A CO2‐stable hollow‐fiber membrane with high hydrogen permeation flux

A Mo‐substituted lanthanum tungstate mixed proton‐electron conductor, La_5.5W_0.6Mo_0.4O_11.25?δ (LWM04), was synthesized using solid state reactions. Dense U‐shaped LWM04 hollow‐fiber membranes were successfully prepared using wet‐spinning phase‐inversion and sintering. The stability of LWM04 in a CO₂‐containing atmosphere and the permeation of hydrogen through the LWM04 hollow‐fiber membrane were investigated in detail. A high hydrogen permeation flux of 1.36 mL/min cm² was obtained for the U‐shaped LWM04 hollow‐fiber membranes at 975°C when a mixture of 80% H₂?20% He was used as the feed gas and the sweep side was humidified. Moreover, the hydrogen permeation flux did not significantly decrease over 70 h of operation when fed with a mixture containing 25% CO₂, 50% H₂, and 25% He, indicating that the LWM04 hollow‐fiber membrane has good stability under a CO₂‐containing atmosphere. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1997–2007, 2015     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

Modeling of hydrogen separation through porous YSZ hollow fiber‐supported graphene oxide membrane

In this work, hydrogen (H₂) permeation fluxes through 230 nm‐thick graphene oxide (GO) membrane deposited on porous YSZ hollow fiber were measured and correlated to an explicit H₂ permeation model. H₂ fluxes through such GO‐YSZ hollow fiber membrane increased from 4.83 × 10^?8 mol cm^?2 s^?1 to 2.11 × 10^?7 mol cm^?2 s^?1 with temperature rise from 20 to 100 °C. The activation energy of H₂ permeation was determined by the linear regression of the experimental data and was applied in the theoretical calculations. The model predictions fit well the temperature dependent and the argon sweep gas flow rate dependent H₂ fluxes data. Using the derived permeation model, the effects of vacuum pressure at lumen side and H₂ partial pressure at shell side, membrane area, and GO membrane film thickness on the membrane performance were simulated and discussed to provide insights for practical applications. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2711–2720, 2018     

The effect of ethane on the performance of commercial polyphenylene oxide and Cardo-type polyimide hollow fiber membranes in CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation applications

Impurities such as hydrogen sulfide, water vapor and heavy hydrocarbons in natural gas have considerable effects on the membrane performance. Small amounts of condensable and polymer soluble components in the feed gas cause swelling or plasticization of glassy membranes, leading to a reduction in membrane selectivity. In the present research the influence of ethane was investigated on the permeance and selectivity of two commercially available hollow fiber membranes, namely Cardo-type polyimide and PPO hollow fibers for CO₂/CH₄ separations. It was concluded that the gas mixture permeation rate was increased in the presence of C₂H₆. However, the CO₂/CH₄ separation factors remained almost the same in the presence and absence of the C₂H₆.     

Preparation and oxygen permeation of U‐shaped perovskite hollow‐fiber membranes

The oxygen permeation of dense U‐shaped perovskite hollow‐fiber membranes based on Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ prepared by a phase inversion spinning process is reported. The perovskite hollow fibers with totally dense wall were obtained with the outer diameter of 1.147 mm and the inner diameter of 0.691 mm. The dependences of the oxygen permeation on the air flow rate on the shell side, the helium flow rate on the core side, the oxygen partial pressures, and the operating temperatures were experimentally investigated. According to the Wagner theory, it follows that the oxygen transport through the U‐shaped hollow‐fiber membrane is controlled by both surface reaction and bulk diffusion at the temperature ranges of 750–950°C. High oxygen permeation flux of 3.0 ml/(min cm²) was kept for about 250 h at 950°C under the conditions of the air feed flow rate of 150 ml/min and the helium flow rate of 50 ml/min. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Partial oxidation of methane in hollow‐fiber membrane reactors based on alkaline‐earth metal‐free CO2‐tolerant oxide

The U‐shaped alkaline‐earth metal‐free CO₂‐stable oxide hollow‐fiber membranes based on (Pr_0.9La_0.1)₂(Ni_0.74Cu_0.21Ga_0.05)O_4+δ (PLNCG) are prepared by a phase‐inversion spinning process and applied successfully in the partial oxidation of methane (POM) to syngas. The effects of temperature, CH₄ concentration and flow rate of the feed air on CH₄ conversion, CO selectivity, H₂/CO ratio, and oxygen permeation flux through the PLNCG hollow‐fiber membrane are investigated in detail. The oxygen permeation flux arrives at approximately 10.5 mL/min cm² and the CO selectivity is higher than 99.5% with a CH₄ conversion of 97.0% and a H₂/CO ratio of 1.8 during 140 h steady operation. The spent hollow‐fiber membrane still maintains a dense microstructure and the Ruddlesden‐Popper K₂NiF₄‐type structure, which indicates that the U‐shaped alkaline‐earth metal‐free CO₂‐tolerant PLNCG hollow‐fiber membrane reactor can be steadily operated for POM to syngas with good performance. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3587–3595, 2014     

Modeling study of oxygen permeation through an electronically short‐circuited YSZ‐based asymmetric hollow fiber membrane

Here, oxygen fluxes through an electronically short‐circuited asymmetric Ag‐YSZ|YSZ|LSM‐YSZ hollow fiber prepared via a combined spinning and sintering route were tested and correlated to an explicit oxygen permeation model. The average oxygen permeation through such asymmetric hollow fiber with a 27 μm‐thick YSZ dense layer reached 0.52 mL (STP) cm^?2 min^?1 at 1173 K. From the model results, we can obtain the characteristic thickness, the effects of the temperature, and the effect of He sweep gas flow rate to the individual step contribution. The oxygen partial pressure variation in the permeate side, the local oxygen flux, and the three‐different resistance distribution along the axial direction of the asymmetric hollow fiber are theoretically studied; providing guidelines to further improve the membrane performance for oxygen separation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3491–3500, 2017     

Highly scalable ZIF‐based mixed‐matrix hollow fiber membranes for advanced hydrocarbon separations

ZIF‐8/6FDA‐DAM, a proven mixed‐matrix material that demonstrated remarkably enhanced C₃H₆/C₃H₈ selectivity in dense film geometry, was extended to scalable hollow fiber geometry in the current work. We successfully formed dual‐layer ZIF‐8/6FDA‐DAM mixed‐matrix hollow fiber membranes with ZIF‐8 nanoparticle loading up to 30 wt % using the conventional dry‐jet/wet‐quench fiber spinning technique. The mixed‐matrix hollow fibers showed significantly enhanced C₃H₆/C₃H₈ selectivity that was consistent with mixed‐matrix dense films. Critical variables controlling successful formation of mixed‐matrix hollow fiber membranes with desirable morphology and attractive transport properties were discussed. Furthermore, the effects of coating materials on selectivity recovery of partially defective fibers were investigated. To our best knowledge, this is the first article reporting successful formation of high‐loading mixed‐matrix hollow fiber membranes with significantly enhanced selectivity for separation of condensable olefin/paraffin mixtures. Therefore, it represents a major step in the research area of advanced mixed‐matrix membranes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2625–2635, 2014     

Design of metallic nickel hollow fiber membrane modules for pure hydrogen separation

Cost‐effective and robust nickel (Ni) membrane for H₂ separation is a promising technology to upgrade the conventional H₂ industries with improved economics and environmental benignity. In this work, Ni hollow fibers (HFs) with one closed end were fabricated and assembled into a membrane module for pure H₂ separation by applying vacuum to the permeate side. The separation behavior of the HF module was investigated both experimentally and theoretically. Results indicate that H₂ recovery can be improved significantly by changing the operation conditions (temperature or feed pressure). Ni HF is a promising membrane geometry, but the negative effect of pressure drop when H₂ passes through the lumen cannot be ignored. Under the vacuum operation mode, there is little difference in term of H₂ recovery efficiency whether the feed gas flow is controlled in countercurrent or recurrent operation. This work provides important insight to the development of superior membrane H₂ separation system. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3662–3670, 2018     

Oxygen permeation simulation of La0.8Ca0.2Fe0.95O3−δ-Ag hollow fiber membrane at different modes and flow configurations

Mixed ionic-electronic conducting La_0.8Ca_0.2Fe_0.95O_3−δ-Ag (LCF-Ag) ceramic hollow fiber membranes possess high structural stability and up to 2.24-fold higher oxygen permeation fluxes relative to LCF hollow fibers. In this work, the oxygen permeation of LCF-Ag hollow fiber membrane module is simulated under sweep gas and vacuum operation modes, whereas the kinetic parameters were obtained by fitting the experimental data with the simplified Tan–Li model. The good correlation obtained from the data regression confirmed the compatibility of the selected model on the LCF-Ag hollow fiber membrane. The simulated results revealed that the countercurrent flow configuration is generally favored in sweep gas operation given its potential of complete oxygen separation under optimized conditions. For vacuum operation, the oxygen yield is practically the same for both flow configurations at a moderate vacuum setting. At a very low vacuum pressure setting, however, cocurrent flow is preferred over countercurrent flow for maximizing the oxygen yield.     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Permeation of H2, N2, CH4, C2H6, and C3H8 through asymmetric polyetherimide hollow‐fiber membranes

Permeation properties of pure H₂, N₂, CH₄, C₂H₆, and C₃H₈ through asymmetric polyetherimide (PEI) hollow‐fiber membranes were studied as a function of pressure and temperature. The PEI asymmetric hollow‐fiber membrane was spun from a N‐methyl‐2‐pyrrolidone/ethanol solvent system via a dry‐wet phase‐inversion method, with water as the external coagulant and 50 wt % ethanol in water as the internal coagulant. The prepared asymmetric membrane exhibited sufficiently high selectivity (H₂/N₂ selectivity >50 at 25°C). H₂ permeation through the PEI hollow fiber was dominated by the solution‐diffusion mechanism in the nonporous part. For CH₄ and N₂, the transport mechanism for gas permeation was a combination of Knudsen flow and viscous flow in the porous part and solution diffusion in the nonporous part. In our analysis, operating pressure had little effect on the permeation of H₂, CH₄, and N₂. For C₂H₆ and C₃H₈, however, capillary condensation may have occurred at higher pressures, resulting in an increase in gas permeability. As far as the effect of operating temperature was concerned, H₂ permeability increased greatly with increasing temperature. Meanwhile, a slight permeability increment with increasing temperature was noted for N₂ and CH₄, whereas the permeability of C₂H₆ and C₃H₈ decreased with increasing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 698–702, 2002     

Gas permeation performance of cellulose hollow fiber membranes made from the cellulose/N‐methylmorpholine‐N‐oxide/H2O system

Cellulose hollow fiber membranes (CHFM) were prepared using a spinning solution containing N‐methylmorpholine‐N‐oxide as solvent and water as a nonsolvent additive. Water was also used as both the internal and external coagulant. It was demonstrated that the phase separation mechanism of this system was delayed demixing. The CHFM was revealed to be homogeneously dense structure after desiccation. The gas permeation properties of CO₂, N₂, CH₄, and H₂ through CHFM were investigated as a function of membrane water content and operation pressure. The water content of CHFM had crucial influence on gas permeation performance, and the permeation rates of all gases increased sharply with the increase of membrane water content. The permeation rate of CO₂ increased with the increase of operation pressure, which has no significant effect on N₂, H₂, and CH₄. At the end of this article a detailed comparison of gas permeation performance and mechanism between the CHFM and cellulose acetate flat membrane was given. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1873–1880, 2004     

Preparation and characterization of microporous polyethylene hollow fiber membranes

Microporous polyethylene (PE) hollow fiber membrane with a porosity of 43% and N₂ permeation of 4.96 cm³ (STP)/cm² s cmHg was prepared by melt‐spinning and cold‐stretching method. It was found that PE with a density higher than 0.96 g/cm³ should be used for the preparation of microporous PE hollow fiber membranes. By increasing the spin–draw ratio, both the porosity and the N₂ permeation of the hollow fiber membranes increased. Annealing the nascent hollow fiber at 115°C for 2 h was suitable for attaining membranes with good performance. By straining the hollow fiber to higher extensions, the amount and size of the micropores in the hollow fiber wall increased, and the N₂ permeation of the membranes increased accordingly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 203–210, 2002; DOI 10.1002/app.10305     

Preparation and performances of poly(phthalazinone ether sulfone ketone) hollow fiber membranes with excellent thermotolerance

The cloud points of PPESK/NMP/H₂O ternary system at different temperatures were measured by titrimetric method. The binodal lines in the ternary phase diagram of the poly(phthalazinone ether sulfone ketone (PPESK) dope system was determined, on the basis of the cloud point experimental data being linearly fitted with the semiempirical linear cloud point correlation. Furthermore, phase separation behavior during the phase inversion of PPESK membrane‐forming system was discussed in terms of the phase diagram. Then, dry–wet spinning technique was employed in manufacturing PPESK hollow fiber membranes by immersion precipitation method. The cross‐section morphologies of hollow fibers were observed by scanning electronic microscopy. Also, the effects of dope solution composition and spinning parameters, including the coagulant composition and the spinning temperature on the separation performances of fibers, were evaluated by permeability measurements. The thermotolerance of the PPESK hollow fiber membranes prepared in the work was examined for the permeation operation at different temperatures and pressure differences. The experimental results showed that pure water flux increases several fold along with the temperature increases from 20 to 80°C at different operation pressures, while the solute rejection only decreases slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 878–884, 2006     

Pervaporation of water/alcohol mixtures through chitosan/cellulose acetate composite hollow‐fiber membranes

For the purpose of separating aqueous alcohol by the use of pervaporation technique, a composite membrane of chitosan (CT) dip‐coated cellulose acetate (CA) hollow‐fiber membranes, CT‐d‐CA, was investigated. The effects of air‐gap distance in the spinning of CA hollow‐fiber membranes, chitosan concentration, and sorts of aqueous alcohol solutions on the pervaporation performances were studied. Compared with unmodified CA hollow‐fiber membrane, the CT‐d‐CA composite hollow‐fiber membrane effectively increases the permselectivity of water. The thickness of coating layer increases with an increase in chitosan concentration. As the concentration of chitosan solution increased, the permeation rate decreased and the concentration of water in the permeate increased. In addition, the effects of feed composition and feed solution temperature on the pervaporation performances were also investigated. The permeation rate and water content in permeate at 25°C for a 90 wt % aqueous isopropanol solution through the CT‐d‐CA composite hollow‐fiber membrane with a 5‐cm air‐gap distance spun, 2 wt % chitosan dip‐coated system were 169.5 g/m² h and 98.9 wt %, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1562–1568, 2004     

Dual-phase membrane reactor for hydrogen separation with high tolerance to CO2 and H2S impurities

Catalytic membrane reactors based on oxygen-permeable membranes are recently studied for hydrogen separation because their hydrogen separation rates and separation factors are comparable to those of Pd-based membranes. New membrane materials with high performance and good tolerance to CO₂ and H₂S impurities are highly desired. In this work, a new membrane material Ce_0.85Sm_0.15O_1.925–Sr₂Fe_1.5Mo_0.5O_6-δ (SDC–SFM) was prepared for hydrogen separation. It exhibits high conductivities at low oxygen partial pressures, which is benefit to electron transfer and ion diffusion. A high hydrogen separation rate of 6.6 mL cm⁻² min⁻¹ was obtained on a 0.5-mm-thick membrane coated with Ni/SDC catalyst at 900°C. The membrane reactor was operated steadily for 532 h under atmospheres containing CO₂ and H₂S impurities. Various characterizations reveal that SDC–SFM has good stability in the membrane reactor for hydrogen separation. All facts confirm that SDC–SFM is promising for hydrogen separation in practical applications. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1088–1096, 2019     

Application of polyhedral oligomeric silsesquioxane to the stabilization and performance enhancement of poly(4‐methyl‐2‐pentyne) nanocomposite membranes for natural gas conditioning

The application of octatrimethylsiloxy polyhedral oligomeric silsesquioxane (POSS) nanoparticles was investigated in the fabrication of novel reverse‐selective poly(4‐methyl‐2‐pentyne) (PMP) nanocomposite membranes for the separation of heavier hydrocarbons from methane. Generally, PMP and PMP–fumed silica (FS) nanocomposite membranes suffer severe physical aging with approximately 40% permeation flux reduction over 120 days. A straightforward strategy was introduced to suppress the physical aging of PMP and also to improve the thermal stability without compromising the selectivities and permeabilities through the incorporation of a functionalized POSS–FS binary filler system. Fourier transform infrared spectroscopy and scanning electron microscopy proved productive interactions between the fillers and polymer, with a fair compatibility between them. Thermogravimetric analysis confirmed that the thermal stability of the neat PMP was enhanced by the incorporation of the fillers into the nanocomposites. The addition of POSS and FS led to improved operational performance, such as in the permeability and selectivity, over the neat PMP. The permeation stabilities of the PMP–POSS and PMP–FS–POSS nanocomposite membranes were clearly improved over a long time (120 days). The permeation data indicated that the PMP–3 wt % POSS–20 wt % FS nanocomposite membrane is promising for C₃H₈/N₂ and C₃H₈/CH₄ separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45158.     

Enhancing oxygen permeation via multiple types of oxygen transport paths in hepta‐bore perovskite hollow fibers

The multiple types of efficient oxygen transport paths were demonstrated in high‐mechanical‐strength hepta‐bore Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ hollow fiber membranes. These types of paths play a prominent role in enhancing oxygen permeation fluxes (17.6 mL min^?1 cm^?2 at 1223 K) which greatly transcend the performance of state‐of‐the‐art Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ hollow fiber membranes, showing a good commercialization prospect. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4273–4277, 2017     

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.