite layer for access of molecules entering into the membrane structure with the highest number of crystals oriented with the b-axis (the one with straight channels) perpendicular to the support surface. The scanning electron micrographs (SEM) analysis of the membranes revealed a dense and continuous surface morphology with the highest crystal size of silicalite-1 around 1.5 μm on the surface of the support with the 0.45 μm pore size. SEM micrographs also showed a continuous layer grown over four supports out of five supports with different pore sizes that were investigated, with no layer observed on the 1.4 μm pore size support. The average thickness of the zeolite layer was in the range of 0.7–1.4 μm, depending on the pore size of the support. The supports with 0.2 and 0.45 μm pore sizes had the most uniform zeolite layer thickness while the support with 0.8 μm pore size active layer had the least uniform zeolite layer thickness. The electron diffraction spectrometer (EDS) analysis confirmed the formation of pure silicalite-1 layer at the surface as well as inside the pores of all supports. The highest silicalite-1 crystal penetration was for the supports with 0.45 and 1.4 μm pore sizes. Single gas permeation experiments with He and N₂ gases at 293 K illustrated that regardless of the pore size of the support, the He and N₂ permeances were constant despite the change of the pressure across the membranes. The highest permeances were observed for the membrane prepared using the 0.45 μm pore size support, while the lowest permeances were for the membrane prepared using the 1.4 μm pore size support. These results confirmed the selective properties of the prepared membranes. No matter what is the pore size of the support or the feed pressure, N₂ permeances were around three times higher than those for He.     

Influence of surface properties on the dip coating behavior of hollow fiber membranes

Coating processes have become an important fabrication step in membrane production, either to form a separation layer on a porous substrate or to tune specific properties. The coating procedure depends to a large extent on the membrane properties which substantially impedes a prediction of the coating thickness. To give an insight into the coating properties of various hollow fiber membranes, a selection of membranes with different pore sizes was coated with aqueous poly(vinyl alcohol) solutions at various coating velocities. It was found that material properties and pore sizes of the membranes have great influence on coating thicknesses. An intrusion of coating material into the membrane structure was determined with increasing pore size. Pure intrusion without formation of a dense surface layer took place when using a membrane with a mean pore size of ca. 500 nm. Coating results were correlated with the theoretical LLD law and for some membranes the coating thickness can be predicted quite well by the LLD law and its enhancements. When a significant amount of coating material penetrated into the membrane structure the LLD law loses its validity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46163.     

The membrane properties of alumina-coated alumina support layers and alumina-coated diatomite–kaolin composite support layers

ABSTRACT

Porous ceramic membranes are a current research focus because of their outstanding thermal and chemical stability. Recent research has utilised inexpensive natural materials such as diatomite to reduce the expense of these porous ceramic membranes. However, insufficient data exist for microfiltration applications using the diatomite-based membranes. The measured membrane properties of alumina-coated alumina support layers and alumina-coated diatomite–kaolin composite support layers have been compared. These experiments have been used to determine whether the average pore size could be reduced effectively by controlling the thickness of the alumina coating layer, while maintaining acceptable water permeability. The membrane properties of the alumina-coated alumina support layers and the alumina-coated diatomite–kaolin composite support layers were examined using the scanning electron microscopy, mercury porosimetry, and a dead-end microfiltration system.     

Transfer of gas to dissolved oxygen in water via porous and nonporous polymer membranes

The transfer rates of oxygen via polymer membranes in gas–membrane–gas and gas–membrane–water (dissolved oxygen) were investigated with various porous membranes and compared with results of silicone rubber sheet (nonporous, homogeneous polymer membrane). With a nonporous membrane, the permeability constant obtained by gas–membrane–gas represents the true membrane permeability in gas–membrane–water system, and consequently the transport resistance due to boundary layer can be quantitatively estimated. With a porous membrane, the data in gas–membrane–gas system (under applied pressure) merely represent the gas effusion rate of the membrane and are not directly related to the dissolved oxygen transfer rate in gas–membrane–water system. The penetration of liquid water into the pores of porous membrane is the most important controlling factor for the dissolved oxygen transfer rate of a porous membrane. With a porous membrane in which liquid water does not penetrate into the pore, the overall transfer rate of dissolved oxygen reaches the level which corresponds to that of the boundary layer found with silicone rubber membrane.