Separation characteristics of pervaporation membrane separation processes using modified poly(vinyl alcohol) membranes

Modified poly(vinyl alcohol) (PVA) membranes prepared by the ‘solution technique’ were tested for ethanol-water mixtures by varying the reaction density (X_cr = 0.05, 0.1) at various temperatures. The results are compared with those of PVA membranes (X_cr = 0.05) prepared by the technique of the GFT Company, Germany.     

Separability of SO2 from SO2/N2 mixture through sulfoxide-modified poly(vinyl alcohol) and cellulose membranes

Separability of SO₂ from mixtures of SO₂ and N₂ gases was studied for membranes of poly(vinyl alcohol) (PVA) and cellulose modified with methyl, ethyl, t-butyl, and phenyl vinyl sulfoxides. Of these sulfoxide-modified polymers, the phenyl vinyl sulfoxide-modified PVA membranes were found to give the best separation of SO₂. In the phenyl vinyl sulfoxide modified PVA membranes, the permeability coefficient of SO₂ increased with sulfoxide content while separability of SO₂ was maximum at a sulfoxide content of 23.5 mol %; the separation factor of SO₂ was about 170 at this sulfoxide content. © 1993 John Wiley & Sons, Inc.     

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     

Properties of modified poly(vinyl alcohol) membranes prepared by the grafting of new polyelectrolyte copolymers for water–ethanol mixture separation

For the preparation of a water‐selective membrane for the pervaporation separation of an azeotropic solution, a series of grafted copolymers were synthesized by the reaction of poly(vinyl alcohol) (PVA) with poly(sodium salt styrene sulfonic acid‐co‐maleic acid) (PSStSA‐co‐MA). The esterification was performed between the hydroxyl groups of PVA and the carboxylic groups of the copolymer with a heat treatment. PSStSA‐co‐MA was prepared with sodium salt styrene sulfonic acid and maleic anhydride copolymerization in dimethyl sulfoxide with azobisisobutyronitrile as an initiator. The reaction mechanism and resultant structure were confirmed with IR spectra. The effect of the heat‐treatment time on the gel content was investigated. The permeation flux decreased and the separation factor increased as the crosslinking agent content rose. A membrane containing 15 wt % PSStSA‐co‐MA was used for water–ethanol azeotropic solution pervaporation at 30°C, and a flux of 0.43 kg/m² h and a separation factor of 190 were obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2854–2859, 2002     

Decomposition of acetic acid by advanced oxidation processes

Decomposition of acetic acid, known as a non-degradable organic compound, was conducted for several advanced oxidation processes such as TiO₂-UV-H₂O₂, Fe²⁺-H₂O₂-UV, UV-H₂O₂ and TiO₂-UV system. Acetic acid was efficiency decomposed within 120 minutes of UV radiation under the initial concentration of 500 ppm. The initial chemical oxygen demands (COD _cr ) tended to increase as H₂O₂ was added in most reactions. However, the initial COD _cr was not increased as H₂O₂ was consumed for the oxidation of iron salt in the photo-Fenton oxidation process. COD _cr and concentration of acetic acid rapidly decreased as the mole ratio of hydrogen peroxide increased owing to rapid decomposition of the reactant at the beginning of reaction. All reactions show first order pseudo reaction rate. The COD _cr removal rate and the decomposition efficiency of acetic acid were fastest in the UV-H₂O₂ process.     

Crosslinked blended poly(vinyl alcohol)/N-methylol nylon-6 membranes for the pervaporation separation of ethanol–water mixtures

Crosslinked blended membranes of poly(vinyl alcohol) (PVA) and N-methylol nylon-6 were prepared either by thermal crosslinking at 180°C or by chemical crosslinking with maleic acid. The pervaporation performance for the separation of ethanol–water mixtures of these membranes was investigated in terms of feed concentration, PVA content, and crosslinking agent content. The pervaporation performance of two differently crosslinked membranes was strongly influenced by the nature of the crosslinkage. Significant improvement in the pervaporation separation index can be achieved for chemically crosslinked membranes. From the comparison between the pervaporation and sorption tests, it is suggested that, for hydrophilic membranes, sorption properties dominate the pervaporation performance at feed solutions of higher water content, while diffusion properties govern at feed solutions of higher ethanol content. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 317–327, 1998     

Pervaporative Dehydration of Organic Solvents

Abstract

Pervaporative separation of acetone/water and isopropanol (IPA)/water systems has been studied in the water-lean range of composition of the feed mixtures. Poly(vinyl alcohol) (PVA) membranes crosslinked with citric acid, adipic acid, maleic acid, glutaraldehyde, and glyoxal were used for this purpose. The sorption characteristics of all the membranes indicate that these membranes have a good sorption selectivity for water in view of the hydrophilic nature of PVA. The type of crosslinker used for crosslinking has been shown to have an important bearing on the permeation characteristics of the membranes. Thus, the trifunctional citric acid yields the highest selectivity but lowest flux. A comparison of the productive capacities of the various membranes indicates that the glutaraldehyde crosslinked membrane has the maximum productive capacity for IPA dehydration whereas maleic acid crosslinked membrane yields the highest productive capacity for acetone dehydration.     

Branched Polyvinyl Alcohol Hybrid Membrane for Acid Recovery via Diffusion Dialysis

A branched polymer was prepared by grafting allyltrimethylammonium chloride onto polyvinyl alcohol (PVA) via free‐radical polymerization. Afterwards, a series of hybrid membranes were prepared by sol‐gel cross‐linking between quaternary ammonium‐PVA and tetraethoxysilane. The obtained membranes were characterized in terms of infrared spectroscopy, ion exchange capacity, water uptake, linear expansion ratio, and acid resistance. The thermal properties of the membranes were investigated as well. The diffusion dialysis performances of the membranes were tested by using a simulated feed solution containing HCl and FeCl₂. The diffusion dialysis coefficients and the separation factors were much better than those of the commercial DF‐120 membrane.     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of solvent adsorption on solution properties of poly(vinyl alcohol)/dimethylsulfoxide/water ternary systems

In this study, the solvent adsorption phenomena of poly(vinyl alcohol) (PVA) in cosolvent mixtures of dimethylsulfoxide (DMSO; solvent 1) and water (solvent 2) were investigated. Typically, this cosolvent mixture could form hydrogen‐bonded DMSO/(water)₂ complexes, involving one DMSO and two water molecules. Because of the complex formation in the cosolvent mixtures, PVA chains preferentially adsorb water molecules at DMSO mole fraction X₁ < 0.33, but preferentially adsorb DMSO molecules at X₁ > 0.33. The preferential adsorption of DMSO (a good solvent for PVA) could cause the relatively extended conformation of PVA chains in solutions because of the increase in excluded volume effect. Because of various interactions between PVA chains and cosolvent mixtures, the aggregation and gelation behaviors of PVA solutions were significantly affected by the composition of cosolvent mixture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3211–3217, 2004     

Poly(ether sulfone) supported hybrid poly(vinyl alcohol)–maleic acid–silicone dioxide membranes for the pervaporation separation of ethanol–water mixtures

Microporous poly(ether sulfone) (PES) supported hybrid polymer–inorganic membranes were prepared by the crosslinking of poly(vinyl alcohol) (PVA), maleic acid (MA), and SiO₂ via an aqueous sol–gel route and a solution‐casting method. The membrane performance was tested for the pervaporation separation of ethanol–water mixtures from 20 to 60 °C with a feed ethanol concentration of 96 wt %. The membrane characterization results reveal that different SiO₂ loadings affected the crystallinity and roughness of the membranes. The PVA–MA–SiO₂ membrane containing 10 wt % SiO₂ showed that SiO₂ nanoparticles were well dispersed within the polymer matrix; this resulted in significant enhancements in both the flux and selectivity. The membrane achieved a high water permeability of 1202 g·μm·m^?2 h^?1 kPa^?1 and a selectivity of 1027 for the separation of a 96 wt % ethanol‐containing aqueous solution. This enhanced membrane performance might have been due to the dense crosslinking membrane network, increased free volume, and uniform distribution of SiO₂ nanoparticles. Both the water and ethanol fluxes increased with the feed water concentration and temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44839.     

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     

Changes in free volume and gas permeation properties of poly(vinyl alcohol) nanocomposite membranes modified using cage-structured polyhedral oligomeric silsesquioxane

The present work reports the effect of various organically functionalized polyhedral oligomeric silsesquioxane (POSS) particles on the gas transport properties (N₂, O₂, and CO₂ molecules) in poly(vinyl alcohol) (PVA) membranes. The incorporation of polyethylene glycol-POSS (PEG-POSS), octa-tetramethylammonium-POSS (Octa-TMA-POSS) and m-POSS (Octa-TMA-POSS molecule was modified using cetyltrimethyl ammonium bromide) led to the enhancement in CO₂ separation performance of PVA, among which, PEG-POSS exhibited highest CO₂ separation due to the dipole-quadrupolar interaction of CO₂ with ethylene oxide group in POSS. Octa-TMA-POSS and m-POSS reduced the O₂ and N₂ permeability of the PVA membrane due to the reduction in the number of permeating pathways as compared to pure PVA. Free volume of the membranes was evaluated by positron annihilation lifetime spectroscopic (PALS) and coincidence Doppler broadening measurements. PALS confirms the increase in polymer free volume in PVA/POSS system due to the presence of rigid and spherical POSS molecule, which could enter in the polymer chain and provide viable pathway for molecular transport. Maxwel–Wagner–Sillar and Higuchi models were applied for the theoretical prediction of permeability of the fabricated membranes.     

Mechanical characteristics of modified unsaturated polyester resins derived from poly(ethylene terephthalate) waste

The depolymerization of poly(ethylene terephthalate) (PET), by an alcoholysis reaction is an easy operation and gives prospects for the utilization of wastes. PET waste was first depolymerized by glycolysis reaction at three different molar ratios of diethylene glycol (DEG), in the presence of manganese acetate as a transesterification catalyst. Copolyesters of PET modified with varied mole ratios of p‐hydroxybenzoic acid (PHBA) were reported to exhibit excellent mechanical and chemical properties due to their liquid crystalline behaviour. Here we study the effect of incorporating (PHBA) units into the building structures of different unsaturated polyesters synthesized originally from glycolysed PET waste. Modified unsaturated polyesters were synthesized by depolymerizing PET with DEG, and the obtained oligoesters were reacted with PHBA and maleic anhydride (MA). The molar ratio of the added PHBA was varied to investigate its effect on the mechanical characteristics of these modified unsaturated polyesters. The data obtained reveal that increasing the molar ratio of PHBA within the studied range of concentrations leads to a pronounced improvement in the mechanical characteristics, which is represented mainly by the values of/maximum compression strength (σ_max) and Young's modulus (E_Y). © 2002 Society of Chemical Industry     

Dehydration of light oil by pervaporation using poly(vinyl alcohol)–poly(acrylic acid‐co‐maleic acid) membranes

A new blended membrane was prepared and tested by pervaporation of light oil, a mixture of five alcohols plus water. The blended membrane was synthesized by blending poly(vinyl alcohol) and poly(acrylic acid‐co‐maleic acid) sodium salt in the presence of sulfuric acid to dope the reaction. We tested several membranes in order to choose the adequate composition to have the best permselectivity. The PVA(60)–PAA‐co‐maleic acid(40) membrane was selected as it was found to be highly selective. Sorption experiments were performed using binary and ternary water–alcohol solutions. The influence of temperature and feed composition on the selectivity and flux in pervaporation was investigated for two different binary mixtures (water/ethanol, water/isobutanol) and one ternary system (water/ethanol/isobutanol). This membrane presents good permselective properties, high water flux, and good selectivity and can even be used for high‐water activities The performances of this new membrane were compared to those obtained with the PVA(90)–PAA(10) membrane synthesized recently: The fluxes observed for the water–ethanol separation were of the same order of magnitude but the selectivity was found to be much higher. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1709–1716, 2002     

Pervaporation of ethanol-water mixtures through poly(vinyl alcohol-g-acrylic acid) membranes prepared by use of Fenton's reagent in grafting

Ionic crosslinking of the ferric ions and the carboxylic groups in the poly(vinyl alcohol-g-acrylic acid) (poly(VA-g-AA)) membranes improves the size screening effect in the pervaporation of ethanol-water separation. In the grafting polymerization of acrylic acid monomer onto poly(vinyl alcohol) (PVA), ferric ions are remained in the polymer membranes as the Fenton's reagent(Fe²⁺-H₂O₂) is used to initiate the reaction. Completely reversed trends in terms of the degree of swelling, the pervaporation selectivity, and the flux of permeates are obtained depending on that the ferric ions are present or absent in the membranes. The degree of swelling decreases, the pervaporation selectivity increases, and the flux decreases as the grafting percentage increases for the membranes containing ferric ions. The degree of swelling and the flux of permeates increase but the pervaporation selectivity is reduced as the grafting percentage increases for the membranes which were washed with acid to remove ferric ions.     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.     

Study of glycolysis of poly(ethylene terephthalate) recycled from postconsumer soft‐drink bottles. III. Further investigation

A modified glycolysis reaction of recycled poly(ethylene terephthalate) (PET) bottles by ethylene glycol (EG) was investigated. Influences of the glycolysis temperature, the glycolysis time, and the amount of catalysts (per kg of recycled PET) were illustrated in this study. The manganese acetate was used as a glycolysis catalyst in this study. Bis‐2‐hydroxyethyl terephthalate (BHET) and its dimer were predominately glycolysis products. It was found the optimum glycolysis temperature is 190°C. And the best glycolysis condition is 190°C of glycolysis temperature, 1.5 h of glycolysis time, and 0.025 moles of manganese acetate based on per kg of recycled PET. If the best glycolysis condition is conducted, the glycolysis conversion may be as high as 100%. For a given reaction time (1.0 h), the ln(% glycolysis conversion) is linear to 1/T (K^?1) and the activation energy (E) of glycolysis reaction is around 92.175 kJ/(g mole). The glycolysis conversion rate increases significantly with increasing the glycolysis temperature, the glycolysis time, or the amount of manganese acetate (glycolysis catalyst). Thermal analyses of glycolysis products were examined by a differential scanning calorimetry (DSC) and a thermogravimetric analysis (TGA). According to the definition of a 2³ factorial experimental design, the sequence of the main effects on the glycolysis conversion of the recycled PET, in ascending order, is the glycolysis time (0.18) < the amount of catalyst per kg of the recycled PET (0.34) < the glycolysis temperature (0.40). Meanwhile, the prediction equation of glycolysis conversion from the result of a 2³ factorial experimental design is ? = 0.259+0.20X₁+0.09X₂+0.17X₃+0.06X₁ X₂+0.145X₁X₃+0.05X₂X₃+0.035X₁X₂X₃. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2004–2010, 2003     

Blends of aliphatic polyesters. IV. Morphology,swelling behavior,and surface and bulk properties of blends from hydrophobic poly(L-lactide) and hydrophilic poly(vinyl alcohol)

Blend films were prepared from hydrophobic poly(L -lactide) (PLLA) and hydrophilic poly(vinyl alcohol) (PVA) with different PLLA contents [X_PLLA (w/w) = PLLA/(PVA + PLLA)] by solution casting and melt quenching. Their morphology, swelling behavior, and surface and bulk properties were investigated. Polarizing optical microscopy, scanning electron microscopy, differential scanning calorimetry, X-ray diffractometry, and tensile testing revealed that PLLA and PVA were phase separated in these blend films and the PLLA-rich and PVA-rich phases both formed a continuous domain in the blend film of X_PLLA = 0.5. The water absorption of the blend films was higher for the blend films of low X_PLLA values when compared at the same immersion time, and it was larger than expected from those of nonblended PLLA and PVA films. The dynamic contact angles of the blend films were linearly increased with an increase in X_PLLA. The tensile strength and Young's modulus of the dry blend films decreased with a rise in X_PLLA, but this dependence was reversed because of the large decreases in tensile strength and Young's modulus for the blend films having high X_PLLA values after immersion in water. The elongation at break was higher for the wet blend film than for the dry blend film when compared at the same X_PLLA and that of the dry and wet blend films decreased with an increase in X_PLLA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2151–2160, 2001     

Preparation and characterization of PVA membrane modified by water‐soluble hyperbranched polyester (WHBP) for the dehydration of n‐butanol

Water‐soluble hyperbranched polyester (WHBP) was synthesized through the esterification reaction of the fourth generation hyperbranched polyester and maleic anhydride. A novel cross‐linked WHBP/PVA membrane was prepared by adding WHBP into poly(vinyl alcohol) (PVA) solution with glutaraldehyde as the cross‐linker. WHBP was characterized by Nuclear Magnetic Resonance and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR‐FTIR), while WHBP/PVA membranes were characterized by ATR‐FTIR, X‐ray Diffraction, Scanning Electron Microscopy, Thermogravimetric Analysis, mechanical capacity, and water contact angle. Testing results showed that maleic anhydride was grafted on the surface of WHBP; compared with PVA membrane, WHBP/PVA membrane had lower crystallinity, weaker mechanical strength, higher hydrophilicity, and better thermal stability. Sorption and diffusion behaviors of n‐butanol and water in WHBP/PVA membrane were investigated; pervaporation performances of WHBP/PVA membrane were studied through the dehydration of the 90 wt % n‐butanol aqueous solution at 40°C. With an increase of the WHBP content from 0 to 30 wt %, both n‐butanol uptake and n‐butanol diffusion coefficient first decreased then increased; n‐butanol flux first decreased from 10 to 2 g·m^?2·h^?1 then increased to 213 g·m^?2·h^?1; both sorption selectivity and diffusion selectivity first increased then decreased; separation factor first increased from 88 to 1309 then decreased to 16. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43533.