Perfluorosulfonic acid—Tetraethoxysilane/polyacrylonitrile (PFSA‐TEOS/PAN) hollow fiber composite membranes prepared for pervaporation dehydration of ethyl acetate–water solutions

Preparation of organic‐inorganic composite membranes and their pervaporation (PV) permeation and separation characteristics for the aqueous solution of ethyl acetate were described. Polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane as support membrane, the mixtures of perfluorosulfonic acid (PFSA) and tetraethoxysilane (TEOS) by the sol‐gel reaction as the coating solution, the PFSA‐TEOS/PAN hollow fiber composite membranes by the different annealing conditions were prepared. The swelling of PFSA in ethyl acetate aqueous solutions was inhibited with addition of TEOS. The PFSA‐TEOS/PAN composite membranes containing up to 30 wt % TEOS in coating solution exhibited high selectivity towards water, then the selectivity decreased and permeation flux increased with increasing the TEOS concentration more than 30 wt %. When the PFSA‐TEOS/PAN composite membranes were annealed, the separation factor increased with increasing annealing temperature and time. Higher annealing temperature and longer annealing time promoted the crosslinking reaction between PFSA and TEOS in PFSA‐TEOS/PAN composite membranes, leading to the enhanced selectivity towards water. For the PFSA/PAN and PFSA‐TEOS/PAN composite membrane with 5 and 30 wt % TEOS annealed at 90°C for 12 h, their PV performance of aqueous solution 98 wt % ethyl acetate were as follows: the separation factors were 30.8, 254 and 496, while their permeation flux were 1430, 513 and 205 g/m² h at 40°C, respectively. In addition, the PV performance of PFSA‐TEOS/PAN composite membranes was investigated at different feed solution temperature and concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes for pervaporation separation of ethanol/water solution

Polysulfone (PSF) hollow fiber membranes were spun by phase‐inversion method from 29 wt % solids of 29 : 65 : 6 PSF/NMP/glycerol and 29 : 64 : 7 PSF/DMAc/glycol using 93.5 : 6.5 NMP/water and 94.5 : 5.5 DMAc/water as bore fluids, respectively, while the external coagulant was water. Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes were prepared after PSF hollow fiber membranes were coated using different PVA aqueous solutions, which were composed of PVA, fatty alcohol polyoxyethylene ether (AEO₉), maleic acid (MAC), and water. Two coating methods (dip coating and vacuum coating) and different heat treatments were discussed. The effects of hollow fiber membrane treatment methods, membrane structures, ethanol solution temperatures, and MAC/PVA ratios on the pervaporation performance of 95 wt % ethanol/water solution were studied. Using the vacuum‐coating method, the suitable MAC/PVA ratio was 0.3 for the preparation of PVA/PSF hollow fiber composite membrane with the sponge‐like membrane structure. Its pervaporation performance was as follows: separation factor (α) was 185 while permeation flux (J) was 30g/m²·h at 50°C. Based on the experimental results, it was found that separation factor (α) of PVA/PSF composite membrane with single finger‐void membrane structure was higher than that with the sponge‐like membrane structure. Therefore, single finger‐void membrane structure as the supported membrane was more suitable than sponge‐like membrane structure for the preparation of PVA/PSF hollow fiber composite membrane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 247–254, 2005     

PFSA-TiO2(or Al2O3)-PVA/PVA/PAN difunctional hollow fiber composite membranes prepared by dip-coating method

PFSA-TiO₂(or Al₂O₃)-PVA/PVA/PAN difunctional hollow fiber composite membranes with separation performance and catalytic activity have been prepared by dip-coating method. The good separation performance was brought about by the glutaraldehyde (GA) surface cross-linked PVA/PAN composite membrane, and the good catalytic activity of the membrane was achieved by the perfluorosulphonic acid (PFSA) used. The difunctional hollow fiber membranes were characterized by XRD, TGA, EDX, SEM, and FTIR. The separation performance was measured by dehydration of azeotropic top product of ethanol-acetic acid esterification, and the catalytic activity was obtained by investigating the esterification of ethanol and acetic acid. The FTIR spectra and the morphologies of difunctional hollow fiber composite membranes were similar for samples prior to esterification and post-esterification with ethanol and acetic acid for 24?h. Difunctional hollow fiber composite membranes with 2% PFSA, 8% TiO₂ (named as DM-T1), and 2% PFSA, 8% Al₂O₃ (named as DM-A1) (all by weights) showed the best catalytic activity. They displayed fluxes of 165 and 173?g/m^2?h, separation factors of water to ethanol of 279 and 161, PFSA contents in difunctional hollow fiber composite membrane of 3.2 and 2.4%, the ratios of PFSA to feed solution (acetic acid?Cethanol) of 0.031 and 0.023%, and the equilibrium conversion of ethanol at 53.5 and 57.6%, in the given order for TiO₂ and Al₂O₃ containing samples.     

影响渗透汽化中空纤维复合膜分离性能的制备工艺研究

采用聚乙烯醇（ＰＶＡ）为分离层的模材料,以浸涂工艺把ＰＶＡ复合到聚砜（ＰＳ）或聚丙烯腈（ＰＡＮ）的中空纤维支撑层上,在长度为０．４ｍ的不锈钢管中组装若干根中空纤维复合膜测定对乙醇水溶液的渗透汽化（ＰＶ）分离性能。结果表明,ＰＶＡ／ＰＡＮ中空纤维复合膜的性能优于ＰＶＡ／ＰＳ,内径较大（１．３ｍｍ）的优于内径上（０．４ｍｍ）者,ＰＶＡ水溶液在中空纤维支撑层上的涂复次数对复合膜ＰＶ分离性能、以及ＰＶＡ／     

Pervaporation dehydration of ethyl acetate aqueous solution using the doubly modified polyvinyl alcohol (PVA) composite membrane

Polyvinyl alcohol–tetraethoxysilane–perfluorosulfonic acid (PVA–TEOS–PFSA) hybrid membrane was prepared by sol–gel method through PVA being modified doubly by PFSA and TEOS. With polyacrylonitrile (PAN) ultrafiltration membrane as a substrate membrane, PVA–TEOS–PFSA/PAN composite membrane was fabricated by dip-coating method for pervaporation (PV) dehydration of ethyl acetate (EAc) aqueous solution. The hybrid membrane was characterized by swelling degree, static contact angle, Fourier transform infrared spectra and scanning electron microscope. Effects of PFSA and TEOS contents in coating solution on PV performance of composite membrane were investigated, respectively. With increasing PFSA content, the permeation flux of composite membrane increased, while the separation factor decreased. Just the opposite, the increase of TEOS content resulted in the decrease in permeation flux and the increase in separation factor. In addition, the PV performances of composite membranes were also investigated at different feed temperatures and water concentrations in feed, respectively. The PVA–TEOS–PFSA/PAN composite membrane, which was prepared from coating with PVA/PFSA mass ratio of 80/20 and TEOS content of 20 wt%, exhibited the permeation flux of 347.9 g m^?2 h^?1 and the separation factor of 2218 for PV dehydration of 2 wt% water of EAc solution at 40 °C.     

全氟磺酸改性聚乙烯醇渗透汽化膜分离乙酸乙酯-水溶液

以聚乙烯醇(PVA)为原材料,全氟磺酸(PFSA)为共混改性材料,以聚丙烯腈(PAN)中空纤维超滤膜为底膜制备了PVAfPAN、PVA-PFSA/PAN复合膜,并用于乙酸乙酯脱水.考察了共混涂膜液中PVA、PFSA配比,交联剂酒石酸(Tat)用量以及原料液温度与浓度对PVA、PAN、PVA-PFSA、PAN复合膜分离件能的影响.实验结果表明,Tac交联的PVA,PAN、PVA-PFSA/PAN复合膜均对水具有较好的分离选择性.共混涂膜液中PVA/PFSA质量比为1/1、Tac/PVA质量比为l/5时所制备的PVA-PFSA/PAN复合膜渗透汽化分离性能最佳.40下℃此复合膜用于分离98%(wt)的乙酸乙酯水溶液时,其渗透通量和分离因予分别为81.1 g·m-2·h-1和1890.同样条件下,与交联PVA/PAN复合膜相比,交联PVA-PFSA/PAN复合膜的渗透通量显著提高.     

膜结构填料涂覆改性对精馏分离异丙醇/水体系的影响

采用聚二甲基硅氧烷(PDMS)对聚砜(PSf)、聚偏氟乙烯(PVDF)两种不同材料中空纤维膜结构填料进行了疏水涂覆改性,并研究了改性前后膜结构填料在异丙醇/水体系精馏分离中的材料性能变化。实验结果表明:PDMS涂覆使PVDF膜的分离效果提高了约20%,但使PSf膜的分离效果下降3%~10%。经涂覆后,膜结构填料的传质单元高度均在20 cm以下,最小可达5 cm左右;所有膜结构填料均可突破传统精馏操作弹性限制,其传质时间小于10 s,水力学特性和传质效率更优。     

Modified poly(vinyl alcohol)/chitosan blended membranes for isopropanol dehydration via pervaporation: Synthesis optimization and modeling by response surface methodology

Box–Behnken (BB) design of response surface methodology (RSM) was effectively applied to optimize fabrication conditions of modified poly(vinyl alcohol) (PVA) and chitosan (CS) blended pervaporation (PV) membranes. The PVA/CS membranes were crosslinked either by chemical reaction with glutaraldehyde (GA) or by heat‐treating at different temperatures. The main objectives were to determine the optimal levels of fabricating parameters and also to investigate interactions among the variables. CS content in the blended membranes, concentration of crosslinking agent and heat‐treating temperature were the fabrication parameters, the main effects and interaction effects of which on membrane structure and PV performance toward isopropanol (IPA)/water dehydration were investigated, and for which regression models were established. The modified PVA/CS blended membranes were characterized by means of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) as well as X‐ray diffraction (XRD). It was found that the CS content is the most significant factor influencing flux and separation factor among the three studied variables and the experimental results are in excellent accordance with predicted values from the developed RSM regression models. The RSM results indicated that under preparation conditions of 80 wt % CS in the blended membrane, 0.58 wt % GA concentration, and 77 °C heat‐treating temperature, the maximum separation factor of 5222.8 and the normalized flux of 9.407 kg µm/m²h can be acquired with feed content of 85 wt % IPA at 25 °C, showing that the prepared membrane is highly efficient for PV dehydration of IPA. The models were satisfactorily validated against experimental data. Furthermore, the optimum membrane presents excellent separation performance at different feed compositions and temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44587.     

Polymer membranes for separating organic mixtures

Polyvinyl alcohol (PVA), polyacrylonitrile (PAN), and cellulose ester were respectively chosen as the separation layer and the support in the composite membranes based on the concept of the solubility parameter and the permselectivities for separating ethanol/water mixture, isopropanol/water mixture, and caprolactam/water mixture. The effects of the membrane materials and the construction of the composite membrane on the separation performance were preliminary discussed. The separation performance of the membranes prepared by several making‐membrane techniques, i.e., the polymer solution making‐membrane technique, and the membrane treatment technique (heat treatment, organic solvent modification) were presented. The composite membranes of PVA/PAN and PVA/cellulose acetate, and cellulose triacetate hollow fiber membrane modified, which possess good performance in separating the organic systems, were developed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1160–1164, 2006     

Enhancement of pervaporation performance of composite membranes through in situ generation of silver nanoparticles in poly(vinyl alcohol) matrix

Composite membranes were prepared from an aqueous solution of poly(vinyl alcohol) (PVA) and silver sulphate. The silver nanoparticles were generated in situ before crosslinking PVA matrix by reduction of silver ions using sodium borohydride. Physico‐chemical properties of the resulting composite membranes were studied using Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy (UV–vis), thermogravimetric analysis (TGA), Wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and universal testing machine (UTM). The UV–vis spectrum shows a single peak at 410 nm due to surface plasmon absorption of silver nanoparticles. This surely specified that silver nanoparticles are generated in PVA matrix. The membranes were under go pervaporation (PV) for separation of water from isopropanol at different temperatures. The results indicated that hydrophilicity and amorphous nature of the membranes were increased with increasing silver nanoparticles in PVA matrix. The swelling and separation performance of the membranes were studied. Both permeation flux and separation factor were increased with increasing silver nanoparticles in PVA matrix. The results showed that the membrane containing 2.5 mass% of Ag salt exhibited excellent PV performance. The values of total flux and flux of water are almost closed to each other, indicating that membranes could be effectively used to break the azeotropic point of water‐isopropanol. The long‐term test was performed at room temperature and ascertained that membranes were durable up to 30 days for the dehydration of IPA. On the basis of the estimate Arrhenius activation energy values, the efficiency of the membranes was discussed. The calculated ΔH_s values are negative for all the membranes, indicating that Longmuir's mode of sorption is predominant. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41248.     

Characterization and performance of PVA/Psf composite hollow fiber UF membrane prepared with interfacial polymerization

A new composite hollow fiber ultrafiltration (UF) membrane was prepared with the interfacial polymerization method. A dense layer of polyvinyl alcohol (PVA) was coated on the surface and embedded into the pores of the support polysulfone (PSf) membrane through a dead‐end filtration process and cross‐linked reaction with diisocyanate (TDI) at room temperature. The surface morphology and functional groups of the composite membrane were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Fourier transformation infrared spectrometer (FTIR). Anti‐fouling experiments were conducted to study the hydrophilicity and anti‐fouling properties of the support and composite membranes. The performances of the composite membrane were significantly influenced by preparation conditions. The composite membrane that performed most efficiently was prepared at an optimal condition: 30 min of dead‐end filtration, 0.25 wt% of PVA, 0.50 vol% of TDI, and 60 sec of interfacial reaction. Laboratory scale tests demonstrated that the new composite PVA/PSf membrane has a higher anti‐fouling capability and higher flux for oily wastewater treatment. The hydrophilic groups (? OH) enriched in the PVA molecules on the composite surface could play an important role for the improvement of the anti‐fouling property and the enhancement of flux recovery rate of the composite membrane. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Pervaporation separation of water/isopropanol mixtures through crosslinked carboxymethyl chitosan/polysulfone hollow‐fiber composite membranes

Carboxymethyl chitosan (CMCS)/polysulfone (PS) hollow‐fiber composite membranes were prepared through glutaraldehyde (GA) as the crosslinking agent and PS hollow‐fiber ultrafiltration membrane as the support. The permeation and separation characteristics for dehydration of isopropanol were investigated by the pervaporation method. Pure chitosan, carboxymethyl chitosan, and crosslinked carboxymethyl chitosan membranes were characterized by Fourier transform infrared (FT‐IR) spectroscopy and X‐ray diffraction (XRD) to study the crosslinking reaction mechanism and degree of crystallinity, respectively. The effects of feed composition, crosslinking agent, membrane thickness, and feed temperature on membrane performance were investigated. The results show that the crosslinked CMCS/PS hollow‐fiber composite membranes possess high selectivity and promising permeability. The permeation flux and separation factor for isopropanol/water is 38.6 g/m²h and 3238.5, using 87.5 wt % isopropanol concentration at 45°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1959–1965, 2007     

Comparative behavior of PVA/PAN and PVA/PES composite pervaporation membranes in the pervaporative dehydration of caprolactam

Flat‐sheet composite membranes were developed by the traditional phase inversion technique using poly;(vinyl alcohol) (PVA). PVA composite pervaporation (PV) membranes were prepared with crosslinked PVA selective layer and porous polyacrylonitrile (PAN) and polyether sulfone (PES) substrate layer material as supports for separating heat sensitivity substance ε‐caprolactam (CPL) from CPL/water mixtures. Glutaraldehyde was used as crosslinking agent. The effect of the composition of glutaraldehyde on membrane stability and structure were investigated. The operating parameters, such as feed concentration and operating temperature, remarkably affected PV performance of the composite membranes. The composite membranes with PVA casted on PAN (PVA/PAN) showed superior PV performance than that casted on PES (PVA/PES). This study has also shown that the type of porous support plays an important role in the PV performance. As a result, this work has presented the information needed of the behavior of PV membranes for dehydration applications of industrial caprolactam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4005–4011, 2007     

Positively charged hollow‐fiber composite nanofiltration membrane prepared by quaternization crosslinking

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by interfacial polymerization to develop a positively charged dense network structure. According to this mechanism, a positively charged hollow‐fiber composite nanofiltration (NF) membrane was prepared by quaternization to achieve a crosslinked PDMAEMA gel layer on the outer surface of polysulfone hollow‐fiber ultrafiltration (UF) membranes with a PDMAEMA aqueous solution as a coating solution and p‐xylylene dichloride as an agent. The preparation conditions, including the PDMAEMA concentration, content of additive in the coating solution, catalyzer, alkali, crosslinking temperature, and hollow‐fiber substrate membrane, were studied. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the structure of the membranes. This membrane had a rejection to inorganic salts in aqueous solution. The rejection of MgSO₄ (2 g/L aqueous solution at 0.7 MPa and 25°C) was above 98%, and the flux was about 19.5 L m^?2 h^?1. Moreover, the composite NF membranes showed good stability in the water‐phase filtration process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

中空纤维PVA/PAN复合膜填料的乙醇水溶液精馏性能

以乙醇/水溶液为分离对象,中空纤维PVA/PAN复合膜作为精馏填料,考察了不同膜组件的传质分离效率。实验结果表明:各种组件的分离效率均随塔釜加热功率的增加而减小;和大多数中空纤维膜接触器一样,其总传质系数Ky随中空纤维膜组件填充密度φ的增加而减少;相比于传统精馏填料而言,用中空纤维膜做精馏填料分离乙醇水溶液的分离效果更好,可以在常规填料不能操作的液泛线以上进行操作。当塔釜加热功率为120 W,45根中空纤维膜封装在内径为1.6 cm玻璃管中的传质单元高度(HTU)为5.64 cm。     

热处理条件对PVA/PAN和PPVA/PAN渗透汽化复合膜分离性能的影响

制备了以聚乙烯醇（PVA）、磷酸酯化聚乙烯醇（PPVA）和活性分离层的PVA／PAN、PPVA／PAN渗透汽化复合膜并用于乙醇－水恒沸混合物的分离。考察了热处理条件对复合膜分离性能及吸附性能的影响。结果表明,复合膜的分离性能主要是由热处理温度决定的,并且,PPVA／PAN复合膜比PVA／PAN复合膜具有更好的分离性能。确定了最佳的热处理条件,对于PVA／PAN复合膜：在403K下,热处理时间不小于4h,对于PPAV／PAN复合膜：在423K下,热处理时间不小于2h。     

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。     

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.     

含有MCM-41分子筛的混合基质复合膜用于CO2分离

为了提高CO₂分离膜的性能,将接枝了氨基的MCM-41分子筛(MCM-NH₂)添加到聚乙烯基胺(PVAm)水溶液中配制涂膜液,并将PVAm-MCM-NH₂涂膜液涂覆到聚砜(PSf)超滤膜上制备PVAm-MCM-NH₂/PSf混合基质复合膜。复合膜分离层较薄,有利于CO₂渗透速率的提高。接枝的胺基提高了分子筛与聚合物的相容性和膜内胺基含量,有利于膜渗透选择性能的提高。使用CO₂/N₂混合气(15% CO₂ + 85% N₂,体积分数)考察了不同MCM-NH₂添加量的PVAm-MCM-NH₂/PSf膜的渗透选择性能。当涂膜液中m_MCM-NH2/m_PVAm为0.2、湿涂层厚度为50 μm,测试温度为22℃ 、进料气压力为0.11 MPa时,膜的CO₂渗透速率可达4.66×10^-7 mol·m^-2·s^-1·Pa^-1,CO₂/N₂分离因子可达150。较高的CO₂/N₂分离性能表明PVAm-MCM-NH₂/PSf膜在烟道气碳捕集领域具有良好的应用前景。此外,考察了湿涂层厚度、热处理、添加小分子胺等条件对膜渗透选择性能的影响。     

Preparation of water‐swollen hydrogel membranes for gas separation

Water‐swollen hydrogel (WSH) membranes for gas separation were prepared by the dip‐coating of asymmetric porous polyetherimide (PEI) membrane supports with poly(vinyl alcohol) (PVA)–glutaraldehyde (GA), followed by the crosslinking of the active layer by a solution method. Crosslinked PVA/GA film of different blend compositions (PVA/GA = 1/0.04, 0.06, 0.08, 0.10, 0.12 mol %) were characterized by differential scanning calorimetry (DSC) and their water‐swelling ratio. The swelling behavior of PVA/GA films of different blend compositions was dependent on the crosslinking density and chemical functional groups created by the reaction between PVA and GA, such as the acetal group, ether linkage, and unreacted pendent aldehydes in PVA. The permeation performances of the membranes swollen by the water vapor contained in a feed gas were investigated. The behavior of gas permeation through a WSH membrane was parallel to the swelling behavior of the PVA/GA film in water. The permeation rate of carbon dioxide through the WSH membranes was 10⁵ (cm³ cm^?2 s^?1 cmHg) and a CO₂/N₂ separation factor was about 80 at room temperature. The effect of the additive (potassium bicarbonate, KHCO₃) and catalyst (sodium arsenite, NaASO₂) on the permeation of gases through these WSH membranes was also studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1785–1791, 2001