Ultra-thin skin carbon hollow fiber membranes for sustainable molecular separations

A transformative platform is reported to derive ultra-thin carbon molecular sieve (CMS) hollow fiber membranes from dual-layer precursor hollow fibers with independently tuned skin layer and substrate properties. These ultra-thin CMS hollow fiber membranes show attractive CO₂/CH₄ separation factors and excellent CO₂ permeances up to ~1,400% higher than state-of-the-art asymmetric CMS hollow fiber membranes. They provide a unique combination of permeance and selectivity competitive with zeolite membranes, but with much higher membrane packing density and potentially much lower costs.     

Physical aging in carbon molecular sieve membranes

This paper considers physical aging in carbon molecular sieve (CMS) membranes. Moreover, the performance of stabilized membranes under practical operating conditions is discussed. Physical aging has been studied extensively in glassy polymers, but aging in CMS membranes has previously focused primarily on adsorption: either chemisorption of oxygen, or physical adsorption of water and organics in the pore structures. Experimentally, in this study, for the samples considered, all of the above adsorption-induced aging mechanisms were excluded as significant factors through thoughtful experimental design. Physical aging appears to be the primary cause for rapid changes of transport properties in early stages after membrane fabrication for samples derived from high fractional free volume precursors. The CMS pores are believed to age analogously to the “unrelaxed free volume” in glassy polymers. Over time, these pores tend to shrink in order to achieve thermodynamically more stable states. Results of sorption tests in CMS also support the above hypothesis. The significance of physical aging phenomena on membrane testing protocols, structural tailoring, and performance evaluation are discussed. A long term permeation test demonstrated excellent stability of stabilized CMS membranes under realistic conditions.     

Improved microstructure of asymmetric niobium pentoxide hollow fiber membranes

Asymmetric niobium pentoxide (Nb₂O₅) hollow fiber membranes were prepared by the phase inversion and sintering process at temperatures ranging from 1000 to 1350°C. The effects of extrusion parameters on the morphology and properties of the produced membranes were systematically explored. Asymmetric hollow fibers with regular inner contour were obtained at extrusion flow rates of 15 and 25 ml min⁻¹ of ceramic suspension and internal coagulant, respectively. Hollow fibers sintered at temperatures greater than 1200°C presented modifications in the morphology of Nb₂O₅ grains, which were also evidenced by X-ray diffraction and Raman analyses. Hollow fibers produced with an air gap of 50 mm presented a dense outer sponge-like layer and micro-voids formed from the inner surface. These hollow fibers sintered at 1200°C presented suitable bending resistance and water permeability (24.2 ± 0.60 MPa and 3.00 ± 0.01 L h^-1 m^-2 kPa^-1, respectively). The outer sponge like layer was mitigated when the fibers were produced without air-gap.     

炭分子筛膜的制备与改性

炭分子筛膜足近年来发展起来的高效、新型气体分离膜,具有良好的气体分离选择性,高的热和化学稳定性,但其气体分离选择性与气体渗透通量却不能同时达到很高的要求.综述了炭分子筛膜的制备材料,重点讨论了化学方法和物理方法对制备炭膜的前驱体进行改性,展望了炭分子筛膜的未来发展方向.     

Tailoring the morphology of self-assembled block copolymer hollow fiber membranes

Isoporous asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) hollow fiber membranes were successfully made by a dry-jet wet spinning process. Well-defined nanometer-scale pores around 20–40 nm in diameter were tailored on the top surface of the fiber above a non-ordered macroporous layer by combining block copolymer self-assembly and non-solvent induced phase separation (SNIPS). Uniformity of the surface-assembled pores and fiber cross-section morphology was improved by adjusting the solution concentration, solvent composition as well as some important spinning parameters such as bore fluid flow rate, polymer solution flow rate and air gap distance between the spinneret and the precipitation bath. The formation of the well-organized self-assembled pores is a result of the interplay of fast relaxation of the shear-induced oriented block copolymer chains, the rapid evaporation of the solvent mixture on the outer surface and solvent extraction into the bore liquid on the lumen side, and gravity force during spinning. Structural features of the block copolymer solutions were investigated by small-angle X-ray scattering (SAXS) and rheological properties of the solutions were examined as well. The scattering patterns of the optimal solutions for membrane formation indicate a disordered phase which is very close to the disorder-order transition. The nanostructured surface and cross-section morphology of the membranes were characterized by scanning electron microscopy (SEM). The water flux of the membranes was measured and gas permeation was examined to test the pressure stability of the hollow fibers.     

气体分离用管状炭分子筛膜

以无机陶瓷管为支撑体、热塑性酚醛树脂为原料,经高温炭化制备了炭分子筛膜。用低温N2吸附的方法测定了炭分子筛膜的比表面积,用扫描电子显微镜对膜的形貌和厚度进行了表征。考察了膜的气体透过率以及气体的理想选择性随温度的变化关系:H2、CO2、O2、N2和CH4的透过率随温度的升高而增大;理想选择性α(H2/N2)、α(CO2/N2)、α(CO2/CH4)随温度的升高而减小,而α(O2/N2)随温度的升高先增大后减小,在90℃左右气体选择性达到最大。最后由阿累尼乌斯公式计算了气体透过炭分子筛膜的活化能,进一步说明气体透过机理为活化扩散。     

Composite phenolic resin-based carbon molecular sieve membranes for gas separation

Composite carbon molecular sieve membranes (c-CMSM) were prepared from phenolic resin loaded with boehmite by a single dipping–drying–pyrolysis step. The composite membrane was analyzed by scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, mercury porosimetry, CO₂ adsorption and permeation experiments. It was produced a 2 μm thick composite uniform layer on top of a α-Al₂O₃ support. The composite top layer exhibited nanowires of Al₂O₃ 1–2 nm thick and 10–30 nm long well dispersed in a microporous carbon matrix. The micropores network accounted for 63% of the total pore volume (DR isotherm). The c-CMSM exhibited ideal O₂/N₂ and C₃H₆/C₃H₈ permselectivities of 5 and 15, respectively. The performance of the c-CMSM for pair C₃H₆/C₃H₈ was above the upper bound curve for polymeric membranes, making it a promising vehicle for olefin purification.     

Preparation of carbon hollow fiber membranes by pyrolysis of polyetherimide

The preparation of carbon membranes by pyrolysis of polyetherimide hollow fibers and the influence of process variables on the final membrane morphology using a statistical experimental design are described in this work. The characterization of polymers and membranes was carried out by thermal analysis and scanning electron microscopy (SEM). The carbonization process was accompanied by mass spectroscopy to monitor the products formed. Similar to carbonization of others polymers, H₂O, CO₂ and CO evolution from 420 to 680 °C, and hydrogen evolution from 450 to 800 °C, indicate the formation of crosslinking of polymeric chains and formation of a graphite-like structure. These experiments permitted the production of thermostable carbon hollow fibers and selection of best treatment conditions. The extent of membrane exposure under oxidizing atmosphere and the maximum temperature of stabilization were decisive in the final membrane morphologic characteristics and properties. When the stabilization temperature was above 500 °C an intensive degradation of the fiber was observed. An initial exposure to an oxidizing atmosphere seems to be fundamental in order to control the final membrane properties. In this atmosphere, heating rates as low as 1 °C min⁻¹ during stabilization reduce cracks in the surface of final membranes.     

Interfacial resistance of dual-layer asymmetric hollow fiber pervaporation membranes formed by co-extrusion

Interface is critical for dual-layer membranes fabricated by co-extrusion and dry-jet wet spinning. In this work, for the first time, the importance of interface structure in overall membrane transport property was revealed by using Polysulfone (outer layer)/Matrimid (inner) dual-layer hollow fibers as a demonstration system. Due to the dope formulations of the two layers, dense skins came into formation at the shell side of Matrimid inner layer facing the interface. The Matrimid inner layer obtained from the dual-layer hollow fiber with the thinnest Polysulfone outer layer exhibited a flux around 1.0 × 10⁻³ kg/m²-s and a separation factor of ~800 in tert-butanol dehydration (feed flow rate 30 L/h, temperature 80 °C, permeate pressure 2 mbar, the same for the other tests). An estimation based on resistance model clearly indicated the dominance of Matrimid inner layer in the overall mass transfer of corresponding dual-layer membrane. As for hollow fibers with the thickest Polysulfone outer layer, the bulk substrate comprising the interfacial dense skin of Matrimid inner layer also displayed significant resistance and appreciable selectivity. Conclusively, the function of interface should not be ignored. The rule for the evolution of interface structure requires further exploration for fully understanding and utilizing the composite membrane by co-extrusion and phase inversion approach.     

Composite hollow fiber membranes

Composite polysulfone hollow fibers consisting of a polysulfone porous substrate coated with crosslinked polyethyleneimine (PEI) or furan resin are reported. These composite hollow fibers are analogous to the flat-sheet composite membranes known as NS-100 and NS-200. The surface structure of the porous substrate was rigorously studied before and after coating. Scanning electron microscope observations and reverse osmosis transport studies showed that the support fiber must have surface pore diameters of less than 0.2 μm to obtain a durable composite hollow fiber membrane. The curing process would normally follow in situ condensation of the PEI or the cationic polymerization of the furfuryl alcohol. However, since both the dense layer and surface of the porous substrate contract when exposed to the curing temperature (110–150°C), it was found to be profitable to cure the hollow fiber before applying the coating. When tested in a reverse osmosis rig, PEI/TDI-coated polysulfone hollow fiber bundles displayed 98% salt rejection and a flux of 5–7 gfd for a feed solution of 10,000 ppm NaCl at a hydraulic pressure of 400 psi. A new method of depositing furan resin on the polysulfone hollow fiber is described. The furfuryl alcohol is instantaneously polymerized by exposing the alcohol-soaked fiber to a 60% solution of concentrated sulfuric acid. It has been demonstrated that in such a polymerization procedure a dense, semipermeable layer is formed on top of the porous substrate; the resulting composite hollow fiber membrane yields salt rejections higher than 98% when tested under the above reverse osmosis conditions.     

Toluene and n-heptane sorption in Matrimid asymmetric hollow fiber membranes

Equilibrium and transient sorption isotherms were obtained for toluene and n-heptane in both annealed and non-annealed Matrimid^® asymmetric hollow fiber membranes at 35 °C. Equilibrium sorption follows the dual mode model except for toluene sorption into annealed fibers above a pressure of 0.5 psia. Except at the highest toluene exposure pressure, the equilibrium uptake of penetrant in annealed fibers was signigicantly less than in non-annealed fibers at a given pressure due to the significant reduction of excess free volume. Changes in the dual mode model parameters for the annealed samples may reflect not only reductions in sample free volume, but also charge transfer formation. The Berens-Hopfenberg model successfully describes all of the various transient sorption behaviors observed for toluene and n-heptane in Matrimid^® with a significant relaxation-controlled contribution to the overall mass uptake over much of the experimental range explored. Purely diffusion-controlled (Fickian) uptake was seen only for toluene sorption in annealed fibers for a change in activity from 0 to 0.05, while purely relaxation-controlled (non-Fickian) uptake was observed for n-heptane sorption in non-annealed fibers for a change in activity from 0 to 0.09. A reduced value of D_A/L², the effective Fickian diffusion time, in non-annealed fibers for toluene at a low activity level provides evidence of antiplasticization, while at intermediate to high activity, the value of D_A/L² increases with activity for all of the systems studied in this work indicating plasticization.     

镍基非对称中空纤维膜用于乙醇自热重整制氢

采用纺丝-烧结技术制备了具有内表面致密皮层的外支撑式金属镍非对称中空纤维膜,并用于乙醇自热重整（EATR）制氢,研究了温度、进料流速、吹扫气流速、水醇比（S/C）以及氧醇比（O₂/C）等操作条件对膜制氢性能的影响。结果表明,金属镍非对称中空纤维膜既具有优异的EATR催化活性,又有良好的透氢性能。在500～1000℃、S/C=4、O₂/C=0.8的条件下乙醇可完全转化,H₂产率和H₂渗透通量可分别达到81.59%和13.99 mmol/（m²·s）,增加进料中氧气含量可显著抑制膜表面积炭,但同时也会降低氢气产率和一氧化碳选择性。     

Separation of carbon dioxide by asymmetric hollow fiber membrane of cellulose triacetate

Permeation behavior of pure CO₂, O₂, and N₂ and separation characteristics of CO₂–air mixtures were examined using hollow fiber modules of asymmetric cellulose triacetate membrane at 30°C. The ideal separation factor for CO₂ relative to N₂ ranged from 21 to 24. Permeation behavior for pure CO₂ was interpreted in terms of the total immobilization model, i.e., a limiting case of the dual-mode mobility model for glassy polymer, where the diffusion coefficient for Henry's law mode is not assumed to be constant and depends on gas pressure via a modified free-volume model. Based on pure gas permeabilities to CO₂, O₂, and N₂, simulation for the separation of CO₂–air mixtures was made using a counter-current plug flow model, and the result fitted the corresponding experimental data fairly well. Membrane plasticization induced by CO₂ had negligible effect on permeation to mixture of CO₂ and air in the range of CO₂ composition up to 50% and upstream total pressure up to 1.5 MPa.     

Thermo-responsive mixed-matrix hollow fiber membranes

Up to date, preparation of thermo-responsive mixed-matrix membranes (MMM) has only be described as small scale flat membranes or multi-step processes for hollow fiber membranes. In this work, the development of thermo-responsive MMM hollow fibers composed of polyethersulfone as membrane polymer and poly(N-isopropylacrylamide) (PNIPAM) microgel particles via the wet spinning process is presented. PNIPAM particles are synthesized with (NP-S, z_{avg 20°C} = 105 nm) and without (NP-L, z_{avg 20°C} = 250 nm) sodium dodecyl sulfate and their thermo-responsive behavior is characterized by dynamic light scattering. Particle size (NP-S, NP-L), particle content (10%, 15%) and the extrusion pressure in the wet spinning process (1.0–3.0 bar) are investigated as experimental parameters. Reversible thermo-responsive behavior of the hollow fibers is demonstrated by water permeability measurements at different temperatures (20 and 50°C). The largest switching factors (R) are observed for the hollow fibers containing NP-L. For 15% NP-L and 1 bar extrusion pressure, water permeances between 0.5 and 6.0 L m⁻² h⁻¹ bar⁻¹ are observed, corresponding to R = 12 and a dextran (500 kDa) rejection of 91% at 25°C.     

炭分子筛的表征

炭分子筛是浓缩煤层气变压吸附机组的关键材料,性能的好坏直接影响变压吸附机组的性能。通过在77 K下N2的吸脱附等温线对炭分子筛的比表面积、孔径分布进行测定,通过吸附试验对炭分子筛吸附N2,O2,CO2,CH4,H2的能力及N2和CH4在炭分子筛上的吸附速度进行比较,以确定不同炭分子筛分离气体的能力。     

Characterization of crosslinked hollow fiber membranes

As the applications for polymeric membranes expand, new challenges arise. One of the largest of these challenges is the plasticization caused by strongly swelling penetrants such as carbon dioxide at elevated pressures. A considerable amount of material research has investigated crosslinking of dense film membranes to increase plasticization resistance. This paper extends such materials research to include more practically relevant asymmetric hollow fibers. Crosslinkable polyimide fibers were spun and an ester crosslinking reaction was studied using chemical and spectroscopic techniques to characterize the extent of crosslinking and to relate the effect of the reaction on fiber stability. CO₂ permeance and CO₂/CH₄ selectivity were studied at a variety of pressures and temperatures over time to yield indications of real-world separation performance.