Superior gas separation performance of dual-layer hollow fiber membranes with an ultrathin dense-selective layer

A concept demonstration has been made to simultaneously enhance both O₂ and CO₂ gas permeance and O₂/N₂ and CO₂/CH₄ selectivity via intelligently decoupling the effects of elongational and shear rates on dense-selective layer and optimizing spinning conditions in dual-layer hollow fiber fabrication. The dual-layer polyethersulfone hollow fiber membranes developed in this work exhibit an O₂/N₂ selectivity of 6.96 and an O₂ permeance of 4.79 GPU which corresponds to an ultrathin dense-selective layer of 918 Å at room temperature. These hollow fibers also show an impressive CO₂/CH₄ selectivity of 49.8 in the mixed gas system considering the intrinsic value of only 32 for polyethersulfone dense films. To our best knowledge, this is the first time to achieve such a high CO₂/CH₄ selectivity without incorporating any material modification. The above gas separation performance demonstrates that the optimization of dual-layer spinning conditions with balanced elongational and shear rates is an effective approach to produce superior hollow fiber membranes for oxygen enrichment and natural gas separation.     

Composite hollow fiber membranes for CO2 capture

Composite hollow fibers membranes were prepared by coating poly(phenylene oxide) (PPO) and polysulfone (PSf) hollow fibers with high molecular polyvinylamine (PVAm). Two procedures of coating hollow fibers outside and respective inside were investigated with respect to intrinsic PVAm solution properties and hollow fibers geometry and material.The influence of operating mode (sweep or vacuum) on the performances of membranes was investigated. Vacuum operating mode gave better results than using sweep because part of the sweep gas permeated into feed and induced an extra resistance to the most permeable gas the CO₂. The composite PVAm/PSf HF membranes having a 0.7–1.5 μm PVAm selective layer, showed CO₂/N₂ selectivity between 100 and 230. The selectivity was attributed to the CO₂ facilitated transport imposed by PVAm selective layer. The CO₂ permeance changed from 0.006 to 0.022 m³(STP)/(m² bar h) in direct correlation with CO₂ permeance and separation mechanism of the individual porous supports used for membrane fabrication. The multilayer PVAm/PPO membrane using as support PPO hollow fibers with a 40 nm PPO dense skin layer, surprisingly presented an increase in selectivity with the increase in CO₂ partial pressure. This trend was opposite to the facilitated transport characteristic behaviour of PVAm/porous PSf. This indicated that PVAm/PPO membrane represents a new membrane, with new properties and a hybrid mechanism, extremely stable at high pressure ratios. The CO₂/N₂ selectivity ranged between 20 and 500 and the CO₂ permeance from 0.11 to 2.3 m³(STP)/(m² bar h) depending on the operating conditions.For both PVAm/PSf and PVAm/PPO membranes, the CO₂ permeance was similar with the CO₂ permeance of uncoated hollow fiber supports, confirming that the CO₂ diffusion rate limiting step resides in the properties of the relatively thick support, not at the level of 1.2 μm thin and water swollen PVAm selective layer. A dynamic transfer of the CO₂ diffusion rate limiting step between PVAm top layer and PPO support was observed by changing the feed relative humidity (RH%). The CO₂ diffusion rate was controlled by the PPO support when using humid feed. At low feed humidity the 1.2 μm PVAm top layer becomes the CO₂ diffusion rate limiting step.     

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.     

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.     

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.     

Continuous Porous Aromatic Framework Membranes with Modifiable Sites for Optimized Gas Separation

Continuous microporous membranes are widely studied for gas separation, due to their low energy premium and strong molecular specificity. Porous aromatic frameworks (PAFs) with their exceptional stability and structural flexibility are suited to a wide range of separations. Main-stream PAF-based membranes are usually prepared with polymeric matrices, but their discrete entities and boundary defects weaken their selectivity and permeability. The synthesis of continuous PAF membranes is still a major challenge because PAFs are insoluble. Herein, we successfully synthesized a continuous PAF membrane for gas separation. Both pore size and chemistry of the PAF membrane were modified by ion-exchange, resulting in good selectivity and permeance for the gas mixtures H₂/N₂ and CO₂/N₂. The membrane with Br^? as a counter ion in the framework exhibited a H₂/N₂ selectivity of 72.7 with a H₂ permeance of 51844 gas permeation units (GPU). When the counter ions were replaced by BF₄^?, the membrane showed a CO₂ permeance of 23058 GPU, and an optimized CO₂/N₂ selectivity of 60.0. Our results show that continuous PAF membranes with modifiable pores are promising for various gas separation situations.     

The physical aging phenomenon of 6FDA‐durene polyimide hollow fiber membranes

The aging phenomenon of asymmetric 6FDA‐durene polyimide hollow fibers spun with different shear rates for gas separation has been investigated. The permeances and selectivities of different gases, such as H₂, O₂, N₂, CH_4, and CO₂, were experimentally determined as a function of time for around five months at room temperature. It was found that the gas permeation fluxes of the uncoated and silicone rubber‐coated hollow fibers decreased significantly during the first 30 days following fabrication and then slightly deteriorated thereafter. In the early stage of aging, because of different molecular orientations and skin morphologies induced by shear rates, the percentage of permeance drop for uncoated fibers increased with increasing shear rates, then decreased with increasing shear rates. The permeance of 6FDA‐durene hollow fibers coated with silicone rubber dropped more significantly than the uncoated fibers, implying that silicone rubber coating did affect the aging behavior. This might be due to the fact that silicone rubber layer hindered the molecular relaxation and tightened interface molecules between the dense selective layer and silicone rubber, thus the selectivity increased with aging. Thermal analysis data suggest two processes occurring simultaneously during the aging: one is the relaxation of shear oriented chains, and the other is the densification of chain packing through the reduction of interstitial space among chains. The former has been confirmed by an increase in CTE, while the latter was confirmed by an increase in the peak of β‐relaxation temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 765–775, 2000     

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.     

Effect of the preparation conditions on the formation of asymmetric poly(vinylidene fluoride) hollow fibre membranes with a dense skin

Integrally skinned asymmetric poly(vinylidene fluoride) hollow fibre membranes were prepared and characterized. The effects of phase inversion methods (dry-wet or wet) and spinning conditions, such as the type of solvent (NMP, DMAc), the concentration of polymer in dope solution, temperature of the external coagulation bath and the composition of the inner coagulant on the morphology and on the formation of a dense skin layer were investigated. The structure of the membranes was analyzed by scanning electron microscopy and the gas permeation properties with six different gases (He, H₂, N₂, O₂, CH₄ and CO₂) were measured at 25 °C to confirm the integrity of the selective skin layer. Under the proper conditions highly selective and permeable PVDF hollow fibre membranes were thus obtained by dry-wet spinning of a 30 wt.% PVDF solution in DMAc, using hot water (50 °C) as the external coagulant and a bore fluid of pure water as the internal coagulant. The best membrane had a selective outer skin with an effective thickness of approximately 0.2 μm. The ideal selectivity of the hollow fibres approached or even exceeded the intrinsic ideal selectivity of a dense PVDF film, for instance the selectivity for He over N₂ was 86.2 for the hollow fibre, whereas it was 83.5 for a dense PVDF reference film. DSC and FT-IR/ATR analysis indicated a higher fraction of the β-crystal phase in the selective skin and a high overall crystallinity than in the melt-processed film. The latter explains the relatively high selectivity and low permeability of the membranes. Intrinsic polymer properties make the membranes also suitable for vapour transport than for gas separation.     

Fabrication of high performance Matrimid/polysulfone dual-layer hollow fiber membranes for O2/N2 separation

Matrimid/polysulfone (PSf) dual-layer hollow fiber membranes were fabricated by using co-extrusion and dry-jet wet-spinning phase-inversion techniques. The effects of the spinning dope composition, spinneret dimension, spinneret temperature and the air gap distance on the hollow fiber membranes separation performance were studied. Aging phenomenon was also studied. After coated by 3 wt% silicon solution, the hollow fiber membranes have an O₂/N₂ selectivity of 7.55 at 25 °C, 506.625 kPa which exceeds the intrinsic value of Matrimid. The membranes have an O₂ permeance of 9.36 GPU with an apparent dense-layer thickness of 1421 Å calculated from the O₂ permeability. SEM images show the high porosity underneath the dense skin. It indicates that non-solvent addition is not necessary in the inner spinning dope to induce the macroviod formation. The binodals of the Matrimid/solvent/H₂O and PSf/solvent/H₂O indicate that the composition of the spinning dope plays an important role in the structure and the gas separation performance of the dual-layer hollow fiber membranes. The delayed demixing of the inner spinning dope may fabricate low resistance support layers in the dual-layer hollow fiber membranes.     

Tuning the Stacking Modes of Ultrathin Two-Dimensional Metal–Organic Framework Nanosheet Membranes for Highly Efficient Hydrogen Separation

Two-dimensional (2D) metal–organic framework (MOF) membranes are considered potential gas separation membranes of the next generation due to their structural diversity and geometrical functionality. However, achieving a rational structure design for a 2D MOF membrane and understanding the impact of MOF nanosheet stacking modes on membrane separation performance remain challenging tasks. Here, we report a novel kind of 2D MOF membrane based on [Cu₂Br(IN)₂]_n (IN=isonicotinato) nanosheets and propose that synergetic stacking modes of nanosheets have a significant influence on gas separation performance. The stacking of the 2D MOF nanosheets is controlled by solvent droplet dynamic behaviors at different temperatures of drop coating. Our 2D MOF nanosheet membranes exhibit high gas separation performances for H₂/CH₄ (selectivity >290 with H₂ permeance >520 GPU) and H₂/CO₂ (selectivity >190 with H₂ permeance >590 GPU) surpassing the Robeson upper bounds, paving a potential way for eco-friendly H₂ separation.     

Electropolymerization of Molecular‐Sieving Polythiophene Membranes for H2 Separation

Membrane technologies that do not rely on heat for industrial gas separation would lower global energy cost. While polymeric, inorganic, and mixed‐matrix separation membranes have been rapidly developed, the bottleneck is balancing the processability, selectivity, and permeability. Reported here is a softness adjustment of rigid networks (SARs) strategy to produce flexible, stand‐alone, and molecular‐sieving membranes by electropolymerization. Here, 14 membranes were rationally designed and synthesized and their gas separation ability and mechanical performance were studied. The separation performance of the membranes for H₂/CO₂, H₂/N₂, and H₂/CH₄ can exceed the Robeson upper bound, among which, H₂/CO₂ separation selectivity reaches 50 with 626 Barrer of H₂ permeability. The long‐term and chemical stability tests demonstrate their potential for industrial applications. This simple, scalable, and cost‐effective strategy holds promise for the design other polymers for key energy‐intensive separations.     

Defect-free asymmetric hollow fiber membranes from Torlon, a polyamide–imide polymer, for high-pressure CO2 separations

Torlon^®, a polyamide–imide polymer, was used for high-pressure CO₂ separations, as it can form inter- and intra-chain hydrogen bonding that may provide stability against plasticization. Asymmetric hollow fiber membranes with a defect-free selective skin were successfully formed from Torlon^® using a dry–wet spinning process. Dope and spinning parameters were optimized to obtain these fibers, which had CO₂/CH₄ selectivity of 44 and O₂/N₂ selectivity of 7.7. These selectivities are about 85% of the intrinsic (dense film) value of 52 for CO₂/CH₄ and 90% of the intrinsic value of 8.3 for O₂/N₂, respectively. Based on analyses presented, the reduced selectivities are attributed to substructure resistance rather than actual skin layer defects. Macrovoids, which compromise the strength of the fiber, were reduced by increasing the polymer concentration. The resulting fiber could withstand up to 2000 psi of N₂, and a CO₂ permeation study indicates that this fiber can perform selective separations under supercritical conditions of 1100 psi of CO₂ at 35 °C.     

Fabrication of Crystalline Microporous Membrane from 2D MOF Nanosheets for Gas Separation

Metal‐organic frameworks (MOFs)‐based membranes have shown great potentials as applications in gas separation. In this work, a uniform membrane based on 2D MOF Ni₃(HITP)₂ (HITP=2,3,6,7,10,11‐hexaaminotriphenylene) was fabricated on ordered macroporous AAO via the filtration method. To fabricate the membrane, we obtained the Ni₃(HITP)₂ nanosheets as building blocks via a soft‐physical exfoliation method successfully that were confirmed by AFM and TEM. We also studied the H₂, CO₂ and N₂ adsorption isotherms of Ni₃(HITP)₂ powder at room temperature, which shows Ni₃(HITP)₂ has high heats of adsorption for CO₂ and high selectivity of CO₂ over N₂. Gas permeation tests indicate that the Ni₃(HITP)₂ membrane shows high permeance and selectivity of CO₂ over N₂, as well as good selectivity of H₂ over N₂. The ideal separation factors of CO₂/N₂ and H₂/N₂ from sing‐gas permeances are 13.6 and 7.8 respectively, with CO₂ permeance of 3.15×10^?6 mol?m^?2?s^?1?Pa^?1. The membrane also showed good stability, durability and reproducibility, which are of potential interest for practical applications in the CO₂ separations.     

Pebax/TSIL blend thin film composite membranes for CO_2 separation

In this study a thin film composite (TFC) membrane with a Pebax/Task-specific ionic liquid (TSIL) blend selective layer was prepared. Defect-free Pebax/TSIL layers were coated successfully on a polysulfone ultrafiltration porous support with a polydimethylsiloxane (PDMS) gutter layer. Different parameters in the membrane preparation (e.g. concentration, coating time) were investigated and optimized. The morphology of the membranes was studied by scanning electron microscopy (SEM), while the thermal properties and chemical structures of the membrane materials were investigated by thermo-gravimetric analyzer (TGA), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The CO₂ separation performance of the membrane was evaluated using a mixed gas permeation test. Experimental results show that the incorporation of TSIL into the Pebax matrix can significantly increase both CO₂ permeance and CO₂/N₂ selectivity. With the presence of water vapor, the membrane exhibits the best CO₂/N₂ selectivity at a relative humidity of around 75%, where a CO₂ permeance of around 500 GPU and a CO₂/N₂ selectivity of 46 were documented. A further increase in the relative humidity resulted in higher CO₂ permeance but decreased CO₂/N₂ selectivity. Experiments also show that CO₂ permeance decreases with a CO₂ partial pressure increase, which is considered a characteristic in facilitated transport membranes.     

The fabrication of hollow fiber membranes with double-layer mixed-matrix materials for gas separation

The concept of fabricating hollow fibers with double-layer mixed-matrix materials using the same polymeric matrix has been demonstrated for gas separation. Polyethersulfone (PES)–beta zeolite/PES–Al₂O₃ dual-layer mixed-matrix hollow fiber membranes with enhanced separation performance have been fabricated. This study presents an innovative approach of utilizing low cost PES and Al₂O₃ to replace expensive polyimides as the supporting medium for dual-layer mixed-matrix hollow fibers and eliminating interlayer de-lamination problems. The incorporations of 20 wt% beta zeolite in the outer selective layer and 60 wt% Al₂O₃ in the inner layer coupled with spinning at high elongational draw ratios yield membranes with an O₂/N₂ selectivity of 6.89. The presence of Al₂O₃ particles enables the membrane to retain its porous substructure morphology in the course of annealing above the glass transition temperature of PES. Moreover, spinning at high elongational draw ratios results in the re-distribution of Al₂O₃ particles towards both edges of the inner layer. Not only do the permeance and selectivity of the fibers increase, but also greater mechanical properties and lower degree of shrinkages are obtained. Therefore, the combination of PES–beta zeolite and PES–Al₂O₃ nanoparticles with a reasonable draw ratio may be another promising approach to produce hollow fibers with double-layer mixed-matrix materials.     

Oriented Ultrathin π-complexation MOF Membrane for Ethylene/Ethane and Flue Gas Separations

Rational design and engineering of high-performance molecular sieve membranes towards C₂H₄/C₂H₆ and flue gas separations remain a grand challenge to date. In this study, through combining pore micro-environment engineering with meso-structure manipulation, highly c-oriented sub-100 nm-thick Cu@NH₂-MIL-125 membrane was successfully prepared. Coordinatively unsaturated Cu ions immobilized in the NH₂-MIL-125 framework enabled high-affinity π-complexation interactions with C₂H₄, resulting in an C₂H₄/C₂H₆ selectivity approaching 13.6, which was 9.4 times higher than that of pristine NH₂-MIL-125 membrane; moreover, benefiting from π-complexation interactions between CO₂ and Cu(I) sites, our membrane displayed superior CO₂/N₂ selectivity of 43.2 with CO₂ permeance of 696 GPU, which far surpassed the benchmark of other pure MOF membranes. The above multi-scale structure optimization strategy is anticipated to present opportunities for significantly enhancing the separation performance of diverse molecular sieve membranes.     

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.     

Matrimid®5218/PSf双层非对称中空纤维膜的制备及其气体分离性能研究

以商业化聚酰亚胺Matrimid®5218作为功能层材料, 聚砜作为支撑层材料, 采用共挤出法制备双层非对称中空纤维气体分离膜. 所制备的双层非对称中空纤维膜具有致密无缺陷的超薄皮层, 致密皮层厚度约为0.21 μm. 在25 ℃, 0.5 MPa下, CO2/CH4的选择性系数达51.39, CO2的渗透系数为46.29 GPU, O2/N2的选择性系数达到7.13, O2的渗透速率为6.38 GPU. 考察了温度和压力对膜的渗透系数和选择性系数的影响, 并考察了物理老化对膜性能的影响.     

Fabrication of Ultrathin Membranes Using 2D-MOF Nanosheets for Tunable Gas Separation

Two-dimensional (2D) metal-organic frameworks (MOF) nanosheets have emerged as novel membrane materials for gas separation. However, the development of ultrathin MOF membranes with tunable separation performances is still a challenge. Herein, we developed a facile GO-assisted restacking method to fabricate defect-free membranes with monolayer Zr-BTB nanosheets. Obtained ultrathin membranes ranging from 130 nm to 320 nm show tunable separation performances and exceed the 2008 Robeson upper bound by changing the amount of nanolayers in vertical stacking direction. Furthermore, a heating filtration method was used to change the restacking process of nanosheets in the horizontal direction. As a result, H₂/CO₂ selectivity can be enhanced by two times with the same membrane thickness (130 nm) and H₂ permeance is almost maintained to be 7.0×10⁻⁷ mol m⁻² s⁻¹ pa⁻¹. This method may provide a possible way to efficiently tune the gas separation performances of MOF membranes.