Pervaporation separation of aqueous alcohol solution through the membrane of o‐trimethylsilylphenylacetylene initiated by a tungsten carbene complex

A poly(o‐trimethylsilylphenylacetylene) [poly(o‐TMSPA)] initiated by a tungsten carbene complex was investigated under various conditions. The molar mass of poly(o‐TMSPA) increases with increasing the polymerization temperature and decreasing the initiator concentration. The X‐ray diffraction measurements show that poly(o‐TMSPA) has an amorphous structure. The water molecules preferentially permeate through the poly(o‐TMSPA) membranes. The effects of feed compositions, degree of swelling, and the molecular size of alcohols on the pervaporation performances were investigated. The separation factor and the permeation rate increase with increasing ethanol concentration in the feed. The diffusivity contributes to a major part to selective transport. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 647–654, 1999     

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     

Development of methanol selective membranes for separation of methanol–methyl tertiary butyl ether mixtures by pervaporation

Several copolymers of acrylonitrile (AN) were synthesized. Methanol selective membranes were prepared from these copolymers of AN. The other monomers in the copolymers were selected on the basis of their solubility parameter values relative to those of methanol. These were hydroxyethyl methacrylate, methacrylic acid, and vinyl pyrrolidone. Thus, pervaporative separation of methanol from its mixture with methyl tertiary butyl ether over the entire concentration range of 0–100% methanol was studied using these copolymer membranes of AN. For each copolymer of AN three different membranes with different copolymer compositions were prepared. Copolymers of AN with hydroxyethyl methacrylate and methacrylic acid showed high selectivity and moderate flux for methanol (2561, 773, 0.057, and 0.045 kg/m² h, respectively, with a membrane of 50‐μm thickness for a feed mixture containing 5% methanol at 30°C). A copolymer of AN with vinyl pyrrolidone showed comparable flux, but methanol selectivity of this membrane was poor. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2645–2659, 1999     

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     

Sorption and pervaporation separation of ethyl tert—butyl ether and ethanol mixtures through a blended membrane

A new kind of membrane was prepared by blending poly(acrylic acid) with cellulose acetate propionate for the separation of ethyl tert—butyl ether and ethanol mixtures. The properties of the membranes were evaluated by the pervaporation separation of mixtures of ethyl tert—butyl ether/ethanol and the sorption experiments. The experimental results showed that the selectivity and the fluxes of this membrane depend on the blend composition and on that of processed feed mixtures. With respect to temperature, the ethanol fluxes obey the Arrhenius equation. The fluxes increase with the increase of the poly(acrylic acid) content in the blended membrane, the ethanol concentration in the feed, and the experimental temperature. But the selectivity decreases as the poly(acrylic acid) content and the experimental temperature are raised up. When the feed composition is varied, this membrane shows the special characteristics at the azeotropic composition. In the vicinity of the azeotropic point, the minimum values of ethanol concentration in the permeate and in sorption solution are obtained. The swelling ratios increase with an increase in the temperature and the ethanol concentration. The ethanol concentration in the sorption solution is also influenced by the temperature and composition of the mixtures. When the temperature increases, the sorption selectivity of the membrane decreases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1631–1638, 1997     

Characterization of sodium alginate membrane crosslinked with glutaraldehyde in pervaporation separation

Dense sodium alginate (SA) membranes crosslinked with glutaraldehyde (GA) have been prepared by the solution method, wherein a nonsolvent of SA (acetone) was used in a reaction solution instead of an aqueous salt solution. Through infrared radation, X-ray diffractometry, and the swelling measurement, the crosslinking reaction between the hydroxyl groups of SA and the aldehyde groups of GA was characterized. To investigate the selective sorption behavior of the crosslinked SA membranes, swelling measurements of the membranes in ethanol-water mixtures of 70–90 wt % ethanol contents were conducted by equipment that was able to measure precisely the concentration and amount of the liquid absorbed in the membranes. It was observed that the crosslinking could reduce both the solubility of water in the resulting membrane and the permselectivity of the membrane toward water at the expense of membrane stability against water. The pervaporation separation of a ethanol-water mixture was conducted with the membranes prepared at different GA contents in the reaction solution. When the membrane was prepared at a higher GA content, both flux and separation factor to water were found to be reduced, thus resulting from the more crosslinking structure in it. The pervaporation separations of ethanol-water mixtures were also performed at different feed compositions and temperatures ranging from 40 to 80°C. A decline in the pervaporative performance was observed due to the relaxation of polymeric chains taking place during pervaporation, depending on operating temperature and feed composition. The relaxational phenomena were also elucidated through an analysis on experimental data of the membrane performance measured by repeating the operation in the given temperature range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 209–219, 1998     

Pervaporation of water–ethanol mixtures through plasma graft polymerization of polar monomer onto crosslinked polyurethane membrane

To improve the pervaporation performance, the plasma post-graft polymerization of 2,3-epoxypropylmethacrylate (EPMA) onto the crosslinking polyurethane (CPU) membrane, EPMA-g-CPU, was synthesized in this study. The crosslinking between soft–soft hydroxyl-terminated polybutadiene (HTPB) segments were prepared by the introduction of benzoyl peroxide to the HTPB-based PU membrane. The effect of plasma treatment time and plasma supply power on the grafting yield was discussed. The optimum plasma treatment conditions were 10 W supply power and 120 s treatment time. The surface properties of the EPMA-g-CPU membrane were characterized by Fourier transform infrared spectroscopy, electron spectroscopy for chemical analysis, and a contact angle meter. A separation factor of 97 and a 240 g m⁻² h⁻¹ permeation rate through the EPMA-g-CPU membrane with a 4.81 mg/cm² grafting yield for a 90 wt % feed ethanol concentration were obtained. Compared with ungrafted CPU membrane, the EPMA-g-CPU membrane effectively improved the pervaporation performances. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1789–1797, 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     

Characterization of permeation behaviors of ethanol–water mixtures through sodium alginate membrane with crosslinking gradient during pervaporation separation

Dense sodium alginate (SA) membranes crosslinked with glutaraldehyde were prepared by a new solution technique, which had different extents of crosslinking gradient structures. The SA membranes having a crosslinking gradient structure were fabricated by exposing one side of the membrane to the reaction solution while blocking the other side by a polyester film to prevent the reaction solution from contacting it. The extent of the crosslinking gradient was controlled by the exposing time. When the swelling measurements were performed with uniformly crosslinked membranes in aqueous solutions of 70–90 wt % ethanol contents, it was observed that the crosslinking could reduce both the solubility of water in the membrane and the permselectivity of the membrane toward water. The pervaporation separation of the ethanol–water mixture of 90 wt % ethanol content was carried out with membranes with different extents of crosslinking gradients. As the crosslinking gradient was developed more across the membrane, the resulting flux as well as the separation factor to water was found to decrease while the membrane became stable against water. The pervaporation performances of the membranes with different membrane loadings in a membrane cell were also discussed using the schematic concentration and activity profiles of the permeant developed in them. The pervaporation separations of the ethanol/water mixtures through the membrane with an optimal crosslinking gradient were performed at different feed compositions and temperatures ranging from 40 to 80°C. The change in the membrane performance due to the relaxation process during pervaporation was observed with the operating temperature and feed composition. The relaxational phenomena were also elucidated through an analysis of the experimental data of the membrane performance measured by repeating the operation in a given temperature range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1607–1619, 1998     

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