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     

High-flux CO2-stable oxygen transport hollow fiber membranes through surface engineering

The influences of bulk diffusion and surface exchange on oxygen transport of (La_0.6Ca_0.4)(Co_0.8Fe_0.2)O_3-δ (LCCF) hollow fiber membranes were investigated. As an outcome, two strategies for increasing the oxygen permeation were pursued. First, porous LCCF hollow fibers as support were coated with a 22 μm dense LCCF separation layer through dip coating and co-sintering. The oxygen permeation of the porous fiber with dense layer reached up to 5.10 mL min^?1 cm^-2 at 1000 °C in a 50 % CO₂ atmosphere. Second, surface etching of dense LCCF hollow fibers with H₂SO₄ was applied. The surface etching of both inner and outer surfaces leads to a permeation improvement up to 86.0 %. This finding implies that the surface exchange reaction plays a key role in oxygen transport through LCCF hollow fibers. A good long-term (>250 h) stability of the asymmetric hollow fiber in a 50 % CO₂ atmosphere was found at 900 °C.     

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     

Effects of ammonium dibasic phosphate pretreatment time on the structure and properties of PAN‐based activated carbon hollow fibers

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate aqueous solution, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of pretreatment time of PAN hollow fibers in ammonium dibasic phosphate aqueous solution on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the Brunaner–Emmett–Teller (BET) surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increases and reaches 513 m² g^?1 and 66 m² g^?1 respectively, when the dipping time of PAN hollow fibers in ammonium dibasic phosphate aqueous solution is 30 min. The adsorptions to creatinine and VB₁₂ of PAN‐ACHF are much high, reach 95% and 86% respectively, when dipping time is 30 min. The dominant pore sizes of mesopores in PAN‐ACHF range from 2 nm to 5 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2448–2453, 2006     

Preparation and characterization of poly(vinyl chloride)/polystyrene/poly(ethylene glycol) hollow‐fiber ultrafiltration membranes

Hollow‐fiber ultrafiltration (UF) membranes were prepared from blends of poly(vinyl chloride) (PVC) and polystyrene (PS) with a dry/wet phase inversion method. Poly(ethylene glycol) (PEG) and N,N‐dimethylacetamide were used as the additive and solvent, respectively. The effects of the PEG concentration in the dope solution as an additive on the cross sections and inner and outer surface morphologies, permeability, and separation performance of the hollow fibers were examined. The mean pore size, pore size distribution, and mean roughness of both the inner and outer surfaces of the produced hollow fibers were determined by atomic force microscopy. Also, the mechanical properties of the hollow‐fiber membranes were investigated. UF experiments were conducted with aqueous solutions of poly(vinyl pyrrolidone) (PVP; K‐90, M_w = 360 kDa). From the results, we found that the PVC/PS hollow‐fiber membranes had two layers with a fingerlike structure. These two layers were changed from a wide and long to a thin and short morphology with increasing PEG concentration. A novel and until now undescribed shape of the nodules in the outer surfaces, which was denoted as a sea‐waves shape, was observed. The outer and inner pore sizes both increased with increasing PEG concentration. The water permeation flux of the hollow fibers increased from 104 to 367 L m^?2 h^?1 bar^?1) at higher PEG concentrations. The PVP rejection reached the highest value at a PEG concentration of 4 wt %, whereas at higher values (from 4 to 9 wt %), the rejection decreased. The same trend was found also for the tensile stress at break, Young's modulus, and elongation at break of the hollow fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 989‐1004, 2013     

Preparation of polyvinylamine/polysulfone composite hollow‐fiber membranes and their CO2/CH4 separation performance

Fixed‐carrier composite hollow‐fiber membranes were prepared with polyvinylamine (PVAm) as the selective layer and a polysulfone ultrafiltration membrane as the substrate. The effects of the PVAm concentration in the coating solution, the number of coatings, and the crosslinking of glutaraldehyde and sulfuric acid on the CO₂ permeation rate and CO₂/CH₄ selectivity of the composite membranes were investigated. As the PVAm concentration and the number of coatings increased, the CO₂/CH₄ selectivity increased, but the CO₂ permeation rate decreased. The membranes crosslinked by glutaraldehyde or sulfuric acid possessed higher CO₂/CH₄ selectivities but lower CO₂ permeation rates. For the pure feed gas, a composite hollow‐fiber membrane coated with a 2 wt % PVAm solution two times and then crosslinked with glutaraldehyde and an acid solution in sequence had a CO₂ permeation rate of 3.99 × 10^?6 cm³ cm^?2 s^?1 cmHg^?1 and an ideal CO₂/CH₄ selectivity of 206 at a feed gas pressure of 96 cmHg and 298 K. The effect of time on the performance of the membranes was also investigated. The performance stability of the membranes was good during 6 days of testing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1885–1891, 2006     

Oxygen permeability and structural stability of a novel tantalum‐doped perovskite BaCo0.7Fe0.2Ta0.1O3−δ

Dense BaCo_0.7Fe_0.2Ta_0.1O_3?δ (BCFT) perovskite membranes were successfully synthesized by a simple solid state reaction. In situ high‐temperature X‐ray diffraction indicated the good structure stability and phase reversibility of BCFT at high temperatures. The thermal expansion coefficient (TEC) of BCFT was determined to amount 1.02 × 10^?5 K^?1, which is smaller than those of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) (1.15 × 10^?5 K^?1), SrCo_0.8Fe_0.2O_3?δ (SCF) (1.79 × 10^?5 K^?1), and BaCo_0.4Fe_0.4Zr_0.2O_3?δ (BCFZ) (1.03 × 10^?5 K^?1). It can be seen that the introduction of Ta ions into the perovskite framework could effectively lower the TEC. Thickness dependence studies of oxygen permeation through the BCFT membrane indicated that the oxygen permeation process was controlled by bulk diffusion. A membrane reactor made from BCFT was successfully operated for the partial oxidation of methane to syngas at 900°C for 400 h without failure and with the relatively high, stable oxygen permeation flux of about 16.8 ml/min cm². © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Advanced FO membranes from newly synthesized CAP polymer for wastewater reclamation through an integrated FO‐MD hybrid system

A new cellulose acetate propionate (CAP) polymer has been synthesized and used to prepare high‐performance forward osmosis (FO) membranes. With an almost equal degree of substitution of acetyl and propionyl groups, the CAP‐based dense membranes show more balanced physicochemical properties than conventional cellulose acetate (CA)‐based membranes for FO applications. The former have a lower equilibrium water content (6.6 wt. %), a lower salt diffusivity (1.6×10¹⁴ m² s^?1) and a much lower salt partition coefficient (0.013) compared with the latter. The as‐prepared and annealed CAP‐based hollow fibers have a rough surface with an average pore radius of 0.31 nm and a molecular weight cut off of 226 Da. At a transmembrane pressure of 1 bar, the dual‐layer CAP‐CA hollow fibers show a pure water permeability of 0.80 L m^?2 h^?1 bar^?1 (LMH/bar) and a rejection of 75.5% to NaCl. The CAP‐CA hollow fibers were first tested for their FO performance using 2.0 M NaCl draw solution and deionized water feed. An impressive water flux of 17.5 L m^?2 h^?1 (LMH) and a reverse salt flux of 2.5 g m^?2 h^?1 (gMH) were achieved with the draw solution running against the active CAP layer in the FO tests. The very low reverse salt flux is mainly resulting from the low salt diffusivity and salt partition coefficient of the CAP material. In a hybrid system combining FO and membrane distillation for wastewater reclamation, the newly developed hollow fibers show very encouraging results, that is, water production rate being 13–13.7 LMH, with a MgCl₂ draw solution of only 0.5 M and an operating temperature of 343 K due to the incorporation of bulky propionyl groups with balanced physiochemical properties. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1245–1254, 2013     

The effects of carbonization temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate and then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of carbonization temperature of PAN hollow fiber precursor on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based carbon hollow fiber (PAN‐CHF) and PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the surface area of the PAN‐ACHF increased very remarkably, reaching 900 m² g^?1 when carbonization is 1000°C, and the adsorption ratios to creatinine and VB₁₂ of ACHF were much higher than those of CHF, especially to VB₁₂. The different adsorption ratios to two adsorbates including creatinine and VB₁₂ reflect the number of micropores and mesopores in PAN‐ACHF. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2155–2160, 2005     

Fabrication of 6FDA‐durene polyimide asymmetric hollow fibers for gas separation

We have developed defect‐free asymmetric hexafluoro propane diandydride (6FDA) durene polyimide (6FDA‐durene) hollow fibers with a selectivity of 4.2 for O₂/N₂ and a permeance of 33.1 ×10^?6 cm³ (STP)/cm²‐s‐cmHg for O_2. These fibers were spun from a high viscosity in situ imidization dope consisting of 14.7% 6FDA‐durene in a NMP solvent and the inherent viscosities (IV) of this 6FDA‐durene polymer was 0.84 dL/g. Low IV dopes cannot produce defect‐free hollow fibers, indicating a 6FDA‐durene spinning dope with a viscosity in the region of chain entanglement seems to be essential to yield hollow fibers with minimum defects. The effects of spinning parameters such as shear rates within a spinneret and bore fluids as well as air gap on gas separation performance were investigated. Experimental data demonstrate that hollow fibers spun with NMP/H₂O as the bore liquid have higher permeances and selectivities than those spun with glycerol as the bore liquid because the former has a relatively looser inner skin structure than the latter. In addition, the selectivity of hollow fibers spun with NMP/H₂O as the bore liquid changes moderately with shear rate, while the selectivity of hollow fibers spun with glycerol are less sensitive to the change of shear rate. These distinct behaviors are mainly attributed to the different morphologies generated by different bore fluids. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2166–2173, 2001     

Facile Synthesis of Monodispersed In2O3 Hollow Spheres and Application in Photocatalysis and Gas Sensing

Monodispersed, agglomerate‐free In₂O₃ hollow spheres have been prepared via a simple synthetic route involving permeation and anchoring of In³⁺ ions with carbonyl groups of swollen commercial polymer beads in tetrachloroethylene solvent followed by thermal removal of the template cores in ambient air. The as‐synthesized hollow spheres exhibit a narrow size distribution with tunable particle size (0.5–1.2 μm) and shell thickness (62–230 nm) over the process variables examined, i.e., InCl₃ precursor concentration (4.5 × 10^?3–6.7 × 10 ^{? 2} M), reaction temperature (55°C–95°C), and reaction time (1–6 h). Kinetics calculation reveals that the formation of permeating In³⁺‐rich shell in the swollen template beads becomes energetically less favorable to proceed as the reaction time increases. This limits the maximum shell thickness attainable at the given process variables. The shell is nanoporous with a Horvath‐Kawazoe (HK) pore size of ~3 nm, which remains essentially unchanged as the process variables alter. The In₂O₃ hollow spheres with an increased Brunauer‐Emmett‐Teller (BET) surface area (up to 329 m²/g) show an improved capability in photodegradation of aqueous methylene blue (MB) dye under UV exposure as well as an increased sensitivity for CO‐gas detection. This metal‐implantation scheme is general and can be extended to the synthesis of other hollow materials in various solvent liquids.     

Preparation and characterization of BaCe0.95Tb0.05O3−α hollow fibre membranes for hydrogen permeation

BaCe_0.95Tb_0.05O_3?α (BCTb) perovskite hollow fibre membranes were fabricated by spinning the slurry mixture containing 66.67 wt% BCTb powder, 6.67 wt% polyethersulphone (PESf) and 26.67 wt% N-methyl-2-pyrrolidone (NMP) followed by sintering at elevated temperatures. The influence of sintering temperature on the membrane properties was investigated in terms of crystal phase, morphology, porosity and mechanical strength. In order to obtain gas-tight hollow fibres with sufficient mechanical strength, the sintering temperature should be controlled between 1350 and 1450 °C. Hydrogen permeation through the BCTb hollow fibre membranes was carried out between 700 and 1000 °C using 50% H₂–He mixture as feed on the shell side and N₂ as sweep gas in the fibre lumen. The measured hydrogen permeation flux through the BCTb hollow fibre membranes reached up to 0.422 μmol cm^?2 s^?1 at 1000 °C when the flow rates of the H₂–He feed and the nitrogen sweep were 40 mL min^?1 and 30 mL min^?1, respectively.     

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     

Structure and properties of PAN‐based activated carbon hollow fibers: Effect of ammonium dibasic phosphate pretreatment

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate aqueous solution, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of pretreatment concentration of ammonium dibasic phosphate aqueous solution on the microstructure, specific surface, pore size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the Brunaner‐Emmett‐Teller (BET) surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increases and reaches 513 m²g^?1 and 66 m²g^?1 respectively when the concentration of ammonium dibasic phosphate aqueous solution is 4% (wt %). The adsorptions to creatinine are much high, reach more than 90% over all the concentration of ammonium dibasic phosphate aqueous solution. The adsorptions to VB₁₂ of PAN‐ACHF reach 86% when the concentration of ammonium dibasic phosphate aqueous solution is 4% (wt %). The dominant pore sizes of mesopores in PAN‐ACHF range from 2 to 5 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nano‐engineered nickel catalysts supported on 4‐channel α‐Al2O3 hollow fibers for dry reforming of methane

A nickel (Ni) nanoparticle catalyst, supported on 4‐channel α‐Al₂O₃ hollow fibers, was synthesized by atomic layer deposition (ALD). Highly dispersed Ni nanoparticles were successfully deposited on the outside surfaces and the inside porous structures of hollow fibers. The catalyst was employed to catalyze the dry reforming of methane (DRM) reaction and showed a methane reforming rate of 2040 Lh^?1gNi^?1 at 800°C. NiAl₂O₄ spinel was formed when Ni nanoparticles were deposited on alpha‐alumina substrates by ALD, which enhanced the Ni‐support interaction. Different cycles (two, five, and ten) of Al₂O₃ ALD films were applied on the Ni/hollow fiber catalysts to further improve the interaction between the Ni nanoparticles and the hollow fiber support. Both the catalyst activity and stability were improved with the deposition of Al₂O₃ ALD films. Among the Al₂O₃ ALD coated catalysts, the catalyst with five cycles of Al₂O₃ ALD showed the best performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2625–2631, 2018     

Oxygen selective ceramic hollow fiber membranes for partial oxidation of methane

A BaCo_xFe_yZr_zO_3?δ (BCFZ) perovskite hollow fiber membrane was used to construct reactors for the partial oxidation of methane (POM) to syngas. The performance of the BCFZ fibers in the POM was studied (i) without any catalyst, (ii) with catalyst‐coated fibers, and (iii) with catalyst packed around the fibers. In addition to the performance in the POM, the stability of the BCFZ hollow fiber membranes was investigated for the different catalyst arrangements. Best stability of the BCFZ hollow fiber membrane reactor in the POM could be obtained if the reforming catalyst is placed behind the oxygen permeation zone. It was found that a direct contact of the catalyst and the fiber must be avoided which could be achieved by coating the fiber with a gold film. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Pushing the limits of high performance dual‐layer hollow fiber fabricated via I2PS process in dehydration of ethanol

The immiscibility induced phase separation (I²PS) process was introduced as a novel method to fabricate hollow fibers with exceptionally high water permeance and reasonably high water/ethanol selectivity in dehydration of ethanol by pervaporation. As a continuation of the previous work, this study discloses the mechanisms to enhance the performance of hollow fibers spun via I²PS by elucidating the material selection at the inner‐layer. Moreover, it revealed the methods to reduce mass‐transport resistance by enhancing surface porosity for both inner and outer surfaces to further improve the permeation flux of the membranes. The continuous performance test demonstrates that the fibers spun from the I²PS possess a stable dehydration performance throughout the monitored period of 300 h. A comparison with pervaporation membranes in the literatures verifies the superiority of the membranes spun via I²PS process with the highest water permeation flux of 9.5 kg/m² h and the permeate water purity of 95.8 wt % at 80°C. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3006–3018, 2013     

Effects of activation temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of activation temperature of a precursor fiber on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the BET surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increased very remarkably and reached 1422 m² g^?1 and 1234 m² g^?1, respectively, when activation temperature is 1000°C. The adsorptions to creatinine and VB₁₂ of PAN‐ACHF were much high and reached 99 and 84% respectively. In PAN‐ACHF which went through the activation at 700°C and 800°C, the micropore filling mainly occurred at low relative pressures, multimolecular layer adsorption occurred with the increasing of relative pressure, and the filling and emptying of the mesopores by capillary condensation occurred at high relative pressures. But in PAN‐ACHF which went through the activation at 900°C, a mass of mesopores resulted in the large pore filling by capillary condensation. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 nm to 5 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3778–3783, 2006     

SrCo0.9Sc0.1O3−δ perovskite hollow fibre membranes for air separation at intermediate temperatures

SrCo_0.9Sc_0.1O₃ (SCSc) perovskite powders with sub-micron particle size were synthesized by a modified Pechini method combined with a post-treatment of sintering and ball-milling. From the prepared powders, the SCSc hollow fibre membranes with asymmetric structure and gas-tight property were fabricated by spinning a polymer solution containing 58.4 wt% SCSc followed by sintering at 1200 °C for 5 h. The oxygen permeation properties of the obtained SCSc fibres were measured under air/He gradients at 500–800 °C. This showed the oxygen flux of 1 mL cm^?2 min^?1 at 750 °C and 4.41 mL cm^?2 min^?1 at 900 °C. Modeling analysis reveals that the oxygen permeation process is predominated by oxygen surface exchange kinetics with an activation energy of 95.0 kJ mol^?1. The SCSc membranes showed excellent oxygen permeation performance while exhibiting high structural and permeating stability at intermediate temperatures (500–800 °C).     

Non‐dispersive absorption of CO2 in parallel and cross‐flow membrane modules using EMISE

BACKGROUND: This paper reports an analysis of the mass transfer behaviour of CO₂ absorption in hollow fibre membrane modules in parallel and cross‐flow dispositions. The ionic liquid EMISE, 1‐ethyl‐3‐methylimidazolium ethylsulfate, is used to achieve a zero solvent emission process and the experimental results are compared with CO₂ permeation through the membrane, without solvent in the lumenside. RESULTS: Overall mass transfer coefficients K_{overall, CF} = (0.74 ± 0.02) × 10^?6 m s^?1 and K_{overall, PF} = (0.37 ± 0.018) × 10^?6 m s^?1 were obtained for cross‐flow and parallel flow, respectively. These values are one order of magnitude lower than the coefficient obtained in permeability experiments, K_{overall, PERM} = (6.16 ± 0.1) × 10^?6 m s^?1, indicating the influence of the absorption in the process. Including the specific surface and gas volume of each contactor in the analysis, a similar value of a first‐order kinetic rate constant, K_R = 2.7 × 10^?3 s^?1 is obtained, showing that the interfacial chemical reaction CO₂‐ionic liquid is the slow step in the absorption process. CONCLUSION: An interfacial chemical reaction rate constant K_R = 2.7 × 10^?3 s^?1, describes the behaviour of the CO₂ absorption in the ionic liquid EMISE using membrane contactors in parallel and cross‐flow dispositions. Copyright © 2012 Society of Chemical Industry