Sorption equilibria and diffusion coefficients of ethanol and water in the PVA membranes containing cyclodextrin

Effects of cyclodextrin (CD) on the pervaporation characteristics for water/ethanol through the PVA/CD membranes (PVA membranes containing β-CD oligomer) have been investigated in terms of sorption equilibria and diffusion coefficients based on the sorption–diffusion theory. The increase in water selectivity through the pervaporation by CD was due mainly to the changes in the diffusion coefficients by CD, which depended on the feed composition and the cross-linking time. The water selectivity through the sorption equilibria was not increased by the addition of CD, and the ethanol-sorption amount was increased by CD. These effects of CD were interpreted by the inclusion strength in the CD cavity and the cross-linking density of the PVA phase. © 1994 John Wiley & Sons, Inc.     

Prevaporation of water/alcohol mixtures through the PVA membranes containing cyclodextrin oligomer

Prevaporation through the PVA membrame containing β-cyclodextrin oligomer (PVA/CD membrane) was performed for the mixtures of water/ethanol, water/1-propanol, and water/2-propanol. At higher alcohol concentrations, the water selectivities were greatly increased by CD for all the mixtures, in the order of 2-propanol/water>1-propanol/water>ethanol/water. The water permeation rate was decreased by CD, and the alcohol permeation rate was decreased much more for each mixture. At lower alcohol concentrations, the water selectivity for 1-propanol/water was slightly increased by CD, and that for 2-propanol/water was scarcely affeted, whereas that for ethanol/water was greatly increased. The water permeation rate was increased by CD for each mixture, and the relative increases in the water rates for propanols/water were smaller than that for ethanol/water. The permeation rate of 1-propanol as well as that of ethanol was decreased by CD, but the rate of 2-propanol was was increased. These effects of CD can be explained in terms of the inclusion strength. © 1994 John Wiley & Sons, Inc.     

PVA/PEG/TEOS杂化膜制备及性能研究

以聚乙烯醇(PVA)与聚乙二醇(PEG)共混,并与正硅酸乙酯(TEOS)进行交联反应制备杂化膜。FTIR证实杂化溶胶液发生交联反应形成共价键Si—O—C,WXRD观察表明加入TEOS改变了膜结晶度,加入PEG提高了PVA膜对乙醇/水溶液的渗透通量,但分离因子下降,随着TEOS的加入,膜的分离因子提高。在TEOS质量分数为10%时,杂化膜的分离因子达到最大。提高退火温度可以提高膜的分离因子,但通量下降。在100℃下退火12 h的杂化膜对乙醇质量分数为85%的乙醇/水溶液的分离性能最佳。     

新型聚乙烯醇/硅系杂化膜的制备及渗透性能

采用溶胶-凝胶法制备了聚乙烯醇（PVA）/γ-氨丙基三乙氧基硅氧烷（APTEOS）有机/无机杂化膜。用FTIR和XRD对杂化膜进行了表征。测定了膜在乙醇/水溶液中的溶胀行为。考察了杂化膜对85%（质量）的乙醇/水溶液的渗透蒸发分离性能。加入APTEOS降低了PVA的结晶度,有效控制了膜的溶胀,呈现出优良的分离性能。随着APTEOS含量的增加,杂化膜的选择性急剧增加,在5.0%（质量）时达到最大值;同时膜的渗透通量迅速增加。解决了PVA膜trade-off效应。     

Tubular composite PVA ceramic supported membrane for bio-ethanol production

Thin polyvinyl alcohol (PVA) layers loaded with fumed silica were coated on porous ceramic supports. Scanning electron microscope (SEM) was used to characterize the ceramic-supported thin PVA active layers and the effects of coating gel PVA concentration on thickness and density of the active layers were investigated. Pervaporation (PV) dehydration of 90 wt.% ethanol was performed at temperatures of 30, 45 and 60 °C. The values of water flux (0.05–2.92 kg/m² h) and selectivity (3–180) exceed typical values obtained for pure PVA membranes. Besides the pervaporation separation index (PSI) varies from 5.84 to 82.81. Compared to pure PVA membrane with maximum PSI of 47.2, the pervaporation performance was significantly improved. The best separation performance was obtained using the membrane prepared from 5 wt.% PVA solution containing 6 wt.% fumed silica and at pervaporation temperature of 45 °C with permeation flux of 1.69 kg/m² h, and selectivity of 50. The highest permeation flux, selectivity and PSI was 2.92 kg/m² h, 180 and 82.81, obtained at 60, 30 and 45 °C, respectively, while using membranes loaded with 8, zero and 6 wt.% of fumed silica in PVA membrane prepared from 5, 10 and 5 wt.% PVA solutions, respectively. The novel ceramic support increased mechanical strength of the membrane and protected the ultrathin polymeric top active layer under aggressive operating conditions, especially high pressure gradient across the membrane. Incorporation of fumed silica also resulted in higher water permeation flux. Due to these results, the synthesized membranes are suitable for ethanol purification in industrial scales.     

TiO2/PVA杂化膜的渗透蒸发性能及结构表征

通过纳米TiO2粒子填充改性制备了新型TiO2/PVA杂化膜。红外光谱表明纳米TiO2表面的羟基与聚乙烯醇(PVA)链上的羟基存在较强的氢键作用。扫描电镜显示当TiO2的质量分数低于1.5%时,在PVA中分散均匀。X射线衍射显示纳米TiO2的加入降低了膜的结晶度。通过对含水质量分数低于20%的水/乙醇体系的脱水研究了该杂化膜的渗透性能,考察了TiO2粒子填充量、料液质量分数和温度与膜分离性能之间的关系。渗透通量J随着TiO2、水质量分数和温度的升高而增加,分离因子随着温度和水质量分数的升高而下降,在TiO2质量分数为1.5%时分离因子达到最佳值。40℃下分离质量分数85%的乙醇水溶液,分离因子可达1 590,渗透通量为0.049kg/(m2.h)。     

Tunable physicochemical properties of PVA nanocomposite membranes for enhanced pervaporation performance

This study reveals the effect of hydrophilic bentonite nanoclay on the pervaporation separation of azeotropic composition of water and 1,4‐dioxane. The permselectivity of the membrane increased with filler concentration and was selective toward water at minimum filler loading. The intrinsic properties such as membrane permeance and selectivity increased with the concentration of hydrophilic bentonite nanoclay and crosslinked poly(vinyl alcohol) (PVA) with 2 wt% nanoclay membranes showed intrinsic selectivity 443 (532% increment than that of pristine membranes) with water permeance 4,675 gas permeation unit which is significantly higher compared to earlier literature. X‐ray diffraction and Transmission electron microscopy showed the well exfoliated and distributed nanoclay structure in the crosslinked PVA matrix. Interaction of PVA with nanoclay and the hydrophilic character of the membranes were characterized by Fourier transform infrared spectra and contact angle analysis, respectively. Interestingly, in this work the membranes exhibited simultaneous increment in both permeation flux and selectivity with filler loading, rather than the usual inverse trend of flux and selectivity. A predictive model of pervaporation was used to explain the pervaporation behavior and it showed good agreement with experimental results for overall pervaporation performance, preferential sorption of water, and hydrophilic‐hydrophobic nature of the membranes. POLYM. ENG. SCI., 58:849–858, 2018. © 2017 Society of Plastics Engineers     

Pervaporation separation of water–isopropyl alcohol mixture by PVA/LiBr membrane

Hydrophilic polyvinyl alcohol membranes, modified by lithium bromide, were prepared with glutaraldehyde as a crosslinking reagent. The membranes were investigated for the pervaporation dehydration of a water–isopropyl systems. The effect of the feed temperature on permeation flux and membrane selectivity was studied. The characterization of modified membranes was performed using Fourier transform infrared spectroscopy (FT‐IR), differential scanning calorimeter (DSC) and X‐ray diffraction. It was observed that the crystallinity of membranes increased as lithium bromide was added to the polymer. High performance liquid chromatography (HPLC) was used to analyze water content and isopropyl alcohol in the feed and permeate samples The pervaporation tests also confirmed an enhancement in water permeability through adding LiBr to the polymer, because of the high hydrophilic properties of this salt. According to pervaporation experiments conducted at 50°C, the water flux increased from 0.1049 kg/ m² hr to 0.1114 kg/ m² hr as 0.5 wt% of LiBr was added to the polymer matrix. Furthermore, an addition of 1 wt% of LiBr compared to homogeneous PVA membrane increased selectivity from 76 to 779. POLYM. ENG. SCI., 59:E101–E111, 2019. © 2018 Society of Plastics Engineers     

Facile Fabrication of Poly(vinyl alcohol)/Polyquaternium-10 (PVA/PQ-10) Anion Exchange Membrane with Semi-Interpenetrating Network

Anion exchange membranes (AEMs) are one of the core components of AEM fuel cells. A series of poly(vinyl alcohol)/polyquaternium-10 (PVA/PQ-10) AEMs with semi-interpenetrating networks (s-IPNs) are prepared by a simple solution-casting method using glutaraldehyde (GA) as a cross-linking agent. Subsequently, the prepared PVA/PQ-10 cross-linked membranes are characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, mechanical analysis, water uptake and swelling ratio tests, ion exchange capacity (IEC) tests, ionic conductivity measurements, and oxidative/alkaline stability tests. The effects of the mass ratio of PVA and PQ-10 and the amount of cross-linking agent GA on the performance of the PVA/PQ-10 cross-linked membranes are systematically explored. The results show that the cross-linked PVA/PQ-10 AEMs have high IEC and low water uptake and swelling ratio, and its maximum ionic conductivity can reach 79.37 mS cm^–1 at 80 °C. In addition, the PVA/PQ-10 cross-linked membrane has good oxidative and alkaline stability under optimal preparation conditions. These results may provide valuable insights toward more effective scheme designs and new, simple preparation methods for AEMs with s-IPN structures.     

季铵盐烷基醚化阳离子聚乙烯醇制备及性能

引言 渗透汽化膜分离法可分离恒沸物、热不稳定体系、节能环保,日益被重视.渗透汽化过程的核心是分离膜,膜材料的选择、改性及制备是影响膜分离性能的重要因素.近年来,聚电解质复合物(polyelectrolyte complex,PEC)渗透汽化膜的研究有了较大进展.PEC是将聚阳离子和聚阴离子通过库仑力结合形成的[1].PEC膜具有良好的机械性能,对水及水溶性小分子表现出高透过性[1].本文以聚乙烯醇(PVA)、(3-氯-2-羟丙基)-3-甲基氯化铵为原料,制备了一种QAPVA新型聚阳离子电解质.将其与POAPVA聚阴离子电解质制备PEC膜,用于分离醇/水体系,取得了满意的分离效果.     

Preparation and characterization of α-cyclodextrin-containing membranes—application to the selective extraction of xylene isomers

Polymer membranes containing α-cyclodextrin (α-CD) were prepared by the casting method using cross-linking reaction with hexamethylenediisocyanate. The film synthesis conducted with and without dibutyltin dilaurate as catalyst, resulted in two series of materials in which α-CD host entities were chemically linked to polyvinyl alcohol and physically entrapped, respectively. The obtained membranes were successfully applied to the separation of o-/p- and o-/m-xylene isomer mixtures by pertraction from water. p- and m-xylenes were found to be the faster permeants compared to the o-isomer. The separation factor of p-xylene over o-xylene varied from 7.75 to 0.35 depending on the membrane α-CD content and the feed concentration ratio. Permeation rate and separation selectivity data were discussed in terms of molecular recognition by α-CD and of coupling transport effect. Both kinds of materials showed similar behaviour in their permeation performances indicating that inclusion interaction was not changed by the chemical grafting on PVA chains.     

Butanol isomer separation using polyamide-imide/CD mixed matrix membranes via pervaporation

Mixed matrix membranes (MMMs) comprising polyamide-imide (PAI) and α-, β- or γ-cyclodextrin (CD) have been investigated experimentally and computationally for isomeric n-butanol/tert-butanol (n-BuOH/t-BuOH) separation via pervaporation. Consistent with molecular simulation, experimental results show that the CD inclusion ability and butanol discrimination ability are dependent on both CD cavity size and butanol molecular size. The PAI membrane incorporated with α-CD has the smallest cavity and has the highest discrimination ability for the n-BuOH/t-BuOH pair but with a low butanol flux. The mixed matrix membrane embedded with γ-CD has the lowest selectivity and the highest flux. The PAI/β-CD membrane has a comparable selectivity and flux, and exhibits preferential sorption and diffusion selectivity toward n-BuOH. A maximum separation factor of 1.53 with a corresponding flux of 4.4 g/m² h are obtained at an optimal β-CD loading of 15 wt%. Further increments in the CD content eventually lead to a decrease in separation performance because of CD agglomeration and severe phase separation. To better understand the influence of CD on the separation performance of mixed matrix membranes, SEM, FTIR and XRD have been employed for membrane characterizations. The effect of n-butanol/t-butanol ratio in the feed composition has also been studied. It is found that both flux and separation factor decrease with increasing n-butanol content in the feed. The decline is attributed to the change in total vapor pressure at the upstream and the mutual drag effect of isomeric butanol molecules.     

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     

Dehydration of water–alcohol mixtures by vapor permeation through PVA/clay nanocomposite membrane

An organic/inorganic hybrid nanocomposite membrane, poly(vinyl alcohol)/clay (PVAC), was prepared. The morphology of PVAC nanocomposite membranes were characterized using transmission electron microscopy (TEM), X‐ray diffraction (XRD), and atomic force microscopy (AFM). The crystallinity and surface roughness increases with an increasing clay content in the PVAC nanocomposite membrane. Compared with the pure poly(vinyl alcohol) (PVA) membrane, the hybrid nanocomposite membrane (PVAC) shows an improvement in the thermal stability and the prevention of the water‐soluble property. The oxygen permeability and the water‐vapor permeation rate decreases with an increasing clay content (1–3 wt %) in the PVAC nanocomposite membranes. In addition, the effects of the clay content on the vapor‐permeation performance of an aqueous ethanol solution through the PVAC nanocomposite membranes was also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3632–3638, 2003     

Gas permeation through water‐swollen polysaccharide/poly(vinyl alcohol) membranes

The effect of Na‐alginate content on the gas permeation properties of water‐swollen membranes prepared by varying Na‐alginate and poly(vinyl alcohol) (PVA) content in membranes was investigated. The influences of water content and crystallinity of the membranes on the gas permeation performance of the water‐swollen membranes were studied. The gas permeation rate and selectivity of Na‐alginate/PVA water‐swollen membranes were compared with those of the dry membranes. The permeation rates of nitrogen and carbon dioxide through water‐swollen membranes were in the range of 0.4–7.6 × 10^?7 to 3.7–8.5 × 10^?6 cm³ (STP)/cm² s^?1 cmHg^?1, which were 10,000 times higher than those of dry‐state membranes. The permeation rates of mixture gases through water‐swollen Na‐alginate/PVA membranes were found to increase exponentially with the increase of Na‐alginate content, whereas carbon dioxide concentration in permeates was decreased linearly. It was found that the gas permeance of the water‐swollen membranes increased with increasing the Na‐alginate content in the membrane. Gas permeation rates of the water‐swollen Na‐alginate/PVA membranes increased with increasing the water content in the membrane and decreasing the crystallinity of the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3225–3232, 2004     

Pervaporation of benzene/cyclohexane and benzene/n-hexane mixtures through PVA membranes

Poly(vinyl alcohol) (PVA) membranes (both homogeneous and asymmetric) were studied for the pervaporation separation of benzene/n-hexane and benzene/cyclohexane mixtures. The asymmetric PVA membrane with skin and porous layers was prepared through the phase inversion technique. Both asymmetric and homogeneous membranes were benzene-selective for all the feed compositions. The benzene separation factor of homogeneous PVA membrane was smaller than three, and the total permeation flux was several g/m²/h. The benzene selectivity of the asymmetric PVA membrane was much higher than that of the homogeneous membrane; weight fraction of benzene in the permeate side was larger than 90% for all the feed compositions. On the other hand, the total flux was almost unchanged compared with that of the homogeneous membrane. These results indicate that the density of the skin layer of the asymmetric membrane should be much higher than that of the homogeneous membrane. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1061–1065, 1997     

Liquid chromatographic separation of xylene isomers on α-cyclodextrin bonded phases

Mesoporous glass beads and silica were modified with α-cyclodextrin (CD) for the separation of xylene isomers by means of direct bonding, linking spacer group, and cross-linking agent. The separation efficiency of the (α-CD modified silica particles was tested by using simple column chromatography. A strong inclusion complex formation of p-xylene was observed from the column packed with α-CD bonded phases. Spacer group and crosslinking agent decreased the formation of the inclusion complex of p-xylene and increased selectivity between m-xylene and o-xylene. The inclusion complex formation of p-xylene was strongly diminished when the mobile phase was switched from methyl alcohol to toluene. The column packed with the cross-linked a-CD bonded silica showed the best performance in the separation of xylene isomers.     

PVA/OPD改性膜对微生物燃料电池性能的影响

为提高微生物燃料电池（MFC）的性能，以聚乙烯醇（PVA）为黏合剂，分别以磷钨酸（PWA）和邻苯二胺（OPD）为改性剂，采用溶液浸渍法制备了PVA/PWA和PVA/OPD改性膜并搭载于MFC系统，以SEM、电化学阻抗谱（EIS）、循环伏安法（CV）、吸水率表征了膜的性能，并考察膜改性对MFC产电量和化学需氧量（COD）去除率的影响。结果显示，PVA/PWA和PVA/OPD改性膜均能在一定程度上提升MFC性能，但PVA/OPD改性膜效果更佳。PVA/OPD改性膜的吸水率为14.49%，较常规Nafion 117膜（NF）提高了126.05%。采用PVA/OPD改性膜的MFC在测试周期内的产电量为101.75 J，较采用NF时提高了587.50%；对阿莫西林制药废水的COD去除率为66.2%，较采用NF时提高了48.4%。基于PVA/OPD的膜改性方法对提高MFC的产电性能和废水处理效果有显著作用。     

Effects of simultaneous chemical cross-linking and physical filling on separation performances of PU membranes

The novel modified polyurethane (PU) membranes were prepared by β-cyclodextrin (CD) cross-linking and SiO₂/carbon fiber filler, simultaneously. The structures, thermal stabilities, morphologies, and surface properties were characterized by FTIR, TGA, SEM, and contact angle. The results showed that the addition of inorganic particles increased the thermal stabilities of PU membranes. The modified PU membranes possessed more hydrophobic surfaces than pure PU. In the swelling investigation, PU and its modified membranes were swelled gradually with increasing phenol content in the mixture. The membranes modified by CD cross-linking (PUCD) demonstrated the highest swelling degree. Pervaporation (PV) performances were investigated in the separation of phenol from water. Three kinds of modified membranes obtained better permeability and selectivity than PU membranes. With the feed mixture of 0.5 wt% phenol at 60 °C, the modified PU membrane by CD cross-linking and SiO₂ filler (PUCD-S) obtained the total flux of 5.92 kg μm m^?2 h^?1 which was above doubled that of PU (2.90 kg μm m^?2 h^?1). The modified PU membrane by CD cross-linking and carbon fiber filling (PUCD-C) obtained the separation factor of 51.31 which was nearly tripled that of PU (17.72). The PUCD membranes showed both better permeability and selectivity than the pure PU membranes. The increased phenol content induced an increased separation factor of PUCD and PU, but a decreased selectivity of PUCD-S and PUCD-C. The methods of CD cross-linking and inorganic particle filling were effective to develop the overall separation performances, greatly.     

Modification of Thin Film Composite PVA/PAN Membranes for Pervaporation Using Aluminosilicate Nanoparticles

The effect of the modification of the polyvinyl alcohol (PVA) selective layer of thin film composite (TFC) membranes by aluminosilicate (Al₂O₃·SiO₂) nanoparticles on the structure and pervaporation performance was studied. For the first time, PVA-Al₂O₃·SiO₂/polyacrylonitrile (PAN) thin film nanocomposite (TFN) membranes for pervaporation separation of ethanol/water mixture were developed via the formation of the selective layer in dynamic mode. Selective layers of PVA/PAN and PVA-Al₂O₃·SiO₂/PAN membranes were formed via filtration of PVA aqueous solutions or PVA-Al₂O₃·SiO₂ aqueous dispersions through the ultrafiltration PAN membrane for 10 min at 0.3 MPa in dead-end mode. Average particle size and zeta potential of aluminosilicate nanoparticles in PVA aqueous solution were analyzed using the dynamic light scattering technique. Structure and surface properties of membranes were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. Membrane performance was investigated in pervaporation dehydration of ethanol/water mixtures in the broad concentration range. It was found that flux of TFN membranes decreased with addition of Al₂O₃·SiO₂ nanoparticles into the selective layer due to the increase in selective layer thickness. However, ethanol/water separation factor of TFN membranes was found to be significantly higher compared to the reference TFC membrane in the whole range of studied ethanol/water feed mixtures with different concentrations, which is attributed to the increase in membrane hydrophilicity. It was found that developed PVA-Al₂O₃·SiO₂/PAN TFN membranes were more stable in the dehydration of ethanol in the whole range of investigated concentrations as well as at different temperatures of the feed mixtures (25 °C, 35 °C, 50 °C) compared to the reference membrane which is due to the additional cross-linking of the selective layer by formation hydrogen and donor-acceptor bonds between aluminosilicate nanoparticles and PVA macromolecules.