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     

Permeation and Separation Characteristics of Acetic Acid‐Water Mixtures by Pervaporation through Acrylonitrile and Hydroxy Ethyl Methacrylate Grafted Poly(vinyl alcohol) Membrane

Abstract

In this study, acrylonitrile (AN) and hydroxyl ethyl methacrylate (HEMA) were grafted onto poly(vinyl alcohol) (PVA) using cerium (IV) ammonium nitrate as initiator at 30°C. The graft copolymer was characterized using the Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The grafted PVA membranes (PVA‐g‐AN/HEMA) were prepared by a casting method, and used in the separation of acetic acid‐water mixtures by pervaporation. The effects of the membrane thickness, operating temperature, and feed composition on the permeation rate and separation factor for acetic acid‐water mixtures were studied. Depending on the membrane thickness, the temperature and feed composition PVA‐g‐AN/HEMA membranes gave separation factors 2.26–14.60 and permeation rates of 0.18–2.07 kg/m²h. It was also determined that grafted membranes gave lower permeation rates and greater separation factors than PVA membranes. Diffusion coefficients of acetic acid‐water mixtures were calculated from permeation rate values. The Arrhenius activation parameters were calculated for the 20 wt.% acetic acid content in the feed using the permeation rate and the diffusion data obtained at between 25–50°C.     

Permeation and separation characteristics of acetic acid/water mixtures through poly(vinyl alcohol‐g‐itaconic acid) membranes by pervaporation,evapomeation, and temperature‐difference evapomeation

In this study, itaconic acid (IA) was grafted onto poly(vinyl alcohol) (PVA) with cerium(IV) ammonium nitrate as an initiator at 45°C. The grafted PVA was characterized with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. IA‐grafted PVA membranes were prepared with a casting method, and the permeation and separation characteristics of acetic acid/water mixtures were investigated with pervaporation (PV), evapomeation (EV) and temperature‐difference evapomeation (TDEV) methods. The effects of the feed composition, operating temperature, and temperature of the membrane surroundings on the permeation rate and separation factor for the acetic acid/water mixtures were studied. The permeation rates in EV were lower than those in PV, whereas the separation factors were higher. With the TDEV method, the permeation rates decreased and the separation factors increased as the temperature of the membrane surroundings decreased. The prepared membranes were also tested in PV, EV, and TDEV to separate the various compositions of the acetic acid/water mixtures (20–90 wt % acetic acid) at 40°C. The highest separation factor, 686, was obtained in TDEV with a 90 wt % acetic acid concentration in the feed. The activation energies of permeation in PV and EV were calculated to be 8.5 and 10.2 kcal/mol, respectively, for a 20 wt % acetic acid solution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2322–2333, 2004     

Pervaporation separation of binary organic–aqueous liquid mixtures using cross-linked PVA membranes. II. Phenol–water mixtures

The pervaporation separation of water-phenol mixtures was carried out using poly(vinyl alcohol) (PVA) cross-linked membranes with low molecular weight poly(acrylic acid) (PAA) at 30, 40, and 50°C. The separation was concentrated on the second stage of the water-selective process at which the phenol concentration could be 80 wt % of phenol. The high separation factor of α_w/p, = 3580 for the PVA/PAA = 80/20 membrane was obtained for the phenol : water = 80 : 20 solution at 30°C. © 1994 John Wiley & Sons, Inc.     

Pervaporation separation of water–isopropanol mixture using carboxymethylated poly(vinyl alcohol) composite membranes

The pervaporation separation of water–isopropanol mixtures was carried out using carboxymethylated poly(vinyl alcohol) (CMPVA) composite membranes. Carboxymethylated PVA (CMPVA) was synthesized by reacting PVA with various concentrations of monochloroacetic acid. Substitution efficiency of the CMPVA ranged from 12–32%. The cross‐sectional structure of the composite membrane for pervaporation was confirmed by scanning electron microscopy (SEM) exhibiting a 20‐μm active skin layer. Glass transition temperature of the CMPVA was in the range of 74–84°C, and decreased with increasing substitution efficiency. Degree of swelling and permeation flux for water–isopropanol in pervaporation increased with the substitution degree of carboxymethylation. CMPVA composite membrane, having 16% substitution efficiency, showed the following pervaporation performance; permeation flux of 831 g/m² h and separation factor of 362 measured at 80°C and 85 wt % feed isopropanol concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 241–249, 1999     

Pervaporation separation of acetic acid-water mixtures using modified membranes. I. Blended polyacrylic acid (PAA)-nylon 6 membranes

Membranes consisting of ionically crosslinked polyacrylic acid (PAA) and Nylon 6 were prepared and tested for the pervaporation separation of acetic acid-water mixtures. The polyacrylic acid (PAA) membranes were crosslinked in aluminum nitrate aqueous solution while the polyacrylic acid (PAA)-Nylon 6 blends were cast from homogeneous PAA-Nylon 6 mixtures to appropriate thicknesses and then crosslinked in aqueous aluminum nitrate solutions. Optimum pervaporation results were obtained from blends of Nylon 6 and PAA in the weight ratio of 60–75 wt% Nylon 6 and 25–40 wt% PAA which have separation factors (water/acetic acid) of over 60 and flux rates higher than 100 g/m² h at 15°C for the separation of acetic acid-water mixtures. The flux rates and separation factors could be altered by changing the blend composition of the membrane. The effects of the feed composition on the separation factors were investigated.     

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     

Poly(acrylic acid)–poly(vinyl alcohol) semi- and interpenetrating polymer network pervaporation membranes

A series of poly(acrylic acid) (PAA)–poly(vinyl alcoho) (PVA) semiinterpenetrating (SIPN) and interpenetrating (IPN) polymer network membranes were prepared by crosslinking PVA alone or by crosslinking both PVA and PAA. Glutaraldeyde and ethylene glycol were used as crosslinking agents for the PVA and PAA networks, respectively. The presence of PAA increases the permeability of the membranes while the presence of PVA improves their mechanical and film-forming properties. The mechanical properties of the membranes were investigated via tensile testing. These hydrophilic membranes are permselective to water from ethanol–water mixture and to ethanol from ethanol–benzene mixtures. The IPN membranes were employed for the former mixtures and the SPIN membranes for the latter, because the IPN ones provided too low permeation rates. The permeation rates and seperation factors were determined as functions of the IPN or SIPN composition, feed composition, and temperature. For the azeotropic ethanol–water mixture (95 wt % ethanol), the separation factor and permeation rate at 50°C of the PAA-PVA IPN membrane, containing 50 wt % PAA, were 50 and 260 g/m²h, respectively. For the ethanol–benzene mixture, the PAA–PVA SIPN membranes had separation factors between 1.4 and 1200 and permeation rates between 6 and 550 g/m²h, respectively, depending on the feed composition and temperature. © 1996 John Wiley & Sons, Inc.     

Pervaporation separation of binary organic-aqueous liquid mixtures using crosslinked poly(vinyl alcohol) membranes. IV. Methanol–water mixtures

The pervaporation separation of methanol–water (M/W) mixtures was carried out using crosslinked poly(vinyl alcohol) (PVA) membranes with the low molecular weight of poly(acrylic acid) (PAA) as the crossinking agent. The PVA/PAA ratio in the crosslinked membrane was 90/10, 85/15, and 80/20 by weight. The operating temperatures were 50, 60, and 70°C, and the compositions of methanol–water mixtures to be separated were 70/30, 80/20, 90/10, and 95/5 (M/W) solutions. In all cases, the PVA/PAA = 80/20 membrane showed the best results. For M/W = 90/10 solution, the separation factor, α_w/m = 465, and the permeation rate, 0.109 kg/m²h, at 70°C were obtained using the PVA/PAA = 80/20 menbrane. The permeation rate and the separation factor for M/W = 95/5 solution showed 0.033 kg/m²h and α_w/m = 2650, respectively, when PVA/PAA = 80/20 membrane was used. © 1996 John Wiley & Sons, Inc.     

Synthesis of graft copolymeric membranes of poly(vinyl alcohol) and polyacrylamide for the pervaporation separation of water/acetic acid mixtures

Graft copolymers of poly(vinyl alcohol) (PVA) with polyacrylamide were prepared and membranes were fabricated at 48 and 93% grafting of acrylamide onto PVA. These membranes were used in the pervaporation separation of water/acetic acid mixtures at 25, 35, and 45°C. The permeation flux, separation selectivity, diffusion coefficient, and permeate concentration were determined. The highest separation selectivity of 23 for neat PVA at 25°C and the lowest value of 2.2 for 93% acrylamide‐grafted PVA membranes were observed. A permeation flux of 1.94 kg m^?2 h^?1 was found for the 93% grafted membrane at 90 mass % of water in the feed mixture. The diffusion coefficients in a water/acetic acid mixture had an effect on the membrane permselectivity. The Arrhenius equation was used to calculate the activation parameters for permeation as well as for the diffusion of water and of acetic acid. The activation energy values for the permeation flux varied from 97 to 28 kJ/mol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 244–258, 2002     

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.     

Separation of Acetic Acid‐Water Mixtures through Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Alloy Membranes by Using Evapomeation and Temperature Difference Evapomeation Methods

Abstract

Separation of acetic acid‐water mixtures by using evapomeation (EV) method were carried out over the full range of compositions at temperatures varying from 30 to 55°C using poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) (75/25) (v/v) alloy membranes. PVA/PAA membranes gave separation factors of 110–5711 and permeation rates of 2.3×10^?4–1.53×10^?1 kg/m²h, depending on the operation temperature and feed mixture composition. The temperature dependence of the permeation in EV was expressed by the Arrhenius type expression and the activation energy was calculated as 9.15 kcal/mol. More efficient EV technique, which is called temperature difference evapomeation method (TDEV) was also applied to PVA/PAA membranes to separate acetic acid‐water mixtures; high permeation rates (1.7×10^?3–3.0×10^?1 kg/m²h) and separation factors (1335–8924) were obtained for each of the studied feed compositions. Azeotropic mixture of acetic acid and water was also separated by TDEV method with a separation factor of 297 and permeation rate of 1.50×10^?1 kg/m²h.     

Pervaporation separation of binary organic–aqueous liquid mixtures using crosslinked PVA membranes. III. Ethanol–water mixtures

The application of the pervaporation process in biotechnology is rapidly growing. A two stage pervaporation process could be applied to the downstream processing of ethanol fermentation. In this paper, the second stage process—a water-selective process—was investigated in detail using the crosslinked poly(vinyl alcohol) membranes with the low molecular weight of poly(acrylic acid) as the crosslinking agent. The ratio of poly(vinyl alcohol) and poly(acrylic acid) in the membrane was 90/10, 85/15, and 80/20 by weight. The prepared membranes were tested to separate the various compositions of the water–ethanol mixtures, specially 50/50 solution at 60°C and 30/70, 20/80, 10/90, and 4.4/95.6 solutions at 60, 70, and 75°C. For water: ethanol = 50 : 50 solution, the separation factor α_w/e = 260 at 75°C was obtained by using a PVA/PAA = 80/20 membrane. The permeation rate and the separation factor at the azeotropic point of a water–ethanol mixture showed 30 g/m²/h and 5800 at 75°C, respectively, when a PVA/PAA = 80/20 membranes was used. © 1995 John Wiley & Sons, Inc.     

Modification of poly(vinyl alcohol) membranes using sulfur-succinic acid and its application to pervaporation separation of water–alcohol mixtures

For the purposes of the water-selective membrane material development for pervaporation separation, we crosslinked poly(vinyl alcohol) (PVA) with sulfur-succinic acid (SSA), which contains —SO₃OH, by heat treatment and investigated the effect of the crosslinking density on the separation of water–alcohol mixtures by pervaporation technique. The crosslinking reaction between PVA and SSA was characterized through Fourier transform infrared spectroscopy and differential scanning calorimetry tests by varying the amount of the crosslinking agent, the reaction temperature, and the swelling measurements of each pure component. The separation performance of the water–methanol mixture is not good due to the existence of sulfonic acid, hydrophilic group, in the crosslinking agent. However, for the water–ethanol mixture, the flux of 0.291 kg/m²h and the separation factor of 171 were obtained at 70°C when PVA-crosslinked membrane containing 7 wt % SSA was used. The same membrane also showed flux of 0.206 kg/m²h and a separation factor of 1969 at the same operating temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1717–1723, 1998     

Characterization of sodium alginate and poly(vinyl alcohol) blend membranes in pervaporation separation

By blending a rigid polymer, sodium alginate (SA), and a flexible polymer, poly(vinyl alcohol) (PVA), SA/PVA blend membranes were prepared for the pervaporation separation of ethanol–water mixtures. The rigid SA membrane showed a serious decline in flux and a increase in separation factor due to the relaxation of polymeric chains, whereas the flexible PVA membrane kept consistent membrane performance during pervaporation. Compared with the nascent SA membrane, all of the blend membranes prepared could have an enhanced membrane mobility by which the relaxation during pervaporation operation could be reduced. From the pervaporation separation of the ethanol–water mixtures along with the temperature range of 50–80°C, the effects of operating temperature and PVA content in membrane were investigated on membrane performance, as well as the extent of the relaxation. The morphology of the blend membrane was observed with PVA content by a scanning electron microscopy. The relaxational phenomena during pervaporation were also elucidated through an analysis on experimental data of membrane performance measured by repeating the operation in the given temperature range. SA/PVA blend membrane with 10 wt % of PVA content was crosslinked with glutaraldehyde to enhance membrane stability in water, and the result of pervaporation separation of an ethanol–water mixture through the membrane was discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:949–959, 1998     

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.     

Pervaporative permeations of homologous series of alcohol aqueous mixtures through a hydrophilic membrane

The permeation behaviors of permeants were investigated in the pervaporation of a homologous series of alcohol aqueous mixtures through a hydrophilic poly(vinyl alcohol) (PVA). The PVA membrane was crosslinked with glutaraldehyde. A homologous series of alcohols used in this study were methanol, ethanol, 1‐propanol, and 1‐butanol. The pervaporation experiments were carried out with feed having 70–97 wt % of alcohol contents and at various feed temperatures. In a high alcohol content above 92 wt %, the permeation rate was increased in the order of the interaction strength between alcohol and water in the feed. However, in a low alcohol content below 90 wt %, the tendency of the permeation rate was found to be the opposite, indicating that the interactions between permeant constituents play an important role in determining the permeation and separation of the mixtures. These observations were discussed in terms of changes in the interaction between the permeant/permeant or the permeant/membrane in varying feed compositions and feed temperatures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 703–713, 2001     

乙醇/水及乙酸/水体系的渗透汽化分离

以乙醇/水及乙酸/水体系为研究对象,研究了渗透汽化过程中料液浓度、温度因素对分离效果的影响;结合乙醇、乙酸对聚二甲基硅氧烷(PDMS)膜的溶胀特性差别,分析并讨论了两者在渗透汽化过程中可能的分离机理. 研究表明,PDMS膜能够优先透醇,但乙酸分子的缔合物以及羧基与疏水PDMS膜高分子链的强相互作用降低了其在膜中的扩散速率,使低温时乙酸/水体系优先透水,只有当温度在60℃以上时才表现出优先透酸,且分离效果较差.     

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     

Incorporation of multiwalled carbon nanotubes into poly(vinyl alcohol) membranes for use in the pervaporation of water/ethanol mixtures

Multiwalled carbon nanotube (MWNT)/poly (vinyl alcohol) (PVA) blend membranes were prepared by the solution‐casting method to determine the effect of MWNTs with nanoscale empty inner space along the tube length on the pervaporation performance of a PVA membrane in the separation of alcohol/water mixtures. The blend membranes were then characterized with several analytical methods such as transmission electron microscopy, differential scanning calorimetry, and X‐ray diffractometry: Transmission electron microscopy showed that the MWNTs were homogeneously distributed through the PVA matrix. The glass‐transition temperature of the PVA membrane was increased from 69.21 to 78.53°C via blending with MWNTs. The crystallinity of the PVA matrix decreased with increasing MWNTs up to 5 wt % from 41 to 36%. The pervaporation properties of the blend membranes were completely different from those of the pure PVA membrane in the separation of water/ethanol mixtures. The flux of the membrane was increased with the amount of MWNTs, whereas the separation factor was maintained up to 1.0 wt % MWNTs. However, beyond that, it was reduced. These results suggested that two factors, the crystallinity of the membrane and the diameters of the MWNTs, affected the performance of the membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009