Carbon Molecular Sieve Membrane Preparation by Economical Coating and Pyrolysis of Porous Polymer Hollow Fibers

Dip coating and pyrolysis processes are used to create multi‐layer asymmetric carbon molecular sieve (CMS) hollow fiber membranes with excellent gas separation properties. Coating of an economical engineered support with a high‐performance polyimide to create precursor fibers with a dense skin layer reduces material cost by 25‐fold compared to monolithic precursors or ceramic supports. CMS permeation results with CO₂/CH₄ (50:50) mixed gas feed show attractive CO₂/CH₄ selectivity of 58.8 and CO₂ permeance of 310 GPU at 35 °C.     

Natural gas permeation in polyimide membranes

Polyimide membranes derived from 6FDA-DAM:DABA and 6FDA-6FpDA:DABA copolymers have been used to separate 50/50 CO₂/CH₄ mixtures and multicomponent synthetic natural gas mixtures at 35 °C and feed pressures up to 55 atm. For 6FDA-DAM:DABA 2:1 membranes the effects of thermal annealing and covalent crosslinking are decoupled with respect to effects on permeabilities and selectivity. Crosslinking at 295 °C with 1,4-butylene glycol and 1,4-cyclohexanedimethanol increases CO₂ permeabilities by factors of 4.1 and 2.4, respectively, at 20 atm feed pressure, without a loss in selectivity, relative to crosslinking at 220 °C. Thermal annealing and crosslinking also reduce CO₂ plasticization effects. Crosslinking of DABA-containing copolymers, therefore, can produce membranes with tunable transport properties that offer significantly higher performance with better plasticization-resistance than that reported in the literature for the commercial polymers Matrimid^® and cellulose acetate for CO₂ removal from natural gas mixtures. Separation of complex mixtures containing CO₂, CH₄, C₂H₆, C₃H₈, and C₄H₁₀ or toluene results in a significant decrease of the CO₂ permeability, but only a moderate decrease in the CO₂/CH₄ selectivity.     

Formation of high-performance 6FDA-2,6-DAT asymmetric composite hollow fiber membranes for CO2/CH4 separation

We report that 6FDA-2,6-DAT polyimide can be used to fabricate hollow fiber membranes with excellent performances for CO₂/CH₄ separation. In order to simplify the hollow fiber fabrication process and verify the feasibility of 6FDA-2,6-DAT hollow fiber membranes for CO₂/CH₄ separation, a new one-polymer and one-solvent spinning system (6FDA-2,6-DAT/N-methyl-pyrrolidone (NMP)) with much simpler processing conditions has been developed and the separation performance of newly developed 6FDA-2,6-DAT hollow fiber membranes has been further studied under the pure and mixed gas systems.Experimental results reveal that 6FDA-2,6-DAT asymmetric composite hollow fiber membranes have a strong tendency to be plasticized by CO₂ and suffer severely physical aging with an initial CO₂ permeance of 300 GPU drifting to 76 GPU at the steady state. However, the 6FDA-2,6-DAT asymmetric composite hollow fibers still present impressive ultimate stabilized performance with a CO₂/CH₄ selectivity of 40 and a CO₂ permeance of 59 GPU under mixed gas tests. These results manifest that 6FDA-2,6-DAT polyimide is one of promising membrane material candidates for CO₂/CH₄ separation application.     

Study on the effect of process parameters on CO2/CH4 binary gas separation performance over NH2-MIL-53(Al)/cellulose acetate hollow fiber mixed matrix membrane

The aim of current work is to study the interaction of process parameters including, temperature, CO₂ feed composition and feed pressure were towards CO₂ separation from CO₂/CH₄ binary gas mixture over hollow fiber mixed matrix membrane using design of experiment (DoE) approach. The hollow fiber mixed matrix membrane (HFMMM) containing NH₂-MIL-53(Al) filler and cellulose acetate polymer was successfully spun and fibers with outer diameter of approximately 250–290 nm were obtained. The separation results revealed that the increment of temperature from 30 °C to 50 °C reduced the CO₂/CH₄ separation factor while, increasing feed pressure from 3 bar to 15 and increment of CO₂ feed composition from 15 to 42.5 vol% increased the separation factor of HFMMM. The DoE results showed that the feed pressure was the most significant process parameter that intensely affected the CH₄ permeance, CO₂ permeance and CO₂/CH₄ separation factor. Based on the experimental results obtained, maximum CO₂ permeance of 3.82 GPU was achieved at feed pressure of 3 bar, temperature of 50 °C and CO₂ feed composition of 70 vol%. Meanwhile, minimum CH₄ permeance of 0.01 GPU was obtained at feed pressure of 15 bar and temperature of 30 °C and CO₂ feed composition of 70 vol%. Besides, maximum CO₂/CH₄ separation factor of 14.4 was achieved at feed pressure of 15 bar and temperature of 30 °C and CO₂ feed composition of 15 vol%. Overall, the study on the interaction between separation processes parameters using central composite design (CCD) coupled with response surface methodology (RSM) possesses significant importance prior to the application of NH₂-MIL-53(Al)/Cellulose Acetate HFMMM at industrial scale of natural gas purification.     

Preparation and characterization of a composite PDMS membrane on CA support

Polydimethylsiloxane (PDMS) is the most commonly used membrane material for the separation of condensable vapors from lighter gases. In this study, a composite PDMS membrane was prepared and its gas permeation properties were investigated at various upstream pressures. A microporous cellulose acetate (CA) support was initially prepared and characterized. Then, PDMS solution, containing crosslinker and catalyst, was cast over the support. Sorption and permeation of C₃H₈, CO₂, CH₄, and H₂ in the prepared composite membrane were measured. Using sorption and permeation data of gases, diffusion coefficients were calculated based on solution‐diffusion mechanism. Similar to other rubbery membranes, the prepared PDMS membrane advantageously exhibited less resistance to permeation of heavier gases, such as C₃H₈, compared to the lighter ones, such as CO₂, CH₄, and H₂. This result was attributed to the very high solubility of larger gas molecules in the hydrocarbon‐based PDMS membrane in spite of their lower diffusion coefficients relative to smaller molecules. Increasing feed pressure increased permeability, solubility, and diffusion coefficients of the heavier gases while decreased those of the lighter ones. At constant temperature (25°C), empirical linear relations were proposed for permeability, solubility, and diffusion coefficients as a function of transmembrane pressure. C₃H₈/gas solubility, diffusivity, and overall selectivities were found to increase with increasing feed pressure. Ideal selectivity values of 9, 30, and 82 for C₃H₈ over CO₂, CH₄, and H₂, respectively, at an upstream pressure of 8 atm, confirmed the outstanding separation performance of the prepared membrane. Copyright © 2009 John Wiley & Sons, Ltd.     

Upgrading low-quality natural gas with H2S- and CO2-selective polymer membranes: Part II. Process design, economics, and sensitivity study of membrane stages with recycle streams

The cost of membrane separation processes for removing CO₂ and H₂S from low-quality natural gas can be reduced for some concentration ranges of CO₂ and H₂S by utilizing concurrently two different types of polymer membranes, one with a high CO₂/CH₄ selectivity and the other with a high H₂S/CH₄ selectivity. The polymers considered in this exploratory study were 6FDA-HAB polyimide for the removal of CO₂ and [poly(ether urethane urea)] (PEUU) for the removal of H₂S. It was required that the concentrations of CO₂ and H₂S in low-quality natural gas be reduced to US pipeline specifications (≤2 mol% CO₂ and ≤4 ppm H₂S). Low-quality natural gas was simulated in this study by CH₄/CO₂/H₂S mixtures containing up to 40 mol% CO₂ and 10 mol% H₂S. Twenty-seven membrane process configurations (PCs) were examined by computer simulations and optimized in order to determine the most economical configurations. Part I of this study considered only PCs without recycle streams [J. Hao, P.A. Rice, S.A. Stern, Upgrading low-quality natural gas with H₂S- and CO₂-selective polymer membranes. Part I. Process design and economics of membrane stages without recycle streams, J. Membr. Sci. 209 (2002) 177–206]. In Part II, reported below, the study was extended to two- and three-stage PCs with various recycle options. A sensitivity analysis was also made to determine the effects of variations in feed flow rate, feed pressure, membrane module cost, and wellhead price of natural gas on process economics. The economically optimal PCs were found to be either two membrane stages connected in series with or without recycle streams or single stages without recycle, depending on feed composition and selected operating conditions. The optimal two-stage PCs with recycle streams would utilize the H₂S/CH₄-selective membranes in the first stage and either the CO₂/CH₄ or the H₂S/CH₄-selective membranes, or both, in the second stage. Three-stage membrane PCs were not found to be economically competitive under the conditions assumed in this study.     

Suppression of CO2-plasticization by semiinterpenetrating polymer network formation

CO₂-induced plasticization may significantly spoil the membrane performance in high-pressure CO₂/CH₄ separations. The polymer matrix swells upon sorption of CO₂, which accelerates the permeation of CH₄. The polymer membrane looses its selectivity. To make membranes attractive for, for example, natural gas upgrading, plasticization should be minimized. In this article we study a polymer membrane stabilization by a semiinterpenetrating polymer network (s-ipn) formation. For this purpose, the polyimide Matrimid 5218 is blended with the oligomer Thermid FA-700 and subsequently heat treated at 265°C. Homogeneous films are prepared with different Matrimid/Thermid ratios and different curing times. The stability of the modified membrane is tested with permeation experiments with pure CO₂ as well as CO₂/CH₄ gas mixtures. The original membrane shows a minimum in its permeability vs. pressure curves, but the modified membranes do not indicating suppressed plasticization. Membrane performances for CO₂/CH₄ gas mixtures showed that the plasticizing effect indeed accelerates the permeation of methane. The modified membrane clearly shows suppression of the undesired methane acceleration. It was also found that just blending Matrimid and Thermid was not sufficient to suppress plasticization. The subsequent heat treatment that results in the s-ipn was necessary to obtain a stabilized permeability. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1547–1556, 1998     

New polyimide-polyaniline hollow fibers: Synthesis, characterization and behavior in gas separation

New polyimide-polyaniline hollow fibers were produced by dissolution of the polymers in NMP and dry/wet spinning of the resulting solution in a non-solvent (H₂O). The morphology and thermal properties of the fibers, were examined by means of SEM and TGA, and FTIR spectroscopy was used for the study of their chemical structure. Permeability and selectivity measurements in different gases (He, H₂, CH₄, CO₂, O₂ and N₂) were performed in order to evaluate the performance of the membrane in gas separation applications. The results indicate that the novel membrane is a well structured hollow fiber, thermally stable up to 500°. The introduction of polyaniline into the polyimide matrix, results in a great enhancement in fiber permeability (60-600 times) possibly due to increase of the total free volume due to the introduction of shorter polyaniline molecules in the matrix, allowing larger quantities of gases to pass through the composite membrane. Perm-selectivity ratios for the composite membranes H₂/CH₄, He/N₂, H₂/N₂ and H₂/CO₂ were found lower by a factor of 6.4, 8.9, 7.7 and 1.47, respectively, compared to membranes produced using only polyimide. The opposite effect was observed for CH₄/CO₂ and N₂/CO₂ perm-selectivity ratios that showed an increase by a factor of 3.52 and 5.2, respectively. The ratio CH₄/CO₂ is of particular interest for natural gas purification purposes.     

Separation performance of polyimide composite membrane prepared by dip coating process

The effects of the preparation conditions in a dip coating process on polyimide composite membranes have been investigated. Polyimide precursor obtained from pyromellitic dianhidride (PMDA) and 4,4′-oxydianiline (ODA) was mixed with triethylamine and poly(amic acid)tri-ethylamine salt (PAA salt) was made. An asymmetric polyimide membrane (PI-2080) as a supporting membrane was dipped in a PAA salt (concentration 0–5 wt.%) methanol solution. The coating layers of PAA salt were converted to these of polyimide by annealing at 200°C for 3 h in an ordinary vacuum oven.The performance of the polyimide composite membrane was evaluated by gas permeation (N₂, O₂, CO₂, at 1 kg/cm²) and pervaporation (feed: a 95 vol.% ethanol aqueous solution at 30–60°C). The composite membranes prepared using a coating solution of 5 wt.% PAA salt showed the CO₂/N₂ selectivity of over 25 on gas permeation, and separation factor α (H₂O/EtOH) of over 800 with a total flux of 0.21 kg/m² h on pervaporation.     

Gas transport properties of asymmetric polyimide membranes prepared by plasma‐based ion implantation

In this study, we report the gas permeance and selectivity of the asymmetric polyimide membrane prepared by plasma‐based ion implantation (PBII). The asymmetric polyimide membranes were prepared using a dry–wet phase inversion process, and the surface skin layer on the membrane was implantated by He ions at 2.5 keV. The asymmetric membranes treated by PBII were measured using a high vacuum apparatus with a Baratron absolute pressure gauge at 76 cmHg and 35°C. The (O₂/N₂) and (CO₂/CH₄) selectivities in the He⁺‐implanted asymmetric membrane at 60 sec resulted in 1.5 and 1.8 time increases, respectively, when compared to those of the asymmetric membrane before PBII. On the other hand, the O₂ and CO₂ permeances in the asymmetric membrane after PBII decreased with an increase in the He⁺ treatment time. In this paper, we addressed, for the first time, the gas permeation behavior of the asymmetric polyimide membranes prepared by PBII. Copyright © 2009 John Wiley & Sons, Ltd.     

Comparative study between a CMS membrane and a CMS adsorbent: Part I—Morphology, adsorption equilibrium and kinetics

This paper presents a comparative study between a carbon molecular sieve (CMS) membrane and a commercial CMS adsorbent; these materials are suited for selective gas permeation and adsorption-based gas separations, respectively. The purpose of this analysis is to better understand the mass transport mechanism in CMS membranes and how it is related to the material's structure. The structural characterization based on the adsorption of CO₂ at 0 °C revealed that the adsorbent has a greater micropore volume, a smaller mean pore width and a micropore size distribution shifted to the left, when compared to the membrane. This translates into a lower adsorption capacity of the membrane towards N₂, Ar, CO₂ and O₂ at 29.5 °C and 0–7 bar. The adsorption kinetics were also studied and the pressure-dependence of the apparent time constants established; different models were used to predict the experimental results, emphasizing the very important role of the ultramicroporosity on the properties of the materials. The CMS membrane exhibited a pore blockage effect when permeating O₂ and CO₂. Further morphologic characterization was performed by SEM, X-ray diffraction and mercury porosimetry.     

Separation of CO2 and CH4 by a DDR membrane

The permeation of CO₂ and CH₄ and their binary mixtures through a DDR membrane has been investigated over a wide range of temperatures and pressures. The synthesized DDR membrane exhibits a high permeance and maintains a very high selectivity for CO₂. At a total pressure of 101 kPa, the highest selectivity for CO₂ in a 50∶50 feed mixture was found to be over 4000 at 225 K. This is ascribed to the higher adsorption affinity, as well as to the higher mobility for the smaller CO₂ molecules in the zeolite, preventing the bypassing of the CH₄ through the membrane. An engineering model, based on the generalized Maxwell-Stefan equations, has been used to interpret the transport phenomena in the membrane. The feasibility of DDR membranes as applied to CO₂ removal from natural gas or biogas is anticipated.     

Fabricating pyridinic N-B sites in porous carbon as efficient metal-free electrocatalyst in conversion CO2 into CH4

Electrochemical reduction of CO₂ (CO₂RR) to value-added chemicals is an attractive strategy for greenhouse gas mitigation and carbon recycle. Carbon material is one of most promising electrocatalysts but its product selectivity is limited by few modulating approaches for active sites. Herein, the predominant pyridinic N-B sites (accounting for 80% to all N species) are fabricated in hierarchically porous structure of graphene nanoribbons/amorphous carbon. The graphene nanoribbons and porous structure can accelerate electron and ion/gas transport during CO₂RR, respectively. This carbon electrocatalyst exhibits excellent selectivity toward CO₂ reduction to CH₄ with the faradaic efficiency of 68% at −0.50 V vs. RHE. As demonstrated by density functional theory, a proper adsorbed energy of *CO and *CH₂O are generated on the pyridinic N-B site resulting into high CH₄ selectivity. Therefore, this study provides a novel method to modulate active sites of carbon-based electrocatalyst to obtain high CH₄ selectivity.     

Multicomponent gas separation by an asymmetric permeator containing two different membranes

A numerical analysis of an asymmetric permeator containing two different kinds of membranes and capable of separating a ternary feed gas mixture into three product streams has been carried out. For negligible axial pressure drops in the gas streams, equations have been developed and calculation methods illustrated for four flow patterns: cross, parallel, countercurrent and perfectly mixed. The main parameters used in the analysis are pressure ratios, the ratio of the two membrane areas and the permeabilities. Results have been presented for a 50% H₂10% CO₂40% N₂ feed with a permeator having one cellulose acetate (CA) type membrane and one silicone membrane. For both permeate streams, countercurrent achieves highest permeate qualities and requires least membrane area amongst all four flow patterns. The presence of a silicone membrane produces a richer H₂ permeate from the CA membrane than that from a CA-membrane-alone configuration. Simultaneously, an enriched CO₂ permeate is obtained from the silicone membrane. Under the ideal condition of zero pressure ratios, the asymmetric permeator has also been evaluated against the series configuration of a permeator containing a CA membrane only followed by a permeator containing only a silicone (S) membrane. The asymmetric configuration usually performs better than this series configuration for the chosen range of parameters.     

Effect of molecular weight on gas selectivity of oriented thin polyimide membrane

In this study, we focused on effect of the molecular weight of polyimide on the gas selectivity of the asymmetric membrane with an oriented surface skin layer prepared at different shear stresses. Asymmetric polyimide membranes, which have a defect‐free surface skin layer supported by a porous substructure, were prepared by a dry/wet phase inversion process. The structures of the asymmetric polyimides consisted of a thin skin layer and a porous substructure characterized by the presence of finger‐voids. The gas selectivities of the asymmetric polyimide membranes increased with an increase in the shear rate or a decrease in the molecular weight, indicating that the oriented polyimide structure in the surface skin layer provided a high size and shape discrimination between the gas molecules. The selectivity values of (O₂/N₂) and (CO₂/CH₄) in the asymmetric polyimide membrane prepared from the 7.2 × 10⁴ molecular weight material at 1000 sec^?1 shear rate were 12 and 143, respectively. Copyright © 2003 John Wiley & Sons, Ltd.     

ZIF-8 based polysulfone hollow fiber membranes for natural gas purification

Mixed matrix membranes (MMMs) have received worldwide attention for natural gas purification due to their superior performance in terms of permeability and selectivity. The zeolitic imidazole framework-8 (ZIF-8) blended polysulfone (PSf) membranes have been fabricated for natural gas purification. ZIF-8 was selected due to its low cost, remarkable thermal and chemical stabilities, and tunable microporous structure. The neat PSf hollow fiber membrane and mixed matrix hollow fiber membranes incorporated with the various ZIF-8 loadings up to 1.25% were fabricated. The prepared membranes were evaluated using field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and gas separation performance. The low loading of ZIF-8 nanoparticles to the MMM improved thermal stability and glass transition temperature and yielded low surface roughness. MMMs were tested using pure gases with a significant improvement of 36% in CO₂ permeability and 28% in CO₂/CH₄ selectivity compared to the neat membrane. However, the high ZIF-8 loading reduced the separation performances. Moreover, CO₂/CH₄ selectivity decreased at elevated pressure (8 and 10 bar) due to CO₂-induced plasticization. Previously, the incorporation of ZIF-8 particles has primarily been subjected to the fabrication of flat sheet membranes, whereas this work focused on hollow fiber membranes which are rarely investigated. Hence, the promising results obtained at low feed pressure in this study demonstrated the potential of ZIF-8 based hollow fiber membrane for natural gas purification.     

Reforming of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Gliding Arc System: Effect of Gas Components in Natural Gas

The objective of the present work was to study the reforming of simulated natural gas via the nonthermal plasma process with the focus on the production of hydrogen and higher hydrocarbons. The reforming of simulated natural gas was conducted in an alternating current (AC) gliding arc reactor under ambient conditions. The feed composition of the simulated natural gas contained a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20. To investigate the effects of all gaseous hydrocarbons and CO₂ present in the natural gas, the plasma reactor was operated with different feed compositions: pure CH₄, CH₄/He, CH₄/C₂H₆/He, CH₄/C₂H₆/C₃H₈/He and CH₄/C₂H₆/C₃H₈/CO₂. The results showed that the addition of gas components to the feed strongly influenced the reaction performance and the plasma stability. In comparisons among all the studied feed systems, both hydrogen and C₂ hydrocarbon yields were found to depend on the feed gas composition in the following order: CH₄/C₂H₆/C₃H₈/CO₂ > CH₄/C₂H₆/C₃H₈/He > CH₄/C₂H₆/He > CH₄/He > CH₄. The maximum yields of hydrogen and C₂ products of approximately 35% and 42%, respectively, were achieved in the CH₄/C₂H₆/C₃H₈/CO₂ feed system. In terms of energy consumption for producing hydrogen, the feed system of the CH₄/C₂H₆/C₃H₈/CO₂ mixture required the lowest input energy, in the range of 3.58 × 10⁻¹⁸–4.14 × 10⁻¹⁸ W s (22.35–25.82 eV) per molecule of produced hydrogen.     

Preparation of CO_2 selective composite membranes using Pebax/CuBTC/PEG-ran-PPG ternary system

Three phase Pebax~? MH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) with those of PPG(high permeability, amorphous) have been combined with superior properties of mixed matrix membrane(MMMs). The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by CO_2 and CH_4adsorption test. Statistically based experimental design(central composite design, CCD) was applied to analyze and optimize the effect of PEG-ran-PPG(10–50 wt%) and CuBTC(0–20 wt%) mass contents on the CO_2 permeance and CO_2/CH_4 ideal selectivity. Based on the regression coefficients of the obtained models, the CO_2 permeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO_2/CH_4 ideal selectivity. Under the optimum conditions(PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%), nearly 620% increase in the CO_2 permeance and43% enhancement in the CO_2/CH_4 ideal selectivity was observed compared to the neat Pebax. The effect of pressure(3, 9 and 15 bar) on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of CO_2 in the membranes resulted in the enhancement of CO_2 permeability with increase in gas pressure.     

Preparation of carbon molecular sieves from palm shell: effect of benzene deposition conditions

Application of carbon molecular sieve (CMS) for gas separation has been found much attention recently. In this work, CMS was prepared from locally available palm shell through carbonization, steam activation and carbon vapour deposition (CVD) technique. After carbonization step, the char produced was subjected to steam activation at various activation times. The activated carbon obtained at 53.2% burn-off, which contain the highest amount of micropore volume was further used in CVD step by using benzene vapour at various deposition conditions. The performance of CMSs produced was examined by assessing the adsorption kinetics of O₂, N₂, CO₂ and CH₄ gases. All CMS samples showed a small N₂ and CH₄ uptake compared to the O₂ and CO₂. The suitable conditions for CVD were found at 800°C, 30 min and 30 vol% benzene of deposition temperature, time and benzene concentration, respectively. At this point the O₂/N₂ and CO₂/CH₄ uptake ratios arrived 7.1 and 16.0, respectively.     

Fabrication of multi-layer composite hollow fiber membranes for gas separation

Using multilayer composite hollow fiber membranes consisting of a sealing layer (silicone rubber), a selective layer (poly(4-vinylpyridine)), and a support substrate (polysulfone), we have determined the key parameters for fabricating high-performance multilayer hollow fiber composite membranes for gas separation. Surface roughness and surface porosity of the support substrate play two crucial roles in successful membrane fabrication. Substrates with smooth surfaces tend to reduce defects in the selective layer to yield composite membranes of better separation performance. Substrates with a high surface porosity can enhance the permeance of composite membranes. However, SEM micrographs show that, when preparing an asymmetric microporous membrane substrate using a phase-inversion process, the higher the surface porosity, the greater the surface roughness. How to optimize and compromise the effect of both factors with respect to permselectivity is a critical issue for the selection of support substrates to fabricate high-performance multilayer composite membranes. For a highly permeable support substrate, pre-wetting shows no significant improvement in membrane performance. Composite hollow fiber membranes made from a composition of silicone rubber/0.1–0.5 wt% poly(4-vinylpyridine)/25 wt% polysulfone show impressive separation performance. Gas permeances of around 100 GPU for H₂, 40 GPU for CO₂, and 8 GPU for O₂ with selectivities of around 100 for H₂/N₂, 50 for CO₂/CH₄, and 7 for O₂/N₂ were obtained.