Pervaporation separation of meOH/MTBE through CTA membrane

In the present work, the pervaporation (PV) separation of a MeOH/MTBE mixture system was studied using a CTA dense membrane. The PV performances were characterized by changing the operating conditions, such as the feed composition and permeation temperature. The results show that the CTA membrane favors MeOH permeation and exhibits specificity during the PV separation process for the MeOH/MTBE system due to the existence of the plasticization effect from the MeOH component. Furthermore, the swelling sorption measurements reaffirm that the plasticization effect has a dominant effect on the transport of the penetrants through the membrane and substantially determines the PV permeation properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 377–386, 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     

Characterization and preparation of polyion complex composite membranes for the separation of methyl tert‐butyl ether/methanol mixtures

A series of polyion complex (PIC) composite membranes composed of sodium alginate (SA) polyanion and chitosan polycation were prepared by varying the ratio of concentration. The interaction between SA and chitosan was investigated by FTIR, SEM, and X‐ray analysis and was related to mechanical properties and the swelling phenomenon. The overall PIC composite membranes showed the following results: the total thickness of the coating layer was thicker than that of pure SA composite, and increased with increasing the concentration of chitosan solution during PIC formation. This result was attributed to the diffusion of chitosan molecules from the liquid solution into the SA matrix, and the incorporation with SA molecules. For the PIC membranes prepared with different concentrations of polymer solution, their structural differences could not be detected from IR spectra but their morphological differences could be noticeably found from SEM. Furthermore, the amorphousness of PIC membranes and their elongation properties at break increased significantly as a function of polymer contents, whereas the tensile modulus decreased because of the physical transition effect. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 714–725, 2002     

Effects of polymer solvents on the performance of cellulose acetate membranes in methanol/methyl tertiary butyl ether separation

The performances of cellulose acetate membranes prepared with casting solutions, with acetone, dimethylformamide (DMF), and N‐methylpyrrolidone (NMP) as solvents, were studied in a series of methanol/methyl tertiary butyl ether separation experiments. The flux and selectivity of the membrane samples were affected by the type of solvent used to prepare the casting solution. The sample with DMF consistently gave the highest selectivity and lowest flux, followed by the samples with NMP and acetone. The differences in the performances were attributed to the effects of the volatility and evaporation rates of the solvents. Scanning electron microscopy and atomic force microscopy techniques were used for comparing the morphologies of the membranes. In addition, we used Raman spectroscopy as a novel technique to study the sorption selectivities of the membrane samples prepared with the three different solvents. In a parallel study, the relation between the polymer concentration in the casting solution and the morphology and performance of the membrane samples was studied. Under similar preparation conditions, the morphology of the membrane changed from being porous to being dense when the membrane was prepared with casting solutions with increasing polymer concentration. Also, the selectivity increased and the permeability decreased with increasing polymer concentration in the casting solution. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2882–2895, 2001     

Methyl tert-butyl ether decomposition over heteropoly acid catalyst in a cellulose acetate membrane reactor

In this study the methyl tert-butyl ether (MTBE) decomposition over H₃PW₁₂O₄₀ was carried out in a cellulose acetate membrane reactor. The permeability of methanol through the cellulose acetate membrane was about 30 and 300 times higher than that of either isobutene or MTBE, respectively. The isobutene selectivity in the fixed bed reactor was only slightly higher than the methanol selectivity due to the side reaction. In the cellulose acetate membrane reactor, however, the isobutene selectivity in the rejected stream was 68% and the methanol selectivity in the permeated stream was up to 97%. The MTBE conversion in the membrane reactor was about 7% higher than that in the membrane-free fixed bed reactor under the same reaction conditions. The enhanced performance of the membrane reactor in this reversible reaction was mainly due to the selective permeation of methanol which resulted in a methanol-deficient condition suppressing MTBE synthesis reaction.     

Effect of compatibility of cellulose acetate/poly(vinyl butyral) blends on pervaporation behavior of their membranes for methanol/methyl tert‐butyl ether mixture

Binary blends and their blend membranes of cellulose acetate (CA) and poly(vinyl butyral) (PVB) are prepared by solution blending. The compatibility of the blends is studied by viscometry and Fourier transform IR. It is found that the incompatibility of the blends is markedly manifested when the weight fraction of PVB in the CA/PVB blends (W_PVB) is located at higher regions. On the other hand, compatibility is obtained for the CA/PVB blends with lower W_PVB values, especially at about 0.2. This compatibility is believed to play a key role in the good pervaporation behavior of CA/PVB blend membranes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2434–2439, 2002     

Compatibility of PTET‐60/CA blends and separation performance of their membranes for benzene/cyclohexane mixture by pervaporation

Aromatic copolyester of poly(trimethylene‐co‐ethylene terephthalate) (PTET) with different composition was synthesized and the PTET sample with 60% weight fraction of polytrimethylene (PTET‐60) was amorphous. The compatibility of PTET‐60/cellose acetate (CA) blends and the pervaporation of their membranes for separation of benzene/cyclohexane mixtures were investigated. It was found that PTET‐60 is compatible with CA when the weight fraction of PTET‐60 in PTET‐60/CA blends (W_PTET‐60) is lower than 0.35 and more than 0.5. Both the degree of swelling (DS) and the permeation flux (J) of these blend membranes increased with increasing W_PTET‐60 from 0 to 0.35, and a maximum value of the separation factor (α) displayed at W_PTET‐60 = 0.25. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2832–2838, 2006     

聚二甲基硅氧烷膜中乙醇-水的吸附和渗透蒸发行为

以乙醇/水体系为研究对象,结合F lory-Huggins理论,讨论溶胀过程的热力学行为,用以分析和考察聚二甲基硅氧烷(PDMS)膜在乙醇/水中的溶胀特性及组分间的耦合效应。结果表明,在乙醇质量分数20%—40%,膜的溶胀程度最大。渗透蒸发实验表明,水的渗透速率在乙醇质量分数不大于30%范围内变化很小,而乙醇的渗透速率基本随溶液中乙醇质量分数增加而增大。     

Electrospinning of fluorescent fibers from CdSe/ZnS quantum dots in cellulose triacetate

Fluorescent cellulose triacetate (CTA) fibers were prepared by electrospinning solutions of CTA dissolved in an 8 : 2 v/v cosolvent system of methylene chloride (MC) and methanol (MeOH) which contained CdSe/ZnS quantum dots (QDs). The relatively low loading of colloidal nanoparticles was sufficient to impart fluorescence to the fibers but did not significantly alter fiber morphologies, which tended toward smooth surfaces with the occasional longitudinal feature. The fibers were birefringent due to the alignment of the polymer chains which occurred during electrospinning and had widths on the order of a hundred nanometers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Sorption,diffusion and pervaporation of water/ethanol mixtures in polyetherimide membranes

Homogeneous and composite aromatic polyetherimide membranes were prepared by casting from N-methylpyrrolidinone (NMP) solutions and by electrodeposition of polymer at the cathode, respectively. The membranes were evaluated for their sorption, diffusion and pervaporation separation of water from ethanol with emphasis on the breaking of azeotropic composition. The membrane performance was shown to be dependent on the feed concentration, but still selective towards water over the whole composition range of the feed mixture. By looking at the surface energy parameters, the determination of degree of swelling and the calculation of deviation coefficients (ε), an interesting insight was gained into the coupling effect in this solvent/membrane system. From the sorption, diffusion and temperature-dependent permeation behaviour, it could be concluded that in this system the diffusivity of permeant plays a major role in determining the pervaporation performance, rather than the solubility. © 1999 Society of Chemical Industry     

Miscibility enhancement of poly(vinyl chloride)/polystyrene blend: Application to membrane separation of benzene from benzene/cyclohexane mixture by pervaporation

In order to improve the miscibility of poly(vinyl chloride)/polystyrene (PVC/PS) system and to use the prepared material as a membrane to separate benzene from benzene/cyclohexane mixture by pervaporation technique, two poly(styrene-co-N-vinylpyrrolidone) (PSVP) copolymers containing 6.67 and 13.55 mol% of N-vinylpyrrolidone (N-VP) contents were synthesized through a radical polymerization. A comparative study of the miscibility of the PVC/PSVP blends with different compositions was carried out using differential scanning calorimetry, viscosimetry and Fourier transform infrared spectroscopy methods in which the interaction parameters between the two components were widely investigated. To improve the pervaporative flux of PVC membrane to separate benzene from benzene/cyclohexane mixture, a preliminary test of swelling and sorption was performed on PVC/PSVP7 membranes using an azeotropic benzene/cyclohexane mixture. It was revealed that the PVC/PSVP7 membrane containing 10 wt% of PSVP7 showed the best performance and the diffusion behaviour of this mixture through PVC and PVC/PCVP7 membranes has a Fickian behaviour. The pervaporation parameters of this membrane support those of the swelling and selective sorption data and reveal that this membrane could enhance the total flux without significantly affecting its selectivity to benzene.     

Ag+ contained complex membrane for the separation of C4 olefin/paraffin mixture

The C₄ olefin/paraffin mixture was separated by means of the PE modified reversible complexing membrane, polyethylene-g-acrylic acid-Ag₊(PE-g-AA-Ag₊). The olefin could be transported to the other side of the membrane by silver facilitating phenomenon owing to the formation of (Ag-olefin)₊ complex. The SEM-EDX spectrum showed a homogeneous silver ion distribution across the dense complex membrane's cross-section at higher than about 60% grafting. The gas permeation properties measured by a gas chromatographic method implied a silver ions facilitating effect towards olefin. At 30°C and 111.7% grafting, the complex membrane exhibited a trans-2-butene/isobutane selectivity of 12.5 and a cis-2-butene/isobutane selectivity of 9.2. The permeation activation energy of the C₄ olefins became lower than that of C₄ paraffin as a result of the silver ions facilitated effect. The cis-2-butene has a significant higher complex equilibrium constant than that of the trans-2-butene in complexing with the complex membrane.     

Pervaporation characteristics of methyl methacrylate–methacrylic acid copolymer membranes ionically crosslinked with metal ions for a benzene/cyclohexane mixture

Methyl methacrylate–methacrylic acid copolymer (MMA–MAA) membranes ionically crosslinked with Fe³⁺ and Co²⁺ ions (MMA–MAA–Fe³⁺ and –Co²⁺) were prepared, and characteristics of permeation and separation for a benzene/cyclohexane mixture of 50 wt % benzene through these membranes in pervaporation (PV) were studied. Although the introduction of the metal ions to the MMA–MAA membrane enhanced both benzene permselectivity and permeability for a benzene/cyclohexane mixture, the PV characteristics between the MMA–MAA–Fe³⁺ and –Co²⁺ membranes were significantly different. The difference in the PV characteristics between these membranes was strongly governed by the difference of these membrane structures based on the glass transition temperature, contact angle to methylene iodide, degree of swelling, and mixture composition absorbed in the membrane, and so on. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 233–241, 1999     

Pervaporation separation of dimethyl carbonate/methanol mixtures with regenerated perfluoro‐ion‐exchange membranes in chlor‐alkali industry

The waste perfluoro‐ion‐exchange membranes (PFIEMs) in chlor‐alkali industry were regenerated and used to the separation of dimethyl carbonate (DMC)/methanol (MeOH) mixtures by pervaporation process. The energy‐dispersive spectrum (EDS) demonstrates that the impurities on the surfaces of waste PFIEMs can be effectively cleared by the regeneration process. The degree of swelling, sorption, and pervaporation properties of the regenerated PFIEMs with different counter ions were investigated. The results indicate that the counter ions of PFIEMs conspicuously influence the degree of swelling, sorption, and pervaporation properties for DMC/MeOH mixtures. The degree of swelling and solubility selectivity both decreases with the alkali metal counter ions in the sequence: Li⁺ > Na⁺ > K⁺ > Cs⁺. The degree of swelling increases with MeOH concentration increasing in feed liquid. The pervaporation measurements illustrate that the permeation flux decreases and the separation factor increases with the rising in ion radius of counter ions. The increase of feed concentration (MeOH) and feed temperature is advantageous to improve permeation flux while at the cost of separation factor decreasing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Vapor phase dehydrogenation of methanol to methyl formate in the catalytic membrane reactor with Cu/SiO2/ ceramic composite membrane

The Cu/SiO₂/ceramic composite membrane was prepared on the SiO₂/ceramic mesoporous membrane by an ion exchange method, and vapor phase dehydrogenation of methanol to methyl formate in the catalytic membrane reactor was investigated. It showed much better performance in the catalytic membrane reactor than that in the fixed-bed reactor under the same reaction conditions. At 240 °C, 57.3% conversion of methanol and 50.0% yield of methyl formate were achieved in the catalytic membrane reactor and only 43.1% conversion of methanol and 36.9% yield of methyl formate were achieved in the fixed-bed reactor.     

An all-green cellulose acetate/corn cob composite membrane filter: A critical evaluation of its morphology and adsorption characteristics for dyes and heavy metals

Industrial wastewater from various manufacturing sectors poses a significant environmental concern due to the release of dyes, heavy metals, and pollutants into natural water streams. Effective treatment of large volumes of industrial wastewater is crucial to mitigate this issue. Conventional industrial wastewater filtration systems often prove to be inefficient, necessitating the exploration of alternative and cost-effective water filtration methods. In this study, we drew inspiration from the natural adsorption and purification properties of corncob to develop a novel green composite membrane filter. The composite membrane filters, named MCAPCB and MCATPCB, were formulated by incorporating powdered corncob (PCB) and alkali/hydrogen peroxide-treated powdered corncob (TPCB) into cellulose acetate. The adsorption properties of the composite filters were evaluated using UV–Vis spectrophotometry for dye adsorption and inductively coupled plasma optical emission spectroscopy (ICP-OES) and atomic absorption spectroscopy (AAS) for heavy metal adsorption. The results demonstrated that MCATPCB20, incorporating 20 wt% TPCB, exhibited remarkable performance in the removal of methylene blue dye, with an adsorption efficiency of 97.46%. In comparison, MCAPCB20, incorporating 20 wt% PCB, achieved a dye adsorption efficiency of 80.15%. Moreover, MCATPCB20 displayed exceptional heavy metal removal capabilities, effectively rejecting 98% and 95% of cadmium and lead, respectively, from water samples containing 1 ppm of each metal. The composite filter membranes containing 20 wt% TPCB exhibited superior adsorption efficiency, flexibility, and stability. This enhanced performance can be attributed to the higher carboxyl content in TPCB, achieved through alkali treatment, which significantly increased the adsorption capacity of MCATPCB20. Characterization studies employing XRD, SEM, contact angle, BET, ICP-OES, and UV measurements further supported the efficacy of MCATPCB as an effective filter system for water purification.     

NMR study of temperature-induced phase separation and polymer-solvent interactions in poly(vinyl methyl ether)/D2O/ethanol solutions

The changes in the dynamic structure during temperature-induced phase transition in D₂O/ethanol solutions of poly(vinyl methyl ether) (PVME) were studied using NMR methods. The effect of polymer concentration and ethanol (EtOH) content in D₂O/EtOH mixtures on the appearance and extent of the phase separation was determined. Measurements of ¹H and ¹³C spin-spin and spin-lattice relaxations showed the presence of two kinds of EtOH molecules: besides the free EtOH expelled from the PVME mesoglobules there are also EtOH molecules bound in PVME mesoglobules. The existence of two different types of EtOH molecules at temperatures above the phase transition was in solutions with polymer concentration 20 wt% manifested by two well-resolved NMR signals (corresponding to free and bound EtOH) in ¹³C and ¹H NMR spectra. With time the originally bound EtOH is slowly released from globular-like structures. From the point of view of polymer-solvent interactions in the phase-separated PVME solutions both EtOH and water (HDO) molecules show a similar behaviour so indicating that the decisive factor in this behaviour is a polar character of these molecules and hydrogen bonding.