Pervaporation of Methanol/Methyl‐t‐Butyl Ether Mixtures Through Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Blend Membranes

Abstract

Membranes obtained by blending poly(vinyl alcohol) (PVOH) and poly(acrylic acid) (PAA) have been investigated for the separation of methanol and methyl‐t‐butyl ether (MTBE) liquid mixtures through a pervaporation process. Experiments were performed by contacting one side of a polymer dense film with the liquid mixture and removing the vapor on the other side with an inert gas flux, a setup for a process with sweeping gas. The blend membranes, with a COOH/OH ratio in the 0.5–2.5 range, are permeated by methanol preferentially. Higher values of flux and lower values of selectivity are observed when the methanol content in the feed increases. The ratio PAA/PVOH of the membrane influences both flux and selectivity in the same way. A maximum of both flux and selectivity is observed at a COOH/OH ratio of about 2. The swelling of membranes of different composition in the presence of different liquid composition explains the flux behavior in the pervaporation experiments. The observed membrane swelling has been explained on the basis of the solubility parameters of the components of the system.     

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     

Syntheses and characterization of blend membranes of sodium alginate and poly(vinyl alcohol) for the pervaporation separation of water + isopropanol mixtures

The blend membranes of sodium alginate and poly(vinyl alcohol) have been prepared by physical mixing in different ratios (75, 50, and 25%) of sodium alginate with poly(vinyl alcohol). The membranes were crosslinked with glutaraldehyde and used in the pervaporation separation of water + isopropanol mixtures at 30°C. The crosslinking reaction was confirmed by Fourier transform infrared spectra. Permeation flux increased with an increase in mass % of water in the feed mixture as well as with an increase in the amount of poly(vinyl alcohol) in the blend, but separation selectivity decreased. Diffusion coefficients of water + isopropanol mixtures have been calculated using the Fick's equation from the sorption data. Arrhenius activation parameters were calculated for 10 mass % of water in the feed mixture using the values of flux and diffusion coefficients obtained at 30, 40, and 50°C. The diffusion and pervaporation results have been explained on the basis of solution‐diffusion principles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3642–3651, 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.     

Preparation and characterization of CMCS/PVA blend membranes and its sorption and pervaporation performance (I)

Novel pervaporation (PV) membranes for ethanol dehydration were prepared by blend poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCS), followed by the crosslinking reaction with glutaraldehyde; the structure and miscibility of the blend membranes were characterized by Fourier transform infrared, X‐ray diffraction, and differential scanning calorimetry; the results indicated that the blends were miscible. The effect of feed concentration, operation temperature, crosslinking agent content, etc. on sorption performance and PV performance of the blend membrane is investigated. The membrane of CMCS/PVA blend ratio of 8 : 2 exhibited a high separation factor of 2959 with a reasonably high water flux value of 0.14 kg m^?2h^?1 at the azeotropic feed composition (95 wt % of ethanol) at a temperature of 45°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility studies of sodium carboxymethylcellulose/poly(vinyl alcohol) blend membranes for pervaporation dehydration of isopropyl alcohol

Miscibility studies of sodium carboxymethylcellulose/poly(vinyl alcohol) (NaCMC/PVA) blends of different compositions (100/0, 80 : 20, 60 : 40, 50 : 50, 40 : 60, 20 : 80, and 0 : 100) were investigated using viscometric method. NaCMC, PVA, and their blend membranes were prepared by solution‐casting technique and were then crosslinked with glutaraldehyde (GA). The effect of blend composition on mechanical, swelling, and pervaporation results (flux and selectivity) was also investigated in this study. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR–FTIR) results showed that the blends are miscible over the entire studied composition range and further confirmed the crosslinking reaction with GA. FTIR studies reveal that the blends containing 50 : 50 (NaCMC/PVA) are an optimum miscible blend. Thermogravimetric analysis confirms that the thermal stability increased with increase in NaCMC content in NaCMC/PVA blend membrane. XRD and DSC showed a corresponding decrease in crystallinity and increase in melting point with increase in NACMC content, respectively. NaCMC/PVA blends of all the composition under study were used for dehydration of isopropyl alcohol at different compositions of IPA/water mixture (90 : 10, 87.5 : 12.5, 85 : 15, and 82.5 : 17.5) at 35°C. Swelling studies and PV results reveal that increase in NaCMC content in the blend leads to an increase in flux of water, whereas selectivity decreases. The optimum flux and selectivity were observed for the blend containing 50 : 50 NaCMC/PVA content at a feed ratio of 87.5 : 12.5 IPA/water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA), MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmenthanol =350g.m-2.h-1 and separation factor a > 400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Synthesis and characterization of hybrid membranes using poly(vinyl alcohol) and tetraethylorthosilicate for the pervaporation separation of water–isopropanol mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis and cocondensation reaction for the pervaporation separation of water‐isopropanol mixtures. The resulting membranes were characterized by Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry. The glass transition temperature of these membranes varied from 100 to 120°C with increasing TEOS content. Effects of crosslinking density and feed compositions on the pervaporation performances of the membranes were studied. The membrane containing 1.5:1 mass ratio of TEOS to PVA gave the highest separation selectivity of 900 at 30°C for 10 mass % of water in the feed mixture. It was found that the separation selectivity and permeation flux data are strongly dependent on the water composition of the feed and operating temperature. However, the membrane with the highest crosslinking density showed unusual pervaporation properties. The overall activation energy values were calculated using the Arrhenius‐type equation. The activation energy values for the permeation and diffusion varied from 49.18 to 64.96 and 55.13 to 67.31 kJ/mol, respectively. Pervaporation data have also been explained on the basis of thermodynamic quantities. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1304–1315, 2004     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA),MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmethanol = 350 g.m-2.h-1 and separation factor α＞400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Zeolite 4A-Incorporated Polymeric Membranes for Pervaporation Separation of Methanol–Methyl Acetate Mixtures

Zeolite 4A-incorporated poly(vinyl alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) membranes were prepared for pervaporation separation of methanol/methyl acetate mixtures. These membranes were characterized by Infrared spectroscopy, X-ray diffraction and Scanning electron microscopy. The results showed that crystallinity of the membrane decreased with the increase of zeolite 4A content. The effect of zeolite loading, feed composition and temperature on the membrane separation performance were discussed in detail. With the increase of zeolite 4A content, permeation flux increased continuously, but separation factor first increased and then decreased. The addition of 2.5 wt% zeolite 4A in the polymer membrane improved the separation factor from 12.9 (for PVA/PVP membrane) to the maximum value of 34.4 for 20 wt% methanol in feed at 45 °C. The separation factor decreased with increasing feed temperature, however, the flux increased with increasing feed temperature. Zeolite 4A-incorporated PVA/PVP membranes provide an effective method for the separation of methanol/methyl acetate azeotropic mixtures.     

Properties and pervaporation characteristics of chitosan–poly(N‐vinyl‐2‐pyrrolidone) blend membranes for MeOH–MTBE

Clear blends of chitosan with poly(N‐vinyl‐2‐pyrrolidone) (PVP) made from aqueous solutions appear to be miscible from visual appearance. Infrared (IR) spectra used to investigate the carbonyl—hydroxyl hydrogen bonding in the blends indicated compatibility of two polymers on a molecular level. The IR spectra were also used to determine the interaction change accessing with increasing temperature and indicated that a significant conformational change occurred. On the other hand, the blend membranes were evaluated for separation of methanol from methyl tert‐butyl ether. The influences of the membrane and the feed compositions were investigated. Methanol preferentially permeates through all the tested membranes, and the partial flux of methanol significantly increase with the poly(N‐vinyl‐2‐pyrrolidone) content increasing. The temperature dependence of pervaporation performance indicated that a significant conformational change occurred with increasing temperature. Combined with the IR results, the pervaporation properties are in agreement with characteristics of interaction between chain–chain within the blend membranes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1452–1458, 1999     

Dehydration of tetrahydrofuran by pervaporation using crosslinked PVA/PEI blend membranes

Dense blend membranes were prepared by blending hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(ethyleneimine) (PEI), which were then crosslinked by glutaraldehyde (GA) in a mixture of solvents under the catalysis of hydrochloric acid (HCl) for the dehydration of tetrahydrofuran (THF) by pervaporation. The effect of experimental parameters such as feed water concentration, permeate pressure, and membrane thicknesses on permeate parameters, i.e., flux and selectivity were determined with feed water concentration less than 40 wt %. The membranes were found to have good potential for breaking the azeotrope of 94 wt % THF with a flux of 1.072 and 0.376 kg/m² h for plane PVA/PEI and crosslinked PVA/PEI blend membrane, which exhibited high selectivity of 156 and 579 respectively. Selectivity was found to improve with decreasing feed water concentration and increasing membrane thickness, whereas flux decreased correspondingly. High permeate pressure causes a reduction in both flux and selectivity. These effects were clearly elucidated with the aid of the known relationship among plasticization effect, degree of swelling, permeate pressure, and feed water concentration. These blend membranes were also subjected to sorption studies to evaluate the extent of interaction and degree of swelling in pure as well as binary feed mixtures. Further ion exchange capacity studies were carried out for all the crosslinked and uncrosslinked membranes to determine the total number of interacting groups present in the membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1152–1161, 2006     

Pervaporation separation of aqueous organic mixtures through sulfated zirconia‐poly(vinyl alcohol) membrane

Sulfated zirconia‐poly(vinyl alcohol) membranes were prepared, and pervaporation performances for aqueous organic mixtures were investigated. These hydrophilic membranes were formed by crosslinking poly(vinyl alcohol) (PVA) with the solid acid of sulfated zirconia by an acid‐catalyzed reaction. The pervaporation performances were measured as a function of the content ratio of sulfated zirconia to PVA, which affected the degree of swelling for water and the crosslinking density of the membrane. The membrane selectivity in pervaporation of aqueous organic mixtures increased in order of acetic acid < ethanol < 2‐ethoxyethanol without sacrificing the permeation rate, depending on their feed compositions. The effects of feed temperature and concentration on the membrane performance were also significant. It was found that sulfated zirconia in the membrane preparation played an important role as a filler material as well as an effective crosslinking or insolubilization agent in improving and controlling the membrane performance, i.e., permeation rate and selectivity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1450–1455, 2001     

Blend membranes of chitosan and poly(vinyl alcohol) in pervaporation dehydration of isopropanol and tetrahydrofuran

Blend membranes of a natural polymer, chitosan, with a synthetic polymer, poly(vinyl alcohol) (PVA), were prepared by solution casting and crosslinked with a urea formaldehyde/sulfuric acid (UFS) mixture. Chitosan was used as the base component in the blend system, whereas PVA concentration was varied from 20 to 60 wt %. Blend compatibility was studied by differential scanning calorimetry, and Fourier transform infrared spectroscopy was used to study membrane crosslinking. Membranes were tested for pervaporation dehydration of isopropanol and tetrahydrofuran (THF) at 30°C in close proximity to their azeotropic compositions. Membrane performance was assessed by calculating flux and selectivity. Swelling experiments performed in water + organic mixtures at 30°C were used to explain the pervaporation results. The blend membrane containing 20 wt % PVA when tested for 5 and 10 wt % water–containing THF and isopropanol feeds exhibited selectivity of 4203 and 17,991, respectively. Flux increased with increasing concentration of water in the feed. Selectivity was highest for the 20 wt % PVA‐containing blend membrane. The results of this study are unique in the sense that the crosslinking agent used—the UFS mixture—was novel. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1918–1926, 2007     

Swollen-Dry-Layer Model for the Pervaporation of Ethanol-Water Solution through Hydrophilic Membranes

Abstract

A swollen-dry-layer model is presented for the pervaporation of ethanol-water solution through hydrophilic polymer membranes: poly(vinyl alcohol) and carboxymethyl cellulose. Independent measurements were conducted of the sorption equilibrium, the hydraulic permeation rates through the swollen membranes, and the permeabilities of ethanol and water vapors. The hydraulic permeabilities were estimated from the mutual diffusion coefficients of solution in the swollen membrane. Sorption behavior and hydraulic permeabilities showed a dependence on feed concentration. Vapor permeabilities of water and ethanol through dry membranes differ by a factor of about 20. Comparisons between the experimental data from the pervaporation run and the results calculated from the model were made. The model offers a quantitative explanation for the dependency of selectivity and flux on feed concentration. The model explained that the flux dependency caused by a change in the swollen-dry-layer ratio, and that the selectivity is governed by vapor permeabilities through the dry layer.     

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 performance and Transport phenomenon of PVA blend membranes for the separation of THF/water azeotropic mixtures

Summary Dense polymer membranes were made by mixing aqueous solutions of hydrophilic polymers poly(vinyl alcohol) (PVA) and polyethyleneimine (PEI) in different ratios for investigating the separation of Tetrahydrofuran (THF)/water azeotropic mixtures by pervaporation (PV). In order to gain a more detailed picture of the molecular transport phenomenon, we have performed sorption gravimetric experiments at 30 °C to compute diffusion, swelling, sorption and permeability coefficients of PVA/PEI membranes in the presence of THF and water. The membranes were found to have good potential for breaking the azeotrope of THF at 6% concentration of water. An increase in PVA content in the blend caused a reduction in the flux and an increase in selectivity. Among the blends tested in the study, the 5:1 PVA/PEI blend membrane showed the highest separation factor of 181.5, exhibited a flux of 1.28 kg/m²h for THF respectively at azeotropic feed composition.     

Pervaporation separation of isopropanol–water mixtures using mixed matrix blend membranes of poly(vinyl alcohol)/poly(vinyl pyrrolidone) loaded with phosphomolybdic acid

Mixed matrix membranes of poly(vinyl alcohol) and poly(vinyl pyrrilidone) blends were prepared by loading with phosphomolybdic acid (PMA) and their pervaporation (PV) properties were investigated for the PV separation of isopropanol. Membrane performance shown a dependence on the extent of PMA loading. The 4 wt % PMA‐loaded blend membrane had the highest separation factor of 29991, which declined considerably at higher loading. The flux of 4 wt % PMA‐loaded membrane was lower than that of nascent blend membrane. Feed water composition and temperature influenced the PV performance. Solubility selectivity was higher than diffusion selectivity. Degree of swelling was smaller after PMA loading exhibiting better separation ability. The PV results were analyzed using the Flory‐Huggins theory and sorption was dominated by Langmuir's mode. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Separation of Acetic Acid/Water Mixtures by Pervaporation through Poly(Vinyl Alcohol)–Sodium Alginate Blend Membranes

Abstract

Dense pervaporation (PV) membranes were prepared by blending hydrophilic polymers, poly(vinyl alcohol) (PVA), and sodium alginate (SA), which were then crosslinked with glutaraldehyde (GA) for the separation of acetic acid/water mixtures. These membranes (PVA‐SA) were characterized for morphology, intermolecular interactions, thermal stability, and physico‐mechanical properties using XRD, FTIR, TGA and tensile testing respectively. The effect of experimental parameters such as feed composition and permeate pressure on separation performance of the crosslinked membranes was determined. Sorption studies and porosity measurement were carried out to evaluate the extent of interaction and degree of swelling of the polyion membranes, in acetic acid and water as well as in mixtures of acetic acid and water. Further the results were compared with the commercial membrane (Sulzer pervap 2205). The membrane appears to have a good potential for dehydrating 90 wt% acetic acid with a reasonably high selectivity of 21.5 and a substantial water flux of 0.24 kg/m²/h/10 µm. Separation factor was found to improve with decreasing feed water concentration whereas the corresponding flux decreased. Higher permeate pressures caused a reduction in both flux and selectivity.