Permeation through CO2selective glassy polymeric membranes in the presence of hydrogen sulfide

Minor components present in feed gas streams can have a significant influence on the separation performance of polymeric membranes. Hydrogen sulfide is present in many of the processes where CO₂ capture is possible and can therefore undergo competitive sorption with CO₂ for transport through the membrane, as well as influence the membrane morphology inducing plasticization. This study investigates the change in CO₂ permeability and CO₂/N₂ selectivity of two glassy polymeric membranes; polysulfone and 6FDA‐TMPDA, when 500 ppm H₂S is present in the gas mixture. The outcomes of this study reveal that H₂S in trace amounts has a strong influence on the separation performance of both membranes. For both membranes, a plasticization partial pressure ～0.5–0.6 kPa H₂S is observed. H₂S competitive sorption is also observed and is modeled by competitive dual‐sorption theory. Results suggest that mixed gas permeation influences the amount of each gas immobilized within the Langmuir voids in addition to the expected competitive sorption effects. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

CO2 sorption and transport behavior of ODPA-based polyetherimide polymer films

Plasticization phenomena can significantly reduce the performance of polymeric membranes in high-pressure applications. Polyetherimides (PEIs) are a promising group of membrane materials that combine relatively high CO₂/CH₄ selectivities with high chemical and thermal stability. In this work sorption, swelling, and mixed gas separation performance of 3,3′,4,4′-oxydiphthalic dianhydride (ODPA)-based PEI polymers, with 1, 2 or 3 para-aryloxy substitutions in the diamine moeiety, is investigated under conditions where commercial membranes suffer from plasticization. Particular focus is on the influence of the amount of para-aryloxy substitutions and the film thickness. Results are compared with those of commercially available polymeric membrane materials (sulphonated PEEK, a segmented block-co-polymer PEBAX and the polyimide Matrimid).The glassy polymers display increasing CO₂ sorption with increasing T_g. The larger extent of sorption results from a larger non-equilibrium excess free volume. Swelling of the polymers is induced by sorption of CO₂ molecules in the non-equilibrium free volume as well as from molecules dissolved in the matrix. Dilation of the polymer is similar for each molecule sorbed. Correspondingly, the partial molar volume of CO₂ is similar for molecules present in both regions.Mixed gas separation experiments with a 50/50% CO₂/CH₄ feed gas mixture showed high CO₂/CH₄ selectivities for the ODPA PEI films at elevated pressure. This shows that these materials could potentially be interesting for high-pressure gas separation applications, although additional gas permeation experiments using different feed gas compositions and thin films are required.     

Separation of CO2/CH4 through carbon molecular sieve membranes derived from P84 polyimide

The separation of CO₂/CH₄ separation is industrially important especially for natural gas processing. In the past decades, polymeric membranes separation technology has been widely adopted for CO₂/CH₄ separation. However, polymeric membranes are suffering from plasticization by condensable CO₂ molecules. Thus, carbon molecular sieve membranes (CMSMs) with excellent separation performance and stability appear to be a promising candidate for CO₂/CH₄ separation. A commercially available polyimide, P84 has been chosen as a precursor in preparing carbon membranes for this study. P84 displays a very high selectivity among the polyimides. The carbonization process was carried out at 550–800 °C under vacuum environment. WAXD and density measurements were performed to characterize the morphology of carbon membranes. The permeation properties of single and equimolar binary gas mixture through carbon membranes were measured and analyzed. The highest selectivity was attained by carbon membranes pyrolyzed at 800 °C, where the pyrolysis temperatures significantly affected the permeation properties of carbon membranes. A comparison of permeation properties among carbon membranes derived from four commercially available polyimides showed that the P84 carbon membranes exhibited the highest separation efficiency for CO₂/CH₄ separation. The pure gas measurement underestimated the separation efficiency of carbon membranes, due to the restricted diffusion of non-adsorbable gas by adsorbable component in binary mixture.     

Polysulfone membranes containing ethylene glycol monomers: synthesis,characterization, and CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation

Copolymers based on glassy and rubbery units have been developed to take advantage of both domains to enhance solubility and diffusivity. In this study, a series of gas separation membranes from polysulfone (PSF) containing ethylene glycol were synthesized via nucleophilic substitution polycondensation. The structures of copolymers were characterized by nuclear magnetic resonance spectra, Fourier transform infrared spectra, and thermal gravity analysis. The permeability and selectivity of the membranes were studied at different temperatures of 25–55 °C and pressures of 0.5–1.5 atm using single gases CO₂ and CH₄. Gas permeation measurements showed that copolymers with different contents of poly(ethylene glycol) exhibited different separation performances. For example, the membrane from PSF-PEG2000-20 containing 20 wt% poly(ethylene glycol) showed better performance in terms of ideal selectivity over the other seven copolymer membranes. The highest ideal CO₂/CH₄ selectivity was 43.0 with CO₂ permeability of 6.4 Barrer at 1.5 atm and 25 °C.     

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.     

Technico‐economical assessment of MFI‐type zeolite membranes for CO2 capture from postcombustion flue gases

A detailed survey of the effect of moisture on the CO₂/N₂ permeation and separation performance of Mobile Five (MFI) zeolite membranes in view of downstream postcombustion CO₂ capture applications in power plants and incinerators is presented. The membranes, displaying a nanocomposite architecture, have been prepared on α‐alumina tubes by pore‐plugging hydrothermal synthesis at 443 K for 89 h using a precursor clear solution with molar composition 1 SiO₂:0.45 tetrapropylammonium hydroxide:27.8 H₂O. The synthesized membranes present reasonable permeation and CO₂/N₂ separation properties even in the presence of high water concentrations in the gas stream. A critical discussion is also provided on the technico‐economical feasibility (i.e., CO₂ recovery, CO₂ purity in the permeate, module volume, and energy consumption) of a membrane cascade unit for CO₂ capture and liquefaction/supercritical storage from standard flue gases emitted from an incinerator. Our results suggest that the permeate pressure should be kept under primary vacuum to promote the CO₂ driving force within the membrane. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3183–3194, 2012     

Gas permeation properties of silica membranes with uniform pore sizes derived from polyhedral oligomeric silsesquioxane

The sol‐gel method was applied in the fabrication of homogenous polyhedral oligomeric silsesquioxane (HOMO‐POSS)‐derived silica membranes. Single gas permeation characteristics in a temperature range of 100–500^°C were examined to discuss the effect of silica precursor on amorphous silica networks. HOMO‐POSS‐derived membranes showed a CO₂ permeance of 1.1 × 10^?7 mol m^?2 s^?1 Pa^?1 with a CO₂/CH₄ permeance ratio of 131 at 100^°C, which is a superior CO₂/CH₄ separation performance by comparison with tetraethoxysilane (TEOS)‐derived silica membranes. Normalized Knudsen‐based permeance (NKP) was applied for quantitative evaluation of pore size. HOMO‐POSS‐derived membranes had loose amorphous silica structures compared to TEOS‐derived membranes and pore size was successfully tuned by changing the calcination temperatures. The activation energy for a HOMO‐POSS‐derived membrane fired at 550^°C with a uniform pore size of ～ 0.42 nm increased linearly with the ratio of the kinetic diameter of the gas molecule to the pore diameter, λ (=d_k/d_p), and showed a trend similar to that of DDR‐type zeolite membranes. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1733–1743, 2012     

Incorporation of carbon nanofibers into a Matrimid polymer matrix: Effects on the gas permeability and selectivity properties

Composite membranes containing carbon nanofibers (CNFs) and Matrimid were prepared by a solution‐casting method. Prepared Matrimid–CNF composite membranes were characterized with X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and mechanical testing techniques. The mechanical properties of the composite membranes increased over that of the pristine polymeric membranes. To develop a broad fundamental understanding of the connection between the composite architecture and gas‐transport properties, both the gas‐permeability and gas‐separation characteristics were evaluated. The gas‐transport properties of the Matrimid–CNF composite membrane was measured with a single gas‐permeation setup (He, H₂, N₂, CH₄ and CO₂) at ambient temperature with the variable‐volume method. The incorporation of CNFs (0.5–10 wt %) into the Matrimid matrix resulted in approximately a 22% reduction in the gas permeation of various gases, (H₂, He, CO₂, N₂, and CH₄). Moreover, an improvement of 1.5 times in the gas selectivity was observed for CO₂/CH₄, H₂/CH₄, He/CH₄, and H₂/N₂ compared to pristine polymeric membrane. Hence, such polymer–CNF composite membranes could be suitable for gas‐separation applications with high purity requirements. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46019.     

Study of transport of pure and mixed CO2/N2 gases through polymeric membranes

The permeations of pure CO₂ and N₂ gases and a binary gas mixture of CO₂/N₂ (20/80) through poly(dimethylsiloxane) (PDMS) membrane were carried out by the new permeation apparatus. The permeation and separation behaviors were characterized in terms of transport parameters, namely, permeability, diffusion, and solubility coefficients which were precisely determined by the continuous‐flow technique. In the permeation of the pure gases, feed pressure and temperature affected the solubility coefficients of CO₂ and N₂ in opposite ways, respectively; increasing feed pressure positively affects CO₂ solubility coefficient and negatively affects N₂ solubility coefficient, whereas increasing temperature favors only N₂ sorption. In the permeation of the mixed gas, mass transport was observed to be affected mainly by the coupling in sorption, and the coupling was analyzed by a newly defined parameter permeation ratio. The coupling effects have been investigated on the permeation and separation behaviors in the permeation of the mixed gas varying temperature and feed pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 179–189, 2000     

Effects of water vapor on gas permeation and separation properties of MFI zeolite membranes at high temperatures

Understanding the effects of water vapor on gas permeation and separation properties of MFI zeolite membranes, especially at high temperatures, is important to the applications of these zeolite membranes for chemical reactions and separation involving water vapor. The effects of water vapor on H₂ and CO₂ permeation and separation properties of ZSM‐5 (Si/Al ～ 80) zeolite and aluminum‐free silicalite membranes were studied by comparing permeation properties of H₂ and CO₂ with the feed of equimolar H₂/CO₂ binary and H₂/CO₂/H₂O ternary mixtures in 300–550°C. For both membranes, the presence of water vapor lowers H₂ and CO₂ permeance to the same extent, resulting in negligible effect on the H₂/CO₂ separation factor. The suppression effect of water vapor on H₂ and CO₂ permeation is larger for the less hydrophobic ZSM‐5 zeolite membrane than for the hydrophobic silicalite membrane, and, for both membranes, is stronger at lower temperatures and higher water vapor partial pressures. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Polycarbonate/silica nanocomposite membranes: Fabrication,characterization, and performance evaluation

Polycarbonate/silica nanocomposite membranes at low silica loading were fabricated by solution blending and solvent evaporation technique. The functionalized silica nanoparticles used were synthesized by co‐condensing hydrolyzed tetraethylorthosilicate with 3‐aminopropyl trimethoxysilane in the sol–gel process. The membranes morphology, composition, surface, structure, thermal and mechanical properties were analyzed by the standard characterization techniques. The gas permeation tests were conducted in four‐channel permeation cells. Field emission scanning electron microscopy results reveal that membranes above 3 wt % silica content formed distinguishable voids and agglomerates. Fair distribution of silica nanoparticles and absence of residual solvents were observed by energy dispersive X‐ray and thermogravimetric analysis. Fourier transform infrared spectroscopy spectra confirmed the presence of new functional groups (N? H) and (O? H) bonds. The X‐ray diffraction pattern revealed the polymer‐particle interactions, the formation of rigidified polymer chain, and nanostructured silicon crystals. Further, the thermogravimetric analysis results revealed thermal stability enhancement while differential scanning calorimetry results of increased glass transition temperatures confirmed the presence of rigidified polymer chain. Furthermore, enhancements in mechanical strength of the membranes were observed. Moreover, at all feed pressures, increased CO₂, N₂, and CH₄ gas permeation was observed. At 6 bar feed pressure, the CO₂/N₂ and CO₂/CH₄ ideal selectivities of PC membranes with 3 wt % silica loading have increased from 19.2 to 38.0 and 29.2, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45310.     

Preparation of silica xerogel with high silanol content from sodium silicate and its application as CO2 adsorbent

In this study, silica xerogels with high silanol content were synthesized by using sodium silicate as low-cost silica source in the presence of hydrochloric acid and acetic acid via sol–gel process for CO₂ adsorption purpose. The effect of amount of acetic acid on the surface and structural properties of silica xerogel was investigated. Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis (TGA) revealed that the silanol groups existed on the surface of silica xerogel products and their concentration increased with increasing the amount of acetic acid. The BET surface area and total pore volume of the silica xerogel prepared using 6 mL of acetic acid (MMS-6) were found to be 1021 m²/g and 0.72 cm³/g, respectively. The pore structure of silica xerogel products consisted of the interparticle voids between the nanoparticles aggregates, and the interconnected wormhole microporous structure. The latter pore structure was more uniform on increasing the amount of acetic acid. CO₂ adsorption/desorption measurements were carried out using TGA unit with high purity CO₂ (99.999%). The highest CO₂ sorption capacity (83.6 mg_CO2/g_sorbent) was obtained with MMS-6 product. Thermal swing adsorption studies showed that the silica xerogel products exhibited strongly reversible CO₂ adsorption capacity and stable during 5-repeated cycle of adsorption/desorption experiment at 35 °C.     

Size effects of graphene oxide on mixed matrix membranes for CO2 separation

Graphene oxide (GO)‐polyether block amide (PEBA) mixed matrix membranes were fabricated and the effects of GO lateral size on membranes morphologies, microstructures, physicochemical properties, and gas separation performances were systematically investigated. By varying the GO lateral sizes (100–200 nm, 1–2 μm, and 5–10 μm), the polymer chains mobility, as well as the length of the gas channels could be effectively manipulated. Among the as‐prepared membranes, a GO‐PEBA mixed matrix membrane (GO‐M‐PEBA) containing 0.1 wt % medium‐lateral sized (1–2 μm) GO sheets showed the highest CO₂ permeation performance (CO₂ permeability of 110 Barrer and CO₂/N₂ mixed gas selectivity of 80), which transcends the Robeson upper bound. Also, this GO‐PEBA mixed matrix membrane exhibited high stability during long‐term operation testing. Optimized by GO lateral size, the developed GO‐PEBA mixed matrix membrane shows promising potential for industrial implementation of efficient CO₂ capture. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2843–2852, 2016     

Characteristics of ammonia permeation through porous silica membranes

A sol–gel method was applied for the preparation of silica membranes with different average pore sizes. Ammonia (NH₃) permeation/separation characteristics of the silica membranes were examined in a wide temperature range (50–400°C) by measurement of both single and binary component separation. The order of gas permeance through the silica membranes, which was independent of membrane average pore size, was as follows: He > H₂ > NH₃ > N₂. These results suggest that, for permeation through silica membranes, the molecular size of NH₃ is larger than that of H₂, despite previous reports that the kinetic diameter of NH₃ is smaller than that of H₂. At high temperatures, there was no effect of NH₃ adsorption on H₂ permeation characteristics, and silica membranes were highly stable in NH₃ at 400°C (i.e., gas permeance remained unchanged). On the other hand, at 50°C NH₃ molecules adsorbed on the silica improved NH₃‐permselectivity by blocking permeation of H₂ molecules without decreasing NH₃ permeance. The maximal NH₃/H₂ permeance ratio obtained during binary component separation was ～30 with an NH₃ permeance of ～10^?7 mol m^?2 s^?1 Pa^?1 at an H₂ permeation activation energy of ～6 kJ mol^?1. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

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.     

Pervaporation of methanol/dimethyl carbonate using SiO2 membranes with nano‐tuned pore sizes and surface chemistry

Porous silica membranes with different pore sizes (average pore size: 0.3–1.2 nm) and surface chemistry were prepared from SiO₂, steam‐treated SiO₂, SiO₂? ZrO₂, and SiO₂? TiO₂ by sol‐gel processing, and were applied to the pervaporation (PV) separation of methanol (MeOH) /dimethyl carbonate (DMC) mixtures at 50°C. Although SiO₂? ZrO₂ membranes demonstrated a separation factor of <10, the SiO₂ porous membranes had an increased separation factor from 10–160. Silica membranes with an average pore size of 0.3 nm showed the highest permselectivity of methanol with a separation factor of 140 and a methanol flux of 180 mol/(m²h) for MeOH 50 mol% at 50°C. To characterize the surface property of SiO₂ membranes, SiO₂ powdered samples were used for an adsorption experiment of vapor (MeOH, DMC) in single and mixed systems, revealing increased MeOH selective adsorption for SiO₂ powders with hydrophilic and small pores, which was consistent with PV performance. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Synthesis and gas transport properties of novel hyperbranched polyimide–silica hybrid membranes

Physical and gas transport properties of hyperbranched polyimide (HBPI)—silica hybrid membranes prepared with a dianhydride monomer, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and triamine monomers, 1,3,5‐tris(4‐aminophenoxy)triazine (TAPOTZ), and 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), were investigated and compared with those of 6FDA‐TAPOB HBPI system synthesized from 6FDA and 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB). Glass transition and 5% weight‐loss temperatures of the 6FDA‐based HBPI–silica hybrid membranes were increased with increasing silica content. 6FDA‐TAPOTZ HBPI system, however, showed relatively low 5% weight‐loss temperatures, suggesting thermal instability of triazine‐ring in the TAPOTZ moiety. CO₂/CH₄ permselectivity of the HBPI–silica hybrid membranes were increased with increasing silica content, tending to exceed the upper bound for CO₂/CH₄ separation. This result indicated that free volume elements effective for CO₂/CH₄ separation were created by the incorporation of silica for the HBPI–silica hybrid systems. Especially, 6FDA‐TAPB HBPI system had high gas permeabilities and CO₂/CH₄ separation ability, arising from high fractional free volume and characteristic size and distribution of free volume elements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving Physical Adsorption of CO2 by Ionic Liquids‐Loaded Mesoporous Silica

CO₂ sorption capacities of the neat and silica‐supported 1‐butyl‐3‐methylimidazolium‐based ionic liquids (ILs) were measured under atmospheric pressure. The silica‐supported ILs were synthesized by the impregnation‐vaporization method and charactrized by N₂ adsorption/desorption and thermogravimeteric analysis (TGA). Evaluation of the effects of influential factors on sorption capacity demonstrated that by increase of the temperature, flow rate, and the weight percentage of ILs in sorbents, the sorption capacity decreases. Among the sorbents, [Bmim][TfO] and SiO₂‐[Bmim][BF₄](50) had the highest capacity. By increasing the IL portion in SiO₂‐[Bmim][BF₄], the selectivity for CO₂ to CH₄ could be improved. The CO₂‐rich sorbents could be easily recycled.     

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     

Pure and mixed gas permeation study of silica incorporated polyurethane-urea membrane modified by MOCA chain extender

Polyurethane-urea (PUU) nanocomposite membranes have been prepared using various loadings of silica (SiO₂) nanoparticles. A Novel PU was fabricated by a two-step bulk polymerization technique based on polycaprolactone (PCL), hexamethylene diisocyanate (HDI), and diamine chain extender, 4,4-methylenebis(2-chloroaniline) (MOCA). The FTIR spectra indicated that the extent of phase separation reduces with increasing SiO₂ content. The presence of crystal regions in the soft and hard segments was confirmed by DSC and XRD analyses. The obtained results illustrated a decrement in the gases' permeation in the presence of SiO₂ particles. By increasing the filler content up to 15 wt% and pressure of 8 bar, the gas permeation value of the CO₂, O₂, and N₂ decreased 36%, 54%, and 59%, respectively. However, the permselectivity of the CO₂/N₂ and O₂/N₂ increased considerably, 55% and 13% respectively. On the contrary, by raising the temperature, a dramatic augmentation in the permeability of all gases with a simultaneous reduction in the selectivity values of both gas pairs was revealed. Increasing the pressure led to a decrease in the permeability values of all membranes for O₂ and N₂, whereas the permeability for CO₂ increased with the pressure. Nevertheless, the selectivity values for the pair of gases increased (at a pressure of 10 bar, 1.66 and 1.17 times the neat PU for CO₂/N₂ and O₂/N₂, respectively). Furthermore, the permeability of the CO₂, O₂, and N₂ for the mixed gases was smaller than for pure ones at the same gas upstream pressure. Nonetheless, like the pure gas, the selectivity of both pair gases increased.