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 composite membranes with polyimides and poly (amide-imide)s skin via interfacial condensation for air separation

Composite membranes were prepared by the interfacial condensation of water-soluble diamines with an organic solvent (dichloromethane)-soluble dicarbo-methoxy terephthaloyl chloride or carbomethoxy terephthaloyl chloride on top of a porous aluminum oxide support. The morphology of skin on the composite membranes is different in the two different procedures. The polyimide composite membranes with 40-times coatings provide a high gas permeation rate of oxygen and good permselectivity [α(O₂/N₂)]. The composite membrane with the polyimides skin at 40-times coatings had a gas permeation rate of oxygen range from 83 × 10⁻⁵ to 130 × 10⁻⁵ cm³(STP) s⁻¹ cm⁻² cmHg⁻¹, and a permselectivity [α(O₂/N₂)] range of 3.57 to 5.60. The composite membrane with poly (amide-imide)s skin at 40-times coatings had a gas permeation rate of oxygen range from 102 × 10⁻⁵ to 146 × 10⁻⁵ cm³(STP) s⁻¹ cm⁻² cmHg⁻¹, and the permselectivity (α(O₂/N₂)) range from 3.20 to 4.96.     

Fabrication and characterization of polyetherimide/polyvinyl acetate polymer blend membranes for CO2/CH4 separation

This article presents fabrication, characterization, and performance evaluation of polyetherimide (PEI)/polyvinyl acetate (PVAc) blend membranes. Polymer blend membranes with various blend ratios of PEI/PVAc were prepared by solution casting and evaporation technique. Morphology and miscibility of polymer blend membranes were characterized by field emission scanning electron microscope (FESEM) and differential scanning calorimetry (DSC), respectively. The interaction between blend polymers was analyzed by FTIR analysis. Gas separation performance was evaluated in terms of permeability and selectivity. FESEM results revealed that pure polymer and blend membranes were homogeneous and dense in structure. A single glass transition temperature of polymer blend membranes was found in DSC analysis which indicated the miscibility of PEI/PVAc blend. FTIR analysis confirmed the presence of molecular interaction between blend polymers. The permeation results showed that the presence of PVAc (3 wt%) in blend membranes has improved CO₂ permeability up to 95% compared to pure PEI membrane. In addition, CO₂/CH₄ selectivity was found to be 40% higher than pure PEI membrane. This study shows that blending a small fraction of PVAc can improve the gas separation performance of PEI/PVAc blend membranes. POLYM. ENG. SCI., 59:E293–E301, 2019. © 2018 Society of Plastics Engineers     

Novel Tertiary Amino Containing Blinding Composite Membranes via Raft Polymerization and Their Preliminary CO2 Permeation Performance

Facile synthesis of poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) star polymers on the basis of the prepolymer chains, PDMAEMA as the macro chain transfer agent and divinyl benzene (DVB) as the cross-linking reagent by reversible addition-fragmentation chain transfer (RAFT) polymerization was described. The RAFT polymerizations of DMAEMA at 70 °C using four RAFT agents with different R and Z group were investigated. The RAFT agents used in these polymerizations were dibenzyl trithiocarbonate (DBTTC), s-1-dodecyl-s''-(α,α''-dimethyl-α-acetic acid) trithiocarbonate (MTTCD), s,s''-bis (2-hydroxyethyl-2''-dimethylacrylate) trithiocarbonate (BDATC) and s-(2-cyanoprop-2-yl)-s-dodecyltrithiocarbonate (CPTCD). The results indicated that the structure of the end-group of RAFT agents had significant effects on the ability to control polymerization. Compared with the above-mentioned RAFT agents, CPTCD provides better control over the molecular weight and molecular weight distribution. The polydispersity index (PDI) was determined to be within the scope of 1.26 to 1.36. The yields, molecular weight, and distribution of the star polymers can be tuned by changing the molar ratio of DVB/PDMAEMA-CPTCD. The chemical composition and structure of the linear and star polymers were characterized by GPC, FTIR, ¹H NMR, XRD analysis. For the pure Chitosan membrane, a great improvement was observed for both CO₂ permeation rate and ideal selectivity of the blending composite membrane upon increasing the content of SPDMAEMA-8. At a feed gas pressure of 37.5 cmHg and 30 °C, the blinding composite membrane (Cs: SPDMAEMA-8 = 4:4) has a CO₂ permeation rate of 8.54 × 10⁻⁴ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹ and a N₂ permeation rate of 6.76 × 10⁻⁵ cm³ (STP) cm⁻²∙s⁻¹∙cm∙Hg⁻¹, and an ideal CO₂/N₂ selectivity of 35.2.     

Polyvinylidene fluoride and polyetherimide hollow fiber membranes for CO2 stripping in membrane contactor

Porous polyvinylidene fluoride (PVDF) and polyetherimide (PEI) hollow fiber membranes incorporating polyethylene glycol (PEG) were prepared via spinning process for CO₂ membrane stripping. CO₂ loaded diethanolamine solution was used as liquid absorbent while N₂ was used as a strip gas. The characterization study of the fibers was carried out in terms of permeation test, contact angle measurement and liquid entry pressure (wetting pressure). Performance study via membrane contactor stripping was carried out at specific operating condition. The experimental results showed that PVDF membrane have high gas permeation, effective surface porosity and contact angle despite having lower liquid entry pressure in comparison with PEI membrane. PVDF-PEG membrane showed the highest stripping flux of 4.0 × 10⁻² mol m⁻² s⁻¹ at 0.7 ms⁻¹ compared to that of PEI membrane. Although the stripping flux for PEI-PEG membranes was slightly lower than PVDF membrane (e.g. 3.5 × 10⁻² mol m⁻² s⁻¹ at liquid velocity of 0.85 ms⁻¹), the membrane wetting pressure of PEI membrane is higher than hydrophobic PVDF membrane. Long term performance of both membranes showed severe flux reduction but started to level-off after 30 h of operation.     

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO₂/CH₄ separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO₂/CH₄ separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO₂ permeation and CO₂/CH₄ selectivity due to high affinity of the ionic liquid to carbon dioxide. CO₂ permeation significantly increases from 4.3 Barrer (1 Barrer=10^-10 cm³(STP)·cm·cm^-2·s^-1·cmHg^-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH₄ molecules for CO₂ permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO₂/CH₄ separation membranes.     

Preparation of polyvinylamine/polysulfone composite hollow‐fiber membranes and their CO2/CH4 separation performance

Fixed‐carrier composite hollow‐fiber membranes were prepared with polyvinylamine (PVAm) as the selective layer and a polysulfone ultrafiltration membrane as the substrate. The effects of the PVAm concentration in the coating solution, the number of coatings, and the crosslinking of glutaraldehyde and sulfuric acid on the CO₂ permeation rate and CO₂/CH₄ selectivity of the composite membranes were investigated. As the PVAm concentration and the number of coatings increased, the CO₂/CH₄ selectivity increased, but the CO₂ permeation rate decreased. The membranes crosslinked by glutaraldehyde or sulfuric acid possessed higher CO₂/CH₄ selectivities but lower CO₂ permeation rates. For the pure feed gas, a composite hollow‐fiber membrane coated with a 2 wt % PVAm solution two times and then crosslinked with glutaraldehyde and an acid solution in sequence had a CO₂ permeation rate of 3.99 × 10^?6 cm³ cm^?2 s^?1 cmHg^?1 and an ideal CO₂/CH₄ selectivity of 206 at a feed gas pressure of 96 cmHg and 298 K. The effect of time on the performance of the membranes was also investigated. The performance stability of the membranes was good during 6 days of testing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1885–1891, 2006     

Development of CO2-Philic Blended Membranes Using PIM–PI and PIM–PEG/PPG

Blending is a simple method through which one can effectively tailor new polymers exhibiting the properties of their parent ones. Because the original properties of polymers are maintained after blending, various studies have used these films as gas separation membranes. In this study, a new CO₂ separation membrane is developed by physically mixing a polymer of intrinsic microporosity (PIM) with high gas permeability, polyimide (PIM-PI), as the hard segment and CO₂-philic PIM-poly(ethylene glycol)/poly(propylene glycol), or PIM-PEG/PPG, as the soft segment. Prepared by adding 5 mol.% of PIM-PEG/PPG to PIM-PI, the blended membrane PPB-5, with a tensile strength of 54 MPa and 35.5% elongation at break, shows better mechanical properties than commercial high-performance polymer membranes developed for gas separation, PEG-based blended membranes, and corresponding copolymer membranes with similar compositions developed in a previous study. In addition, it shows high CO₂ permeability (1552.6 Barrer) and CO₂/N₂ selectivity (29.3) due to the well-developed microphase separation characteristics originating from the optimal two-component composition, and the gas separation performance is close to the Robeson (2008) upper bound.     

Controlled synthesis of high performance carbon/zeolite T composite membrane materials for gas separation

A simple approach has been developed to synthesize the carbon/zeolite T composite membrane materials with the high gas separation performance. The precursors of the composite membrane are composed of polyimide matrix and dispersed zeolite T particles. The composite membranes prepared by pyrolysis at 973 K show excellent gas (H₂, CO₂, O₂, N₂, and CH₄) permeability and selectivity (O₂/N₂, CO₂/CH₄) for both single gas and mixed-gas. The gas separation performance of the composite membranes can be controlled in a wide range by only changing the zeolite T particle size. The maximum selectivity of O₂ over N₂ (21/79 mol%) for the composite membranes with the least zeolite T particle (0.5 μm) is 15 with an O₂ permeability of 347 Barrers (1 Barrer = 7.5 × 10⁻¹⁸ m² s⁻¹ Pa⁻¹) and the selectivity of CO₂ over CH₄ (50/50 mol%) reaches a value of 179 with a CO₂ permeability of 1532 Barrers. It is believed that the increase of gas permeability is attributed to the ordered microchannels in the zeolite and the interfacial gaps formed between zeolite and carbon matrix in the composite membranes. And the gas selectivity is tuned by the size of interfacial gaps which are varied with the zeolite particle size. This technique will provide a simple and convenient route to efficiently improve the trade-off relationship between the permeability and the selectivity and enable the construction of carbon-based composite materials with novel functionalities in membrane science.     

Heterogeneous membranes based on a composite of a hypercrosslinked microparticle adsorbent and polyimide binder

This paper deals with the preparation and characterization of heterogeneous membranes based on microparticle hypercrosslinked polymeric adsorbents with a polyimide binder. The polyimide based membrane extension is hindered by their low permeability. We enhanced the permeability of polyimide membranes by changed chemical structure and by adding of the new type fillers. Hypercrosslinked polystyrene microparticles of diameter 1–5 μm were prepared by SnCl₄-catalyzed Friedel–Crafts reaction of polystyrene with chloromethyl methyl ether in 1,2-dichlorethane solution. The precursor polyamic acid (PAA) was synthesized by the reaction of equimolar amounts of 4,4′-oxy(bis(phthalic anhydride)) (ODPA) and bis(4,4′-oxydianiline) (ODA) or 4,4′-[(1,4-phenylene)dipropane-2,2-diyl]dianiline (BIS P) in N-methylpyrrolidone (content 10 wt.%). A PAA solution in N-methylpyrrolidone with the adsorbent was spread onto a glass substrate and kept at 60–240 °C for 12 h. Heterogeneous membranes were characterized by thermal, mechanical and separation measurements. The permeability for membrane ODPA–BIS P filled with 10 wt.% of hypercrosslinked adsorbent was 3.5 × 10⁻¹¹ cm³(STP) cm cm⁻² s⁻¹ cmHg⁻¹ for nitrogen and 4 × 10⁻⁹ cm³(STP) cm cm⁻² s⁻¹ cmHg⁻¹ for hydrogen. The permeability of homogeneous polyimide membranes is up to one order of magnitude lower. The diffusion coefficient of heterogeneous membranes increased in the order CH₄ < N₂ < O₂ < CO₂ < H₂. The selectivity of hydrogen–nitrogen separation with the amount of adsorbent decreased from 164 to 69. The prepared membranes are intended for separation of gases and low organic molecules even at enhanced temperature. The present paper aims at giving information on the influence of hypercrosslinked adsorbents and polyimide binding materials on the gas separation properties of membranes.     

Preparation of vinyl amine‐co‐vinyl alcohol/polysulfone composite membranes and their carbon dioxide facilitated transport properties

A vinyl amine–vinyl alcohol copolymer (VAm–VOH) was synthesized through free‐radical polymerization, basic hydrolysis in methanol, acidic hydrolysis in water, and an anion‐exchange process. In the copolymer, the primary amino groups on the VAm segment acted as the carrier for CO₂‐facilitated transport, and the vinyl alcohol segment was used to reduce the crystallinity and increase the gas permeance. VAm–VOH/polysulfone (PS) composite membranes for CO₂ separation were prepared with the VAm–VOH copolymer as a selective layer and PS ultrafiltration membrane as a support. The membrane gas permselectivity was investigated with CO₂, N₂, and CH₄ pure gases and their binary mixtures. The results show that the CO₂ transport obeyed the facilitated transport mechanism, whereas N₂ and CH₄ followed the solution–diffusion mechanism. The increase in the VAm fraction in the copolymer resulted in a carrier content increase, a crystallinity increase, and intermolecular hydrogen‐bond formation. Because of these factors, the CO₂ permeance and CO₂/N₂ selectivity had maxima with the VAm fraction. At an optimum applied pressure of 0.14 MPa and at an optimum VAm fraction of 54.8%, the highest CO₂ permeance of 189.4 GPU [1 GPU = 1 × 10^?6 cm³(STP) cm^?2 s^?1 cmHg^?1] and a CO₂/N₂ selectivity of 58.9 were obtained for the CO₂/N₂ mixture. The heat treatment was used to improve the CO₂/N₂ selectivity. At an applied pressure of 0.8–0.92 MPa, the membrane heat‐treated under 100°C possessed a CO₂ permeance of 82 GPU and a CO₂/N₂ selectivity of 60.4, whereas the non‐heat‐treated membrane exhibited a CO₂ permeance of 111 GPU and a CO₂/N₂ selectivity of 45. After heat treatment, the CO₂/N₂ selectivity increased obviously, whereas the CO₂ permeance decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40043.     

A high CO2 permselective mesoporous silica/carbon composite membrane for CO2 separation

Ordered mesoporous silica/carbon composite membranes with a high CO₂ permeability and selectivity were designed and prepared by incorporating SBA-15 or MCM-48 particles into polymeric precursors followed by heat treatment. The as-made composite membranes were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and N₂ adsorption, of which the gas separation performance in terms of gas permeability and selectivity were evaluated using the single gas (CO₂, N₂, CH₄) and gas mixtures (CO₂/N₂ and CO₂/CH₄, 50/50 mol.%). In comparison to the pure carbon membranes and microporous zeolite/C composite membranes, the as-made mesoporous silica/C composite membranes, and the MCM-48/C composite membrane in particular, exhibit an outstanding CO₂ gas permeability and selectivity for the separation of CO₂/CH₄ and CO₂/N₂ gas pairs owing to the smaller gas diffusive resistance through the membrane and additional gas permeation channels created by the incorporation of mesoporous silicas in carbon membrane matrix. The channel shape and dimension of mesoporous silicas are key parameters for governing the gas permeability of the as-made composite membranes. The gas separation mechanism and the functions of porous materials incorporated inside the composite membranes are addressed.     

CO2 separation performance by chitosan/tetraethylenepentamine/poly(ether sulfone) composite membrane

CO₂ separation from CO₂/N₂ (20:80) gas mixture has been demonstrated by tetraethylenepentamine blended with chitosan (CS‐TEPA) membrane. Optimization of CS and TEPA weight ratio were carried out based on characterization details involving thermogravimetric analysis, Fourier transform infrared spectroscopy, X‐ray diffraction, atomic force microscope, and field emission scanning electron microscope. Effects of water flow rate, pressure, and temperature were concurrently studied on CS‐TEPA membranes through gas permeation. Almost twofold increase in CO₂ permeance (24.7 GPU) was detected in CS blend with 30% (w/w) of TEPA (CS70) as compared to pure CS membrane (12.5 GPU). CS70 yielded CO₂/N₂ selectivity of 80 whereas CS demonstrated a maximum of 54 at 90 °C. The membrane also exhibited improved stability at temperatures less than 120 °C which was evident from TGA isotherm trace. The proposed composite membrane can be a promising candidate for flue gas separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45206.     

Fabrication of asymmetric polyethersulfone membranes for separation of carbon dioxide from methane using polyetherimide as polymeric additive

Polyetherimide (PEI) was used as a polymeric additive for preparing an asymmetric polyethersulfone (PES) membrane for the separation of CO₂ from CH₄. In pure gas experiments, the higher skin layer thickness and the lower porosity of the sub layer for the membrane prepared from the polymer blend with the composition of 98:2 lead to an increase in CO₂/CH₄ selectivity and a decrease in the CO₂ permeance in contrast with a pristine PES. For higher PEI contents, the higher fractional free volume of the membranes improves the gas permeance and reduces the CO₂/CH₄ selectivity. The incorporation of PEI in PES reduces the CO₂ sorption in PES via decreasing the non-equilibrium free volume and imparts antiplasticization properties to the membrane.     

Metal‐organic framework membrane process for high purity CO2 production

Gas separation by metal‐organic framework (MOF) membranes is an emerging research field. Their commercial application potential is, however, still rarely explored due in part to unsatisfied separation characteristics and difficulty in finding suitable applications. Herein, we report “sharp molecular sieving” properties of high quality isoreticular MOF‐1 (IRMOF‐1) membrane for CO₂ separation from dry, CO₂ enriched CO₂/CH₄, and CO₂/N₂ mixtures. The IRMOF‐1 membranes exhibit CO₂/CH₄ and CO₂/N₂ separation factors of 328 and 410 with CO₂ permeance of 2.55 × 10^?7 and 2.06 × 10^?7 mol m^?2 s^?1 Pa^?1 at feed pressure of 505 kPa and 298 K, respectively. High grade CO₂ is efficiently produced from the industrial or lower grade CO₂ feed gas by this MOF membrane separation process. The demonstrated “sharp molecular sieving” properties of the MOF membranes and their potential application in production of value‐added high purity CO₂ should bring new research and development interest in this field. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3836–3841, 2016     

Effects of halloysite nanotubes on the morphology and CO2/CH4 separation performance of Pebax/polyetherimide thin-film composite membranes

Enhancing the performance of gas separation membranes is one of the major concerns of membrane researchers. Thus, in this study, poly(ether-block-amide) (Pebax)/polyetherimide (PEI) thin-film composite membranes were prepared and their CO₂/CH₄ gas separation performance was investigated by means of pure and mixed gases permeation tests. To improve the properties of these membranes, halloysite nanotubes (HNT) were added to Pebax layer at different loadings of 0.5, 1, 2, and 5 wt % to form Pebax-HNT/PEI membranes. Scanning electron microscopy, gas sorption, X-ray diffraction, Fourier-transform infrared, and differential scanning calorimetry tests were also performed to investigate the impact of HNT on structure and properties of prepared membranes. Results showed that both CO₂/CH₄ selectivity and CO₂ permeance increased by adding HNT to Pebax layer up to 2 wt %. By increasing HNT loading to 5 wt %, the CO₂/CH₄ selectivity decreased from 32 to 18, while CO₂ permeance increased from 3.25 to 4.2 GPU. Pebax/PEI and Pebax-HNT/PEI membranes containing 2 wt % of HNT were tested using CO₂/CH₄ gas mixtures at different feed CO₂ concentrations and feed pressure of 4 bar. The results showed that with increasing CO₂ concentration from 20 to 80 vol %, CO₂/CH₄ selectivity of Pebax/PEI composite membranes increased by 19%, while, in Pebax-HNT/PEI membrane, CO₂/CH₄ selectivity decreased by 40%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48860.     

Carbon Membranes Prepared from a Polymer Blend of Polyethylene Glycol and Polyetherimide

Through a dip‐coating technique, carbon membranes were produced from a polymer blend consisting of the thermally stable polymer polyetherimide (PEI) and the thermally labile polymer polyethylene glycol (PEG). The PEG/PEI carbon membranes were synthesized on an alumina support coated with an Al₂O₃ intermediate layer. The polymer blend ratio and carbonization temperature influenced the structure and permeation performance of the derived carbon membranes. The porosity of the PEG/PEI carbon membranes increased with higher PEG content in the blends. However, the derived carbon membranes tended to lose gas permeability with raising the carbonization temperatures. The carbon membranes were successfully optimized in order to achieve the highest CO₂/CH₄ and CO₂/N₂ selectivities.     

Preparation of polyethyleneglycol (PEG) and cellulose acetate (CA) blend membranes and their gas permeabilities

Miscible blend membranes containing 10 wt % PEG of low molecular weight 200, 600, 2000, and 6000, and 10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %, and 60 wt % of molecular weight 20,000 were prepared to investigate the effect of PEG on gas permeabilities and selectivities for CO₂ over N₂ and CH₄. The permeabilities of CO₂, H₂, O₂, CH₄, and N₂ were measured at temperatures from 30 to 80°C and pressures from 20 cmHg to 76 cmHg using a manometric permeation apparatus. It was determined that the blend membrane, which contained 10% PEG 20,000, exhibited higher permeability for CO₂ and higher permselectivity for CO₂ over N₂ and CH₄ than those of the membranes that contained 10% PEG of the molecular weight ranging from 200 to 6000. The high PEG 20,000 content blend membranes showed remarkable permeation properties such that the permeability coefficients of CO₂ and the ideal separation factors for CO₂ over N₂ reached above 200 barrer and 22, respectively, at 70°C and 20 cmHg. Based on the data of gas permeability coefficients, time lags, and characterization of the membranes, it is proposed that the apparent solubility coefficients of all CA and PEG blend membranes for CO₂ were lower than those of the CA membrane. However, almost all of the blend membranes containing PEG 20,000 showed higher apparent diffusivity coefficients for CO₂, resulting in higher permeability coefficients of CO₂ than those of the CA membrane. It is attributed to the high diffusivity selectivities of CA and PEG 20,000 blend membranes that their ideal separation factors for CO₂ over N₂ were higher than those of the CA membrane in the temperature range from 50 to 80°C, even though the ideal separation factors of all CA and PEG blend membranes for CO₂ over CH₄ became lower than those of the CA membrane over nearly the full temperature range from 30 to 80°C. © 1995 John Wiley & Sons, Inc.     

Separation of CO2 from CH4 by pure PSF and PSF/PVP blend membranes: Effects of type of nonsolvent,solvent, and PVP concentration

Complete CO₂/CH₄ gas separation was aimed in this study. Accordingly, asymmetric neat polysulfone (PSF) and PSF/polyvinylpyrrolidone (PVP) blend membranes were prepared by wet/wet phase inversion technique. The effects of two different variables such as type of external nonsolvent and type of solvent on morphology and gas separation ability of neat PSF membranes were examined. Moreover, the influence of PVP concentration on structure, thermal properties, and gas separation properties of PSF/PVP blend membrane were tested. The SEM results presented the variation in membrane morphology in different membrane preparation conditions. Atomic forced microscopic images displayed that surface roughness parameters increased significantly in higher PVP loading and then gas separation properties of membrane improved. Thermal gravimetric analysis confirms higher thermal stability of membrane in higher PVP loading. Differential scanning calorimetric results prove miscibility and compatibility of PSF and PVP in the blend membrane. The permeation results indicate that, the CO₂ permeance through prepared PSF membrane reached the maximum (275 ± 1 GPU) using 1‐methyl‐2‐pyrrolidone as a solvent and butanol (BuOH) as an external nonsolvent. While, a higher CO₂/CH₄ selectivity (5.75 ± 0.1) was obtained using N‐N‐dimethyl‐acetamide (DMAc) as a solvent and propanol (PrOH) as an external nonsolvent. The obtained results show that PSF/PVP blend membrane containing 10 wt % of PVP was able to separate CO₂ from CH₄ completely up to three bar as feed pressure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1139‐1147, 2013     

Preparation,characterization, and applicability of novel calix[4]arene‐based cellulose acetate membranes in gas permeation

Cellulose acetate (CA) is well known glassy polymer used in the fabrication of gas‐separation membranes. In this study, 5,11,17,23‐tetrakis(N‐morpholinomethyl)‐25,26,27,28‐tetrahydroxycalix[4]arene (CL) was blended with CA to study the gas‐permeation behavior for CO₂, N₂, and CH₄ gases. We prepared the pure CA and CA/CL blended membranes by following a diffusion‐induced phase‐separation method. Three different concentrations of CL (3, 10, and 30 wt %) were selected for membrane preparation. The CA/CL blended membranes were then characterized via Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X‐ray diffraction analysis. The homogeneous blending of CL and CA was confirmed in the CA/CL blended membranes by both SEM and AFM analysis. In addition to this, the surface roughness of the CA/CL blended membranes also increased with increasing CL concentration. FTIR analysis described the structural modification in the CA polymer after it was blended with CL too. Furthermore, CL improved the tensile strength of the CA membrane appreciably from 0.160 to 1.28 MPa, but this trend was not linear with the increase in the CL concentration. CO₂, CH₄, and N₂ gases were used for gas‐permeation experiments at 4 bars. With the permeation experiments, we concluded that permeability of N₂ was higher in comparison to those of CO₂ and CH₄ through the CA/CL blended membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39985.