Mixed matrix membranes of Matrimid 5218 loaded with zeolite 4A for pervaporation separation of water–isopropanol mixtures

Mixed matrix membranes were prepared by incorporating zeolite 4A into polyimide of Matrimid 5218 using solution-casting technique. The fabricated membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimeter (DSC) and thermo gravimetric analysis (TGA). It was found that the higher annealing temperature of 250 °C is more favorable to improve adhesion between zeolite and polymer phases. Effects of different parameters such as temperature (30–60 °C), water content in feed (10–40 wt.%), zeolite loading (0–15 wt.%) and polymer content (10 and 15 wt.%) on pervaporation dehydration of isopropanol were studied. Sorption studies were carried out to evaluate degree of swelling of the membranes in feed mixtures of water and isopropanol. The experimental results showed that both pervaporation flux and selectivity increase simultaneously with increasing the zeolite content in the membranes. The membrane containing Matrimid 5218 (10 wt.%)–zeolite 4A (15 wt.%) exhibits the highest separation factor (α) of 29,991 with a substantial permeation flux (J) of 0.021 kg/m² h at 30 °C for 10 wt.% of water in the feed. The PV performance was also studied in term of pervaporation separation index (PSI). Permeation flux was found to follow the Arrhenius trend over the investigated temperature range.     

Pervaporation separation of toluene/n-heptane mixtures using a MSE-modified membrane: Effects of operating conditions

In this work, separation of toluene/n-heptane mixtures via pervaporation using a composite membrane was investigated. Effects of operating conditions such as feed temperature, feed composition and downstream pressure on the membrane performance were studied. Experimental results were obtained at different feed compositions (10–40 wt.%), operating temperatures (25–85 °C) and downstream pressures (2–32 mbar g). The membrane selectivity for toluene was found to be greater than that for n-heptane. According to the results, it was observed that increasing toluene concentration in the feed and operating temperature enhance the membrane swelling and increase the polymeric chain mobility. Therefore, feed concentration and temperature have the same effects on toluene selectivity and permeation flux of the membrane. Permeation flux increases and toluene selectivity decreases with increasing feed concentration and temperature. In contrary, the membrane performance enhances with decreasing downstream pressure. It was found out that for a feed with 10 wt.% of toluene, at a temperature of 85 °C and a downstream pressure of 2 mbar g, the highest PSI value of 18.371 kg/m² h (in which permeation flux = 4.610 kg/m² h and toluene selectivity = 4.985) is achieved.     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Pervaporation dehydration of ethylene glycol by NaA zeolite membranes

Home-made NaA zeolite membranes were used for pervaporation dehydration of ethylene glycol (EG)/water mixtures. Hydrothermal stability of the membranes in pervaporation was investigated for industrial application purpose. The membranes exhibited good stability for water content of less than 20 wt.% at 100 °C. The reduction of operating temperature was effective to improve membrane stability for operating at high feed water content (e.g. 30 wt.%). The influence of feed water content and operating temperature on dehydration of EG was extensively investigated. A permeation flux of 4.03 kg m⁻² h⁻¹ with separation factor of >5000 was achieved at 120 °C for the separation of the solution with 20 wt.% water content. A pilot-scale pervaporation facility with membrane area of 3 m² was built up for dehydration of EG with the water content of 20 wt.%, which showed technical feasibility for industrial application.     

Mixed matrix membranes of sodium alginate and poly(vinyl alcohol) for pervaporation dehydration of isopropanol at different temperatures

Mixed matrix membranes of sodium alginate (NaAlg) and poly(vinyl alcohol) (PVA) containing 5 and 10 wt.% silicalite-1 particles were fabricated by solution casting method and the cured membranes were crosslinked with glutaraldehyde. These membranes were used in pervaporation (PV) dehydration of isopropanol at 30, 40, 50 and 60 °C. Membrane morphology was studied by scanning electron microscopy and universal testing machine to assess their mechanical strengths. Swelling results of the pristine and mixed matrix membranes were correlated with their PV performances. Selectivities of the mixed matrix membranes of NaAlg were 11,241 and 17,991 with the fluxes of 0.039 and 0.027 kg/m² h, respectively, for 5 and 10 wt.% silicalite-1 loadings. Corresponding values for mixed matrix membranes of PVA were 1295 and 2241, and 0.084 and 0.069 kg/m² h, respectively, for 10 wt.% water-containing feed at 30 °C. Pristine membranes of NaAlg and PVA exhibited lower selectivities of 653 and 77 with increased fluxes of 0.067 and 0.095 kg/m² h, respectively. From the temperature dependence of flux and diffusivity data with 10 wt.% water-containing feed, Arrhenius plots were constructed to compute heat of sorption, ΔH_s values. Mixed matrix membranes of NaAlg were better than PVA mixed matrix membranes at all compositions (10-40 wt.%) of water. Molecular dynamics (MD) simulation was employed to compute the interfacial interaction energies of NaAlg and PVA polymers with silicalite-1 filler; also sorption of liquid molecules was computed. Simulated diffusivities compared well with the experimental data. Thermodynamic treatment of sorption, diffusion and permeation processes was attempted based on the Flory-Huggins theory to explain the PV performances of the membranes.     

Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1: Dehydration of solvents

The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m² h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m² h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation.     

Pervaporation of benzene/cyclohexane and benzene/n-hexane mixtures through PVA membranes

Poly(vinyl alcohol) (PVA) membranes (both homogeneous and asymmetric) were studied for the pervaporation separation of benzene/n-hexane and benzene/cyclohexane mixtures. The asymmetric PVA membrane with skin and porous layers was prepared through the phase inversion technique. Both asymmetric and homogeneous membranes were benzene-selective for all the feed compositions. The benzene separation factor of homogeneous PVA membrane was smaller than three, and the total permeation flux was several g/m²/h. The benzene selectivity of the asymmetric PVA membrane was much higher than that of the homogeneous membrane; weight fraction of benzene in the permeate side was larger than 90% for all the feed compositions. On the other hand, the total flux was almost unchanged compared with that of the homogeneous membrane. These results indicate that the density of the skin layer of the asymmetric membrane should be much higher than that of the homogeneous membrane. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1061–1065, 1997     

Study of pervaporation for dehydration of caprolactam through PVA/nano silica composite membranes

We investigated nano silica/PVA composite membranes to propose an improved caprolactam pervaporation (PV) dehydration process. The membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and contact angle measurement. Compared with the pure PVA membranes, the nano silica/PVA composite membranes showed different surface morphologies with enhanced hydrophilicity because of their unique formation. To evaluate PV performance and mechanism, we assessed the permeation flux, separation factor, diffusivity/sorptivity selectivity, and activation energy of the composite membranes. The evaluated results indicate that the nano silica/PVA composite membranes induced a breakthrough in the dehydration of a caprolactam-water mixture with a maximum flux of 3.8 kg m^? 2 h^? 1 and an acceptable separation factor of 150.     

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 aqueous salt solution by pervaporation through hybrid organic–inorganic membrane: Effect of operating conditions

Hybrid polymer-inorganic membranes were prepared by crosslinking poly(vinyl alcohol) (PVA), maleic acid (MA) and silica via an aqueous sol–gel route. Membrane characterisation results revealed silica nanoparticles (< 10 nm) were well dispersed in the polymer matrix and significantly reduced swelling of the membrane. The membranes were tested for pervaporation separation of aqueous salt solution with NaCl concentrations of 0.2–5.0 wt% at temperatures 20–65 °C, feed flowrates 30–150 mL/min and permeate pressures 2–40 Torr. The salt rejection remained high (up to 99.9%) under all operating conditions. A high water flux of 11.7 kg/m² h could be achieved at a feed temperature of 65 °C and a vacuum of 6 Torr. The effect of operating conditions on water flux is discussed in relation to diffusion coefficients of water and fundamental transport mechanism through the membrane. The activation energy for water permeation was found to vary from 23.8 to 20.1 kJ/kmol when the salt concentration in the feed was increased from 0.2 to 5.0 wt%.     

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     

Facilitated transport separation of propylene–propane: Experimental and modeling study

Supported liquid membrane, as one type of facilitated transport membranes, was used for the separation of propylene–propane mixtures. The effect of trans-membrane pressure and carrier concentration on membrane separation performance were evaluated in terms of mixed-gas selectivity, propylene and propane permeances and propylene and propane permeation fluxes. A general dimensionless model for the transport of components across the membrane was proposed and solved numerically by orthogonal collocation method. Experimental results showed that for a 70:30 (vol.%) propylene–propane mixture, at pressure 120 kPa and carrier concentration 20 wt.%, a propylene permeation flux of 1.46 × 10⁻⁴ mol/m² s was obtained. Mathematical results are in well agreement with experimental results. The average deviation between experimental and modeling results was found to be 5.3% for propylene permeation flux and 0.03% for propane permeation flux.     

Pervaporation separation of water/dimethylformamide mixtures using poly(vinyl alcohol)‐g‐polyacrylamide copolymeric membranes

Grafted copolymeric membranes of poly(vinyl alcohol) with acrylamide (PVA‐g‐AAm) were developed and used in the pervaporation separation of water–dimethylformamide mixtures by varying the amount of water in the feed from 0 to 100%. From these data, the permeation flux, pervaporation separation index, diffusion coefficient, swelling index, and separation selectivity were calculated at 25, 35, and 45°C. The Arrhenius activation parameters for permeation flux ranged between 22 and 63 kJ/mol, while the activation energy for diffusion ranged between 23 and 67 kJ/mol. Separation selectivity was between 15 and 22. The highest permeation flux of 0.459 kg m^?2 h^?1 was obtained for the 93% grafted membrane at 90% of water in the feed mixture. The results are discussed using the principles of the solution–diffusion model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 273–282, 2002     

Chitosan/TiO2 nanocomposite pervaporation membranes for ethanol dehydration

Novel chitosan/titanium dioxide (CS/TiO₂) nanocomposite membranes were prepared using tetrabutyl titanate (TBT) as precursor and acetyl acetone as chelating agent by in situ sol-gel process, and characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetry (TG). The characterization results demonstrated that nano-sized TiO₂ particles dispersed homogeneously within the CS matrix, which could be assigned to the hydrogen and titanoxane bonds formed between CS and TiO₂. Moreover, the pervaporation performance of these membranes was investigated using the separation of ethanol-water mixture as model system. Compared with CS/TiO₂ hybrid membranes prepared by blending method, most of CS/TiO₂ nanocomposite membranes prepared by in situ sol-gel process exhibited higher permeation flux and separation factor under the identical conditions. Among all the prepared membranes, CS/TiO₂ nanocomposite membrane containing 6 wt% TiO₂ exhibited the best pervaporation performance, whose averaged permeation flux and separation factor were 0.340 kg m⁻² h⁻¹ and 196 for 90 wt% aqueous solution of ethanol at 80 °C, respectively.     

Chitosan/polyvinylpyrrolidone‐silica hybrid membranes for pervaporation separation of methanol/ethylene glycol azeotrope

Chitosan (CS)/polyvinylpyrrolidone (PVP)‐silica hybrid membranes are prepared to separate the methanol/ethylene glycol (EG) azeotrope. These hybrid membranes are formed in semi‐interpenetrating network structure at the molecular scale via sol‐gel reactions between CS and tetraethoxysilane (TEOS). The physico‐chemical property and morphology of the as‐prepared membranes are investigated in detail. They have lower crystallinity, higher thermal stability, and denser structure than the pristine CS membrane and its blending counterpart. The as‐prepared hybrid membranes demonstrate excellent performances and a great potential in pervaporation separation of methanol/EG. Silica‐hybridization depressed the swelling degree of membranes in the azeotrope, and remarkably enhanced methanol sorption selectivity. The membrane containing 7.77 wt % PVP and 14.52 wt % TEOS has a permeation flux of 0.119 kg m^?2 h^?1 and separation factor of 1899. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pervaporation separation of water–isopropyl alcohol mixture by PVA/LiBr membrane

Hydrophilic polyvinyl alcohol membranes, modified by lithium bromide, were prepared with glutaraldehyde as a crosslinking reagent. The membranes were investigated for the pervaporation dehydration of a water–isopropyl systems. The effect of the feed temperature on permeation flux and membrane selectivity was studied. The characterization of modified membranes was performed using Fourier transform infrared spectroscopy (FT‐IR), differential scanning calorimeter (DSC) and X‐ray diffraction. It was observed that the crystallinity of membranes increased as lithium bromide was added to the polymer. High performance liquid chromatography (HPLC) was used to analyze water content and isopropyl alcohol in the feed and permeate samples The pervaporation tests also confirmed an enhancement in water permeability through adding LiBr to the polymer, because of the high hydrophilic properties of this salt. According to pervaporation experiments conducted at 50°C, the water flux increased from 0.1049 kg/ m² hr to 0.1114 kg/ m² hr as 0.5 wt% of LiBr was added to the polymer matrix. Furthermore, an addition of 1 wt% of LiBr compared to homogeneous PVA membrane increased selectivity from 76 to 779. POLYM. ENG. SCI., 59:E101–E111, 2019. © 2018 Society of Plastics Engineers     

Synthesis and characterization of polyacrylamide‐grafted sodium alginate copolymeric membranes and their use in pervaporation separation of water and tetrahydrofuran mixtures

Polyacrylamide‐grafted sodium alginate (PAAm‐g‐Na‐Alg) copolymeric membranes have been prepared, characterized, and used in the pervaporation separation of 10–80 mass % water‐containing tetrahydrofuran mixtures. Totally three membranes were prepared: (1) neat Na‐Alg with 10 mass % of polyethylene glycol (PEG) and 5 mass % of polyvinyl alcohol (PVA), (2) 46 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA, and (3) 93 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA. Using the transport data, important parameters like permeation flux, selectivity, pervaporation separation index, swelling index, and diffusion coefficient have been calculated at 30°C. Diffusion coefficients were also calculated from sorption gravimetric data of water–tetrahydrofuran mixtures using Fick's equation. Arrhenius activation parameters for the transport processes were calculated for 10 mass % of water in the feed mixture using flux and diffusion data obtained at 30, 35, and 40°C. The separation selectivity of the membranes ranged between 216 and 591. The highest permeation flux of 0.677 kg/m² h was observed for 93% grafted membrane at 80 mass % of water in the feed mixture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 272–281, 2002     

Pervaporation characteristics and structure of poly(vinyl alcohol)/poly(ethylene glycol)/tetraethoxysilane hybrid membranes

Poly(vinyl alcohol) (PVA) blended with poly(ethylene glycol) (PEG) was crosslinked with tetraethoxysilane (TEOS) to prepare organic–inorganic PVA/PEG/TEOS hybrid membranes. The membranes were then used for the dehydration of ethanol by pervaporation (PV). The physicochemical structure of the hybrid membranes was studied with Fourier transform infrared spectra (FT‐IR), wide‐angle X‐ray diffraction WXRD, and scanning electron microscopy (SEM). PVA and PEG were crosslinked with TEOS, and the crosslinking density increased with increases in the TEOS content, annealing temperature, and time. The water permselectivity of the hybrid membranes increased with increasing annealing temperature or time; however, the permeation fluxes decreased at the same time. SEM pictures showed that phase separation took place in the hybrid membranes when the TEOS content was greater than 15 wt %. The water permselectivity increased with the addition of TEOS and reached the maximum at 10 wt % TEOS. The water permselectivity decreased, whereas the permeation flux increased, with an increase in the feed water content or feed temperature. The hybrid membrane that was annealed at 130°C for 12 h exhibited high permselectivity with a separation factor of 300 and a permeation flux of 0.046 kg m^?2 h^?1 in PV of 15 wt % water in ethanol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Pervaporation dehydration of water/ethanol/ethyl acetate mixtures using poly(vinyl alcohol)–silica hybrid membranes

The novel organic–inorganic hybrid membranes were prepared from poly(vinyl alcohol) (PVA) and vinyltriethoxysilane (VTES). They were characterized using Fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), and contact angle metering. The as‐prepared membranes are formed at a molecular scale at a low VTES content. Aggregations in the surface of the as‐prepared membranes were clearly evident above 18.43 wt % VTES loading. The introduction of VTES into the PVA matrix resulted in a decrease in the crystalline and an increase in compactness and thermal stability of the as‐prepared membranes. Silica hybridization reduced the swelling of the as‐prepared membranes in water/ethanol/ethyl acetate mixtures, decreased the permeation flux, and remarkably enhanced water permselectivity in pervaporation dehydration of ethanol/ethyl acetate aqueous solution. The hybrid membrane with 24.04 wt % VTES has the highest separation factor of 1079 and permeation flux of 540 g m^?2 h^?1. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characteristics of permeation and separation for propanol isomers through poly(vinyl alcohol) membranes containing cyclodextrin

Poly(vinyl alcohol) membranes containing cyclodextrin (CD–PVA membrane) were prepared and characteristics of permeation and separation for propanol (PrOH) isomers through the CD–PVA membranes were investigated by pervaporation and evapomeation. Evapomeation was more effective for the separation of PrOH isomers through the CD–PVA membrane than was pervaporation. The CD–PVA membrane more preferentially permeated n-PrOH than i-PrOH from their mixtures. In particular, the mixture of 10 wt % n-PrOH concentration was concentrated to about 45 wt % through the CD–PVA membrane. Both permeability and selectivity for n-PrOH were improved with an increase of CD content in the membrane. The results were supported by the fact that the affinity of CD for n-PrOH was stronger than that for i-PrOH. The permeation mechanism of PrOH isomers through the CD–PVA membrane is discussed based on the solution–diffusion theory. © 1994 John Wiley & Sons, Inc.