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 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     

Pervaporation separation of water/isopropanol mixtures through crosslinked carboxymethyl chitosan/polysulfone hollow‐fiber composite membranes

Carboxymethyl chitosan (CMCS)/polysulfone (PS) hollow‐fiber composite membranes were prepared through glutaraldehyde (GA) as the crosslinking agent and PS hollow‐fiber ultrafiltration membrane as the support. The permeation and separation characteristics for dehydration of isopropanol were investigated by the pervaporation method. Pure chitosan, carboxymethyl chitosan, and crosslinked carboxymethyl chitosan membranes were characterized by Fourier transform infrared (FT‐IR) spectroscopy and X‐ray diffraction (XRD) to study the crosslinking reaction mechanism and degree of crystallinity, respectively. The effects of feed composition, crosslinking agent, membrane thickness, and feed temperature on membrane performance were investigated. The results show that the crosslinked CMCS/PS hollow‐fiber composite membranes possess high selectivity and promising permeability. The permeation flux and separation factor for isopropanol/water is 38.6 g/m²h and 3238.5, using 87.5 wt % isopropanol concentration at 45°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1959–1965, 2007     

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     

Preparation and characterization of PVA/SA composite nanofiltration membranes

Nanofiltration (NF) composite membranes based on poly(vinyl alcohol) (PVA) and sodium alginate (SA) were prepared by coating PVA/SA (95/5 in wt %) mixture solutions on microporous polysulfone (PSF) supports. For the formation of a defect free thin active layer on a support, the PSF support was multi‐coated with a dilute PVA/SA blend solution. The PVA/SA active layer formed was crosslinked at room temperature by using an acetone solution containing glutaraldehyde as a crosslinking agent. The prepared composite membranes were characterized with a scanning electron microscopy (SEM), a Fourier transform infrared spectroscopy (FTIR), an electrokinetic analyzer (EKA) and permeation tests: The thicknesses of the active layers were about 0.25 μm and 0.01 μm depending on the preparation conditions. The crosslinking reaction of the active layers were completed in less than three minutes via the formation of acetal linkage. The surface of the PVA/SA composite membrane was found to be anionic. The permeation properties of the composite membrane were as follows: 1.3 m³/m² day of flux and > 95% of rejection at 200 psi for 1000 ppm PEG600 solution. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 347–354, 2000     

Preparation of water‐swollen hydrogel membranes for gas separation

Water‐swollen hydrogel (WSH) membranes for gas separation were prepared by the dip‐coating of asymmetric porous polyetherimide (PEI) membrane supports with poly(vinyl alcohol) (PVA)–glutaraldehyde (GA), followed by the crosslinking of the active layer by a solution method. Crosslinked PVA/GA film of different blend compositions (PVA/GA = 1/0.04, 0.06, 0.08, 0.10, 0.12 mol %) were characterized by differential scanning calorimetry (DSC) and their water‐swelling ratio. The swelling behavior of PVA/GA films of different blend compositions was dependent on the crosslinking density and chemical functional groups created by the reaction between PVA and GA, such as the acetal group, ether linkage, and unreacted pendent aldehydes in PVA. The permeation performances of the membranes swollen by the water vapor contained in a feed gas were investigated. The behavior of gas permeation through a WSH membrane was parallel to the swelling behavior of the PVA/GA film in water. The permeation rate of carbon dioxide through the WSH membranes was 10⁵ (cm³ cm^?2 s^?1 cmHg) and a CO₂/N₂ separation factor was about 80 at room temperature. The effect of the additive (potassium bicarbonate, KHCO₃) and catalyst (sodium arsenite, NaASO₂) on the permeation of gases through these WSH membranes was also studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1785–1791, 2001     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

A polyvinyl alcohol-based mixed matrix membrane with uniformly distributed Schiff base network-1 for ethanol dehydration

In this study, Schiff base network (SNW)-1 nanoparticles with high hydrophilicity and large specific surface area were used to prepare polyvinyl alcohol (PVA)-based mixed matrix membranes (MMMs), which were evaluated for ethanol dehydration. Because of the low difference of density between SNW-1 and PVA, the as-prepared nanoparticles can be uniformly distributed into the PVA active layer. The effects of SNW-1 loading, feed temperature, and water concentration on pervaporation (PV) performance were further studied. The results showed the MMM with 10 wt% of SNW-1 loading exhibited a separation factor of 1,501 and a permeation flux of 187 g m⁻² h⁻¹ for feeding 95 wt% ethanol/water binary solution at 75°C. Overall, the SNW-1/PVA MMMs showed great prospect in ethanol dehydration via PV.     

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     

Pervaporation dehydration of ethyl acetate aqueous solution using the doubly modified polyvinyl alcohol (PVA) composite membrane

Polyvinyl alcohol–tetraethoxysilane–perfluorosulfonic acid (PVA–TEOS–PFSA) hybrid membrane was prepared by sol–gel method through PVA being modified doubly by PFSA and TEOS. With polyacrylonitrile (PAN) ultrafiltration membrane as a substrate membrane, PVA–TEOS–PFSA/PAN composite membrane was fabricated by dip-coating method for pervaporation (PV) dehydration of ethyl acetate (EAc) aqueous solution. The hybrid membrane was characterized by swelling degree, static contact angle, Fourier transform infrared spectra and scanning electron microscope. Effects of PFSA and TEOS contents in coating solution on PV performance of composite membrane were investigated, respectively. With increasing PFSA content, the permeation flux of composite membrane increased, while the separation factor decreased. Just the opposite, the increase of TEOS content resulted in the decrease in permeation flux and the increase in separation factor. In addition, the PV performances of composite membranes were also investigated at different feed temperatures and water concentrations in feed, respectively. The PVA–TEOS–PFSA/PAN composite membrane, which was prepared from coating with PVA/PFSA mass ratio of 80/20 and TEOS content of 20 wt%, exhibited the permeation flux of 347.9 g m^?2 h^?1 and the separation factor of 2218 for PV dehydration of 2 wt% water of EAc solution at 40 °C.     

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     

聚乙烯醇-二氧化硅/聚丙烯腈杂化复合膜渗透蒸发分离己内酰胺/水溶液

制备了以聚乙烯醇(PVA)填充纳米SiO2改性膜为活性层,聚丙烯腈(PAN)超滤膜为底膜的PVA-SiO2/PAN杂化复合膜,并用于己内酰胺(CPL)脱水。用FTIR,SEM,XRD,TGA分别对膜进行了表征,并考察了膜中纳米SiO2粒子的质量分数、进料组分质量分数和温度对复合膜分离性能的影响。结果表明,引入纳米SiO2后,杂化膜的热稳定性明显提高。当膜中纳米SiO2质量分数为1.0%时,复合膜渗透蒸发分离性能最佳。60℃下此复合膜用于分离质量分数为40%的CPL溶液时,其总通量和分离因子分别达到2 177 g/(m2.h)和349。     

Comparative behavior of PVA/PAN and PVA/PES composite pervaporation membranes in the pervaporative dehydration of caprolactam

Flat‐sheet composite membranes were developed by the traditional phase inversion technique using poly;(vinyl alcohol) (PVA). PVA composite pervaporation (PV) membranes were prepared with crosslinked PVA selective layer and porous polyacrylonitrile (PAN) and polyether sulfone (PES) substrate layer material as supports for separating heat sensitivity substance ε‐caprolactam (CPL) from CPL/water mixtures. Glutaraldehyde was used as crosslinking agent. The effect of the composition of glutaraldehyde on membrane stability and structure were investigated. The operating parameters, such as feed concentration and operating temperature, remarkably affected PV performance of the composite membranes. The composite membranes with PVA casted on PAN (PVA/PAN) showed superior PV performance than that casted on PES (PVA/PES). This study has also shown that the type of porous support plays an important role in the PV performance. As a result, this work has presented the information needed of the behavior of PV membranes for dehydration applications of industrial caprolactam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4005–4011, 2007     

Poly(ether sulfone) supported hybrid poly(vinyl alcohol)–maleic acid–silicone dioxide membranes for the pervaporation separation of ethanol–water mixtures

Microporous poly(ether sulfone) (PES) supported hybrid polymer–inorganic membranes were prepared by the crosslinking of poly(vinyl alcohol) (PVA), maleic acid (MA), and SiO₂ via an aqueous sol–gel route and a solution‐casting method. The membrane performance was tested for the pervaporation separation of ethanol–water mixtures from 20 to 60 °C with a feed ethanol concentration of 96 wt %. The membrane characterization results reveal that different SiO₂ loadings affected the crystallinity and roughness of the membranes. The PVA–MA–SiO₂ membrane containing 10 wt % SiO₂ showed that SiO₂ nanoparticles were well dispersed within the polymer matrix; this resulted in significant enhancements in both the flux and selectivity. The membrane achieved a high water permeability of 1202 g·μm·m^?2 h^?1 kPa^?1 and a selectivity of 1027 for the separation of a 96 wt % ethanol‐containing aqueous solution. This enhanced membrane performance might have been due to the dense crosslinking membrane network, increased free volume, and uniform distribution of SiO₂ nanoparticles. Both the water and ethanol fluxes increased with the feed water concentration and temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44839.     

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     

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     

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     

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.     

Teflon AF2400/Ultem composite hollow fiber membranes for alcohol dehydration by high‐temperature vapor permeation

High‐temperature vapor permeation has a stringent requirement of membrane stability under harsh feed environments. This work reports the design of Teflon AF2400/Ultem composite hollow fiber (HF) membranes for alcohol dehydration via vapor permeation. Fabrication parameters such as Teflon concentration and coating time were systematically investigated. Interestingly, the fabricated composite HF membranes possess an unusual surface with honeycomb‐like microstructure patterns. Owing to the Teflon protective layer, the newly developed composite HF shows a promising and stable separation performance with a flux of 4265 gm^?2 h^?1 and a separation factor of 383 for 95% isopropanol dehydration at 125°C. The composite HF also performs well under extreme vapor feed compositions from 87 to 99 wt % isopropanol. In addition, it exhibits impressive separation performance for the dehydration of ethanol and n‐butanol. This work may provide useful insights of designing thermal‐stable and high‐performance composite polymeric membranes for vapor permeation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1747–1757, 2016