Pervaporation performance of polydimethylsiloxane membranes for separation of benzene/cyclohexane mixtures

Crosslinked polydimethylsiloxane/polyetherimide (PDMS/PEI) composite membranes were prepared, in which asymmetric microporous PEI membrane prepared with phase inversion method was acted as the microporous supporting layer in the flat‐plate composite membrane. The different function composition of the PDMS/PEI composite membranes were characterized by reflection Fourier transform infrared (FTIR) spectroscopy. The surface and section of PDMS/PEI composite membranes were investigated by scanning electron microscope (SEM). The composite membranes prepared in this work were employed in pervaporation separation of benzene/cyclohexane mixtures. Effects of feed temperature, feed composition, concentration of crosslinking agent on the separation efficiency of benzene/cyclohexane mixtures were investigated experimentally. In addition, the swelling rate and stableness of composite membrane during long time operation were studied, which should be significant for practical application. The results demonstrated that the pervaporation method could be very effective for separation of the benzene/cyclohexane mixtures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

Pervaporation separation of water/alcohol mixtures through hydroxypropylated chitosan membranes

The present study investigated the pervaporation performance of novel hydroxypropylated chitosan (HPCS) membranes to separate water from an aqueous alcohol solution. Hydroxypropylated chitosan was prepared from the reaction of chitosan and propylene oxide. The results show that the separation factor decreases and the flux increases with increasing of the substitution degree of the hydroxypropylated chitosan membrane. Crosslinking with glutaraldehyde or treatment with Cu²⁺ can improve the pervaporation performance of modified chitosan membrane grately. The performance data indicate that the crosslinking hydroxypropylated chitosan membrane treated with Cu²⁺ is an excellent pervaporation membrane for the separation of alcohol–water mixtures, and one-stage separation is attainable for some alcohol–water mixtures such as an n-propanol–water and an isopropanol–water system, which has a good separation factor of 220 for the n-PrOH/water system and 240 for the i-PrOH/water system using 85 wt % alcohol concentration at 60°C. The flux for both cases is around 0.5 kg m⁻² h⁻¹. At the same time, the structure of the chemically modified chitosan membranes and their separation characteristics for aqueous alcohol solutions are also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2035–2041, 1998     

Pervaporation separation of n‐heptane/organosulfur mixtures with PDMS membrane: Experimental and modelling

In this paper, polydimethylsiloxane (PDMS) pervaporation membrane was employed to simulate the desulfurization process of gasoline where n‐heptane was selected to stand for gasoline. A modified solution–diffusion model is proposed to account for the mass transport of penetrants in the polymer membrane. In the model, the group contribution method (the UNIFAC‐ZM model) is applied to calculate the activity of penetrants in the polymer membrane, and the free volume theory with some modifications is employed to describe the diffusion behaviour of the penetrants. The effects of operating temperature and feed concentration on pervaporation properties were investigated to validate the model. It has been shown that the results predicted by the solution–diffusion model are in good agreement with the experimental values.     

Pervaporation separation of water‐isopropanol mixtures using polymeric membranes: Modeling and simulation aspects

Pervaporation technique was used to separate water + isopropanol azeotropic mixtures at 30°C using pure sodium alginate, pure poly(vinyl alcohol), and blend membranes of sodium alginate containing 10 and 20 mass % of poly(vinyl alcohol). The membrane performance was studied by calculating flux, selectivity, pervaporation separation index, and enrichment factor. Pure sodium alginate membrane gave the highest pervaporation separation index for all compositions of water. Pervaporation experiments were carried out for 10 mass % containing water + isopropanol mixture at 30, 40, and 50°C. The Arrhenius activation parameters were computed. The PV results have been analyzed by considering complete mixing and plug flow models. Design parameters, like membrane area, permeate concentrations, flux, stage cut, separation selectivity, etc., have been calculated for different feed compositions of water in the mixture. Results are explained in terms of sorption‐diffusion principles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1143–1153, 2005     

Pervaporation separation of water/dimethylformamide mixtures using poly(vinyl alcohol)‐g‐polyacrylamide copolymeric membranes

Grafted copolymeric membranes of poly(vinyl alcohol) with acrylamide (PVA‐g‐AAm) were developed and used in the pervaporation separation of water–dimethylformamide mixtures by varying the amount of water in the feed from 0 to 100%. From these data, the permeation flux, pervaporation separation index, diffusion coefficient, swelling index, and separation selectivity were calculated at 25, 35, and 45°C. The Arrhenius activation parameters for permeation flux ranged between 22 and 63 kJ/mol, while the activation energy for diffusion ranged between 23 and 67 kJ/mol. Separation selectivity was between 15 and 22. The highest permeation flux of 0.459 kg m^?2 h^?1 was obtained for the 93% grafted membrane at 90% of water in the feed mixture. The results are discussed using the principles of the solution–diffusion model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 273–282, 2002     

Mixed matrix membranes of polydimethylsiloxane with activated carbon for ABE separation

The demand for the large-scale biofuels production is very high. The use of ethanol and butanol in flex-fuel vehicles have already been achieved, but still need improvement to decrease the gasoline-dependence. In addition to it, the preparation of ethanol and butanol by eco-friendly routes are still a challenge. The use of ABE route, in which acetone, butanol, and ethanol are prepared by fermentation of 5 or 6 carbon sugars, requires higher yields and better separation performance. The goal of this work was to evaluate the use of pervaporation through asymmetric activated carbon (AC) dispersed polymethylsiloxane membranes for the separation of ABE aqueous solution with 1 wt% total organics. The amount of the filler was varied from 0 to 3 wt%. Membranes were characterized by scanning electronic microscopy, Fourier transformed infrared spectroscopy, swelling in solvents, thermogravimetric analysis, and differential scanning calorimetry. Membrane with 1 wt% of AC membrane showed different behaviors both in thermal resistance, which was increased, and also in pervaporation separation index (PSI). In this condition, membrane total flux, separation factor, and PSI for ethanol were 13.2, 2.6, and 19.9 g m⁻² h⁻¹, so that sorption behavior and diffusion rates were changed. Thus, it was possible to modulate membrane properties.     

Pervaporation separation of MTBE–methanol mixtures using cross‐linked PVA membranes

Poly(vinyl alcohol)(PVA)/poly(acrylic acid)(PAA) and PVA/sulfosuccinic acid (SSA) membrane performances have been studied for the pervaporation separation of methyl tert‐butyl ether (MTBE)/methanol (MeOH) mixtures with varying operating temperatures, amount of cross‐linking agents, and feed compositions. Typically, the separation factor, about 4000, and the permeation rate, 10.1 g/m²/h, were obtained with PVA/PAA = 85/15 membrane for MTBE/MeOH = 80/20 mixtures at 50°C. For PVA/PAA membranes, it could be considered that the flux is affected by the structural changes of the membranes due to the cross‐linking and the free carboxylic acid group also took an important role in the separation characteristics through the hydrogen bonding with PVA and the feed components leading to the increase of flux. The latter membrane of the 5% SSA membrane shows the highest separation factor of 2095 with the flux of 12.79 g/m²/h for MTBE/MeOH = 80/20 mixtures at 30°C. Besides the swelling measurements were carried out for pure MTBE and MeOH, and MTBE/MeOH = 90/10, 80/20 mixtures using PVA/SSA membranes with varying SSA compositions. It has been recognized that there are two factors, the membrane network and the hydrogen bonding in the swelling measurements of PVA/SSA membranes. These two factors act interdependently on the membrane swelling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1699–1707, 2000     

Pervaporation separation of isopropanol/benzene mixtures using inorganic–organic hybrid membranes

A series of pervaporation hybrid membranes were prepared from polyethylene glycol (PEG) and phenylaminomethyl trimethoxysilane (PAMTMS) based on the sol‐gel process, in which PEG was used as an organic moiety to improve the affinity for organic alcohols and silicone of PAMTMS was used as inorganic moiety to increase the permeation flux of organic species. Their application to separate isopropanol/benzene mixtures was investigated. FTIR spectra confirmed the reaction products. DSC measurement revealed that the influence of PEG content on the T_g and thermal behavior of membranes A, B, and C. FE‐SEM images exhibited that phase‐separated structure has occurred when the PEG content elevated to some extent. Pervaporation experiments showed that the permeation flux increased and the separation factor decreased with an increase in isopropanol (IPA) content in feed at 30°C. Meanwhile, the separation factor increased with an increase in feed temperature at 60 vol % IPA content. Moreover, it was found that the permeation flux was independent of the feed temperature, suggesting that feed temperature has little impact on the thermal motion of polymer chains. The increasing cross‐linking degree in hybrid matrix might be responsible for such trend. Based on these findings, it can be concluded that these pervaporation hybrid membranes have potential applications in the separation of isopropanol/benzene binary mixtures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modified polysulfone membranes. III. Pervaporation separation of benzene–cyclohexane mixtures through carboxylated polysulfone membranes*

Membranes prepared from carboxylated polysulfone permeated benzene preferentially from benzene–cyclohexane mixtures by pervaporation. Hydrophilic polysulfones containing carboxyl groups with degrees of substitution (DS) ranging from 0.46 to 1.90 groups per repeating unit were selected for this study. The membrane having a carboxyl group DS of 0.88 showed the best trade‐off between flux and permselectivity. The permselectivity towards benzene was 234 at the weight fraction of benzene in feed of 0.1. From pervaporation and sorption experiments, it was evident that permselectivity toward benzene was due to solubility selectivity. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 407–412, 1999     

Synthesis and characterization of polyacrylamidegrafted sodium alginate membranes for pervaporation separation of water + isopropanol mixtures

Polyacrylamide‐grafted‐sodium alginate copolymers were prepared by persulfate‐induced radical polymerization by using polymer‐to‐monomer ratios of 2 : 1 and 1 : 1. Polymers were characterized by Fourier transform infrared spectroscopy, differential thermal analysis, and viscosity. Membranes were prepared from the polymers, crosslinked with glutaraldehyde, and used in the pervaporation separation of water + isopropanol mixtures at 30°C. Equilibrium swelling experiments were performed for mixtures containing 10 to 80 mass % of water in the feed. Both the grafted copolymer membranes were ruptured while separating 10 mass % of water in the feed mixture. However, beyond 20 mass % of water in the feed mixture, flux increased with increasing grafting ratio, while selectivity decreased. Pervaporation separation experiments were carried out at 30, 40, and 50°C for 20 mass % of water in the feed mixture. By increasing the temperature, flux increased, whereas selectivity decreased. Arrhenius activation parameters for pervaporation and diffusion decreased with increasing grafting ratio of the membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2030–2037, 2004     

聚环糊精填充PDMS渗透蒸发膜分离苯酚水溶液

以聚二甲基硅烷为预聚体,正硅酸乙酯为交联剂,二丁基二月桂酸锡为催化剂,三氯甲烷或正庚烷为溶剂,通过相转化法制备得到了空白聚二甲基硅氧烷（PDMS）膜和聚环糊精（CDP）填充PDMS（CDP-f-PDMS）膜.考察了空白PDMS膜和CDP-f-PDMS膜对苯酚水溶液的渗透蒸发分离性能,证明填充膜优于空白膜.还分别考察了溶剂类型、填充剂用量等制膜因素和操作温度、原料液流量、原料液浓度等操作因素对PDMS膜的渗透蒸发分离性能的影响.当温度为60℃,CDP填充量为1%（质量）时,CDP-f-PDMS膜的渗透通量和分离因子分别可达32.0 g•m-²•h^-1和7.2.     

Pervaporation separation of IPA‐water mixtures through 4A zeolite‐filled sodium alginate membranes

Incorporation of zeolites into natural polymers has been shown experimentally to enhance both the flux and selectivity in pervaporative dehydration separation of organic compounds. Pervaporation is a promising membrane technique for separation of volatile organic compounds (VOCs)/water mixtures. In this study, hydrophilic sodium alginate (SA) mixed membranes were prepared using solution casting technique by incorporating zeolites into the polymer matrix. The prepared membranes were characterized by ATR‐Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), Thermal Gravimetric Analysis (TGA), and differential scanning calorimetry (DSC) were tested in a laboratory scale pervaporation experimental set‐up. The effect of experimental parameters such as the type and composition of zeolites on permeation flux and selectivity was investigated. When tested on IPA‐water mixtures, the zeolite‐filled membrane was found to give much higher selectivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pervaporation and gas separation membranes made from polyimide/polydimethylsiloxane block copolymer

Polyimide/polydimethylsiloxane block copolymers were prepared from oligoimides based on 2-aminopyridine-terminated 3,3′-oxybis(phthalic anhydride) and 1,4-bis(4-amino-α, α-dimethylbenzyl)benzene, and 3-aminopropyl-terminated oligo(dimethylsiloxane)s. Selectivity of homogeneous membranes prepared from the copolymers depends on the polydimethylsiloxane (PDMS) content: Selectivity of copolymers with up to approximately 20 wt % of PDMS is similar to that of polyimide homopolymer, whereas selectivity of copolymers containing more than 20 wt % of PDMS resembles that of pure PDMS. © 1996 John Wiley & Sons, Inc.     

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     

Pervaporation and Vapor Permeation Tutorial: Membrane Processes for the Selective Separation of Liquid and Vapor Mixtures

Pervaporation and vapor permeation are membrane-based processes proposed as alternatives to conventional separation technologies. Applications range from organic solvent removal from water, ethanol, or butanol recovery from fermentation broths, solvent/biofuel dehydration to meet dryness specifications, and organic-organic separations such as the removal of sulfur compounds from gasoline. Unlike membrane filtration processes, which rely on an applied liquid pressure gradient and size sieving to accomplish a separation, pervaporation and vapor permeation separate compounds based on a chemical activity driving force and the sorption and diffusion of the compounds through the membrane. These properties enable the separation of even miscible liquid mixtures.     

Pervaporation separation of methyl tert-butyl ether/methanol mixtures using a high-performance blended membrane

For the separation of methyl tert-butyl ether (MTBE) and methanol mixtures, we investigated the pervaporation performance of a blend membrane made from cellulose acetate and cellulose acetate hydrogen phthalate. At first the influence of the blend composition was studied with a certain feed mixture. We found that all the tested membranes permeate methanol preferentially. The selectivity increases and the permeation rate decreases with increasing cellulose acetate content in the blend. Therefore, an optimal blend composition of 30 wt % in cellulose acetate was chosen to evaluate the influence of the feed composition and the experimental temperature on the pervaporation performance. When the feed temperature or the methanol content in the feed increases, the permeation rates are greatly enhanced and the selectivity decreases. However, the temperature effect is more significant at low methanol content in the feed and becomes negligible at high methanol content in the feed where plasticity effects prevail. A comparison, carried out with all the membranes until now used for the separation of MTBE/methanol mixtures, showed that the blended membrane studied in this present work presents good permselective properties. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 875–882, 1997     

Pervaporation properties of aromatic/nonaromatic hydrocarbons of crosslinked membranes of copolymers based on diethyl vinylbenzylphosphonate

Copoly(diethyl vinylbenzylphosphonate/hydroxyethyl methacrylate) [copoly(VBP–HEMA)] and copoly(diethyl vinylbenzylphosphonate/vinylbenzyl chloride) [copoly(VBP–VBC)] were prepared and their membranes crosslinked by a reaction of ethylene glycol diglycidyl ether and ethylene diamine with, respectively, hydroxyl and methylene chloride groups in their side chains. Pervaporation (PV) and sorption of benzene–n‐hexane (Bz–Hx), benzene–cyclohexane (Bz–Cx), and toluene–n‐octane (Tol–n‐Ot) mixtures were investigated. The membranes were in a rubbery state and preferentially permeable to aromatics. They had higher specific permeation flux and a lower PV separation factor compared with the crosslinked membranes of methacrylate copolymers with analogous pendant groups. They displayed better PV performance for Tol–n‐Ot. Sorption isotherms of Bz–Hx mixtures were represented by the Flory–Rehner model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2177–2185, 2003     

渗透汽化在酯水体系分离中的应用

概述了渗透汽化膜分离技术在酯水体系分离中的应用,着重介绍了渗透汽化-酯化反应耦联膜反应器的动力学模型、膜材料、膜组件及其工业应用实例,指出了新的膜材料的开发与改性、以及全新概念的膜组件设计将是今后膜技术在食品工业中应用研究的重点。