Hollow Fiber Membrane Research Articles

Enhanced water purification performance of composite PVA–ZnO–Al2O3 hollow fiber membrane: A breakthrough approach for high-temperature stability, low-pressure water separation

This work describes the development of a composite Al2O3 hollow fiber combined with multiple-layer ZnO nanoparticles and PVA polymer as the active side for low-pressure saltwater purification. The composite membrane was evaluated with an active layer-facing salt solution, and slight suction condition was applied to the permeate inside the membrane lumen. Results show that varying nanoparticle layers to tune the porosity of the composite membrane influenced its morphology, porosity, and hydrophilicity. The effect of porosity tuning on the membrane characteristics and desalination performance was investigated. A salt rejection rate of >90 % was recorded for all 5 % PVA–ZnO–Al2O3 hollow fiber membranes with the highest salt rejection of 96.34 % and the water flux of 15.49 kg·m−2·h−1. The membrane was further tested with untreated natural seawater to demonstrate its ability to withstand continuous operation. The membrane has acceptable chemical stability when exposed to untreated natural seawater. The optimal PVA–ZnO–Al2O3 hollow fiber membrane exhibited efficient water phase change transfer and high salt rejection, making it a promising candidate for seawater purification.

Spatial variability of cake layer in membrane fouling of full-scale MBR: New insights and implications

The spatial variability of the cake layer formed on the hollow fiber membranes during the operation of a full-scale membrane bioreactor (MBR) has been thoroughly investigated, samples from the bulk phase of the reactor and cakes formed on the membrane surface with different locations (i.e., inner layer of the cake (Cake-I), central layer of the cake (Cake-C), and outer layer of the cake (Cake-O)) were collected. The results showed that the viscous nature of proteins, the main component of extracellular polymeric substances (EPS),as well as the hydrophobicity of the protein secondary structure, were factors that led to variations in particle size (Cake-I = 566 μm > Cake-C = 283 μm > Cake-O = 92.2 μm > Bulk sludge = 59.7 μm) and total interaction energy (Cake-I = −216.39 × 104 KT > Cake-C = −68.35 × 104 KT > Cake-O = −30.42 × 104 KT > Bulk sludge = −30.08 × 104 KT) between the spatially varying cake layers. Numerous filamentous bacteria were found in the MBR, and genes related to membrane plugging processes (such as polysaccharide synthesis, surface attachment, and amino acid degradation) of the microbial community composition were regulated within the cake layers. These new insights could be beneficial to developing fouling control and membrane cleaning strategies.

Enhancement of oxygen flux through Nb-doped La0.4Sr0.6FeO3-δ ceramic hollow fiber membranes by Fe exsolution

In recent years, numerous studies have focused on the use of mixed ionic-electronic conducting oxides for coupled oxygen separation and catalytic reactions in membrane reactors. A promising strategy for the efficient fabrication of oxygen separation membranes involves modification of the membrane surface via exsolved metal nanoparticles decoration. Here, we present a detailed characterization of the structural and transport properties of a novel membrane material La0.4Sr0.6Fe0.95Nb0.05O3−δ (LSFNb5). The exsolution of Fe nanoparticles was observed after heating of LSFNb5 in a reducing atmosphere (5 % Н2/Ar) and was confirmed by X-ray diffraction analysis, Mössbauer spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The formation of Fe nanoparticles on the surface of LSFNb5 hollow fiber membrane in the reduction process leads to the enhancement of oxygen fluxes and reduces the apparent activation energy. Kinetic parameters for oxygen transport through LSFNb5 hollow fiber membrane estimated using two different models, are in good agreement with the experimental results. Furthermore, LSFNb5 hollow fiber membrane demonstrates stable performance both before and after surface treatment.

One-step fabrication of hetero-structured polyethersulfone hollow fiber membranes through surface segregation for pervaporation desalination

Hollow fiber membranes (HFMs) are an ideal configuration for industrial applications of pervaporation desalination (PV) membranes. Currently, the efficient fabrication of PV HFMs is restricted by multi-step post-treatment processes on their outer surfaces to form the selective layer. Herein, we utilized the surface segregation strategy to fabricate a hetero-structured HFM in one step, simultaneously forming the hydrophilic dense outer layer and the porous support layer. During hollow fiber spinning process, the amphiphilic copolymer polyvinylpyrrolidone-polyvinyl acetate (PVP-PVAc) in polyether sulfone (PES) dope solution migrated towards water contacting interface in the coagulation bath and formed the hydrophilic layer by extending hydrophilic segment outwards. This fast in-situ hydrophilization well matched the spinning efficiency. The optimal PVP-PVAc content and phase inversion temperature were investigated and the spinning parameters on the structure and performance of HFMs were studied. The HFMs prepared realized a flux of 26.70 kg m−2 h−1 and the salt rejection of 99.98 %, along with adaptability to solutions with different salinities and excellent anti-organic fouling property. This study may provide a facile method to fabricate HFMs with desirable PV desalination performance and scaling-up potential.

Optimization of hollow fiber membrane contactor system for CO2 mineralization using seawater brine: Comparative analysis of performance and transport mechanisms

Carbon mineralization is a promising approach for carbon capture, utilization, and storage (CCUS) but still faces technical and economic challenges. This study reports on CO2 mineralization using various hollow fiber membrane contactors (HFMCs) to optimize the system and understand the mass transport mechanism. We conducted a quantitative comparative assessment through theoretical and experimental approaches to evaluate the performance of three HFMC types with different morphological and chemical characteristics at various gas and liquid velocities. Results showed that the in-house developed highly porous hollow fiber (HF) membrane exhibited superior CO2 capture efficiency compared to commercial membranes. In contrast to other HFMCs showing a sharp decline in CO2 flux due to internal fouling caused by pore wetting and external fouling, the highly porous HF membrane with surface modification maintained stable performance during continuous operation due to its superhydrophobicity and surface roughness. The HF membrane also achieved the highest overall mass transfer coefficients, closely matching the theoretical non-wetted mode due to negligible partial wetting. We expect that this study will provide insights into optimizing HFMCs for enhanced carbon mineralization efficiency.

Development of a multicomponent counter‐current flow model to evaluate the impact of oxygen and water vapor on CO2 removal performance in a hollow fiber membrane contactor

Development of a multicomponent counter‐current flow model to evaluate the impact of oxygen and water vapor on CO₂ removal performance in a hollow fiber membrane contactor

Reduction in Olfactory Discomfort in Inhabited Premises from Areas with Mofettas through Cellulosic Derivative-Polypropylene Hollow Fiber Composite Membranes.

Hydrogen sulfide is present in active or extinct volcanic areas (mofettas). The habitable premises in these areas are affected by the presence of hydrogen sulfide, which, even in low concentrations, gives off a bad to unbearable smell. If the living spaces considered are closed enclosures, then a system can be designed to reduce the concentration of hydrogen sulfide. This paper presents a membrane-based way to reduce the hydrogen sulfide concentration to acceptable limits using a cellulosic derivative-propylene hollow fiber-based composite membrane module. The cellulosic derivatives considered were: carboxymethyl-cellulose (NaCMC), P1; cellulose acetate (CA), P2; methyl 2-hydroxyethyl-cellulose (MHEC), P3; and hydroxyethyl-cellulose (HEC), P4. In the permeation module, hydrogen sulfide is captured with a solution of cadmium that forms cadmium sulfide, usable as a luminescent substance. The composite membranes were characterized by SEM, EDAX, FTIR, FTIR 2D maps, thermal analysis (TG and DSC), and from the perspective of hydrogen sulfide air removal performance. To determine the process performances, the variables were as follows: the nature of the cellulosic derivative-polypropylene hollow fiber composite membrane, the concentration of hydrogen sulfide in the polluted air, the flow rate of polluted air, and the pH of the cadmium nitrate solution. The pertraction efficiency was highest for the sodium carboxymethyl-cellulose (NaCMC)-polypropylene hollow fiber membrane, with a hydrogen sulfide concentration in the polluted air of 20 ppm, a polluted air flow rate (QH2S) of 50 L/min, and a pH of 2 and 4. The hydrogen sulfide flux rates, for membrane P1, fall between 0.25 × 10-7 mol·m2·s-1 for the values of QH2S = 150 L/min, CH2S = 20 ppm, and pH = 2 and 0.67 × 10-7 mol·m-2·s-1 for the values of QH2S = 50 L/min, CH2S = 60 ppm, and pH = 2. The paper proposes a simple air purification system containing hydrogen sulfide, using a module with composite cellulosic derivative-polypropylene hollow fiber membranes.

Heparin-modified polyether ether ketone hollow fiber membrane with improved hemocompatibility and air permeability used for extracorporeal membrane oxygenation

To expand the selection of raw material for fabricating extracorporeal membrane oxygenation (ECMO) and promote its application in lung disease therapy, polyether ether ketone hollow fiber membrane (PEEK-HFM) with designable pore characteristics, desired mechanical performances, and excellent biocompatibility was selected as the potential substitute for existing poly (4-methyl-1-pentene) hollow fiber membrane (PMP-HFM). To address the platelet adhesion and plasma leakage issues with PEEK-HFM, a natural anticoagulant heparin was grafted onto the surface using ultraviolet irradiation. Additionally, to explore the substitutability of the heparin layer while considering cost and scalability, a heparin-like layer composed of copolymers of acrylic acid and sodium p-styrenesulfonate was also constructed on the surface of PEEK-HFM Even though the successful grafting of heparin and heparin-like layers on the PEEK-HFM surface reduced the pore parameters, improvements in surface hydrophilicity also prevented the platelet-adhesion phenomenon and improved the anticoagulant behaviour, making it a viable alternative for commercial PMP-HFMs in ECMO production. Furthermore heparin-modified and heparin-like modified PEEK-HFMs demonstrated similar performance, indicating that synthetic layers can effectively replace natural heparin. This study holds practical and instructive significance for future research and the application of membranes in the development of oxygenators.

Flexible inner surface of polysulfone membranes prevents platelet adhesive protein adsorption and improves antithrombogenicity in vitro.

We investigated whether the condition of the inner surface of hollow fibers affects the blood compatibility of hemodialyzers. We used scanning probe microscope/atomic force microscopy (SPM/AFM) to investigate the height of the swelling and flexible layers (thickness and softness) on the inner surfaces of the hollow fibers. Next, we tested the blood compatibility between dialyzers comprising a hollow fiber membrane, in which the other dialyzers, except for PVP, were additionally coated using PS membranes coated with other materials. After blood was injected into the dialyzer and plugged, dynamic stimulation was performed by slightly rotating the dialyzer for 4 h, although there was no blood circulation. The vitamin E-coated polysulfone (PS) membrane showed a higher thickness and softness of the flexible layer than the asymmetric cellulose triacetate membrane without polyvinylpyrrolidone (PVP) and the PS membranes with PVP. We found that the dialyzer with vitamin E coating significantly suppressed the decrease in platelets, increase in β-TG, and increase in PF4 compared to those coated with NV polymer. Additionally, as the adsorbed protein on the inner surface, the total protein, fibronectin, and vWF levels were significantly lower in the vitamin E-coated dialyzer. The thickness and softness of the flexible layer of the inner surface of the hollow fiber membrane in vitro affect differences in blood coagulation performance in clinical research. Future clinical trials are required to confirm our results.

The change in thermal-induced interchain distance boosts the gas barrier property of PEI-derived hollow fiber membranes

In order to fulfill diverse special applications (e.g. food packaging, anticorrosion coatings, flame retardant coatings, biomedical industry and lighter-than air applications), the superior gas barrier property is principal requirement. Based on previous researches, the gas barrier property of membranes could be improved to some extent by changing their component, chemical structure, physical property, fabrication parameters or incorporating impermeable fillers. The above-mentioned approaches provide the enhanced gas barrier property owing to increment in resistance for diffusion of tested gas. That implies the intrinsic factors of the membrane such as free volume fraction of membrane are determined effect on permeability to gas. Accordingly, present work investigated the impact of thermal treatment on enhancement of gas barrier property by manipulating the temperature in the range of 200 °C to 240 °C to adjust the orientation of molecular structure. Based on a series of analysis as well as pure gas measurement, the hydrogen permeability of as-treated membrane decreased by almost 2700 times than that of neat membrane, which is due to the absence of amorphousity. The exceptional gas barrier properties of resultant membrane exhibited great potential for special applications and paved the feasible way for other amorphous precursor to prepare the gas barrier membrane.

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi-Purpose Polyamine Functionalization.

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10-30nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm2 and GO layer thicknesses of ≈500nm are fabricated, and they exhibited a stable dye water permeance of 75 L m-2 h-1 bar-1, rejection of >99.5% for Direct red and Congo red, and Na2SO4/dye separation factor of 300-500, superior to state-of-the-art commercial membranes. The versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

Long-term operation of a full-scale membrane bioreactor for industrial wastewater treatment using polyvinyl fluoride hollow fiber membranes: A systematic evaluation during 18-year operation

A membrane bioreactor (MBR) is a robust, high-performance technology for wastewater treatment that has been commercialized and disseminated worldwide since 1990. Despite broad implementation of this technology in the wastewater sector, ultralong operation beyond the membrane lifetime has rarely been reported. Therefore, the objectives of this study were to investigate (1) the effectiveness of a manually-operated feedback strategy to prevent membrane biofouling by dosing with sodium hypochlorite and oxalic acid and (2) the organic carbon removal of industrial wastewater treated by a full-scale MBR system in a chemical plant. The manually-operated feedback strategy consisted of monitoring the transmembrane pressure (TMP) by a test module in a bench-scale MBR to detect an inflection point, that is, the point (15 kPa) at which the TMP switched from growing gradually to exponentially in time. Biocake formation became noticeable at the inflection point, suggesting the TMP at which the membrane should be chemically washed to prevent severe biofouling. A full-scale MBR system was installed with a polyvinylidene fluoride (PVDF) membrane for organic carbon removal. The membrane was washed with 3000 mg/L of sodium hypochlorite and 1 wt% oxalic acid when the TMP reached 15 kPa during operation. The MBR was successfully operated for over 18 years without the PVDF membrane being damaged or compromised by biofouling. Characterization of the foulants on the membrane surface revealed that membrane washing removed inorganic (calcium and iron) and organic (acid amides and polysaccharides) foulants, plausibly by the action of oxalic acid and sodium hypochlorite, respectively. Installing a robust PVDF membrane and performing chemical washing at an inflection point in the TMP dynamics enabled ultralong MBR operation beyond the regular membrane lifetime. The implementation of the advocated strategy paves the way for the low CO2 footprint operation of a PVDF MBR, which does not require frequent membrane replacement and laborious membrane ex-situ cleaning.

A high-throughput sample preparation approach for the determination of nonsteroidal anti-inflammatory drugs in urine samples through membrane-based microextraction employing a green supramolecular solvent

Nonsteroidal anti-inflammatory drugs (NSAIDs) are a class of drugs with antipyretic, analgesic, and anti-inflammatory effects widely used worldwide. This study aimed at developing an environmentally friendly and high-throughput sample preparation method for the determination of six NSAIDs in urine samples followed by high-performance liquid chromatography coupled to diode-array detection (HPLC-DAD). The experimental workflow consisted of hollow-fiber microporous membrane liquid-liquid extraction (HF-MMLLE) using a supramolecular solvent immobilized into the porous of polypropylene hollow membranes (1 cm length). These membranes were attached to a 96-well plate system to permit multiple extractions simultaneously. Under the optimized conditions, limits of detection (LODs) and limits of quantification (LOQs) ranged from 6.06 to 30.3 µg/L and from 20 to 100 µg/L, respectively. The linear ranges varied from 20 to 1000 µg/L for indomethacin and diclofenac, from 50 to 1000 µg/L for ketoprofen and ibuprofen, and from 100 to 1000 µg/L for naproxen and fenoprofen. The coefficients of determination (R²) ranged from 0.9735 to 0.9997. Intraday precision ranged from 6.13 to 20.11 %, interday precision varied from 2.87 to 20.72 %, and accuracy ranged from 92.49 to 126.89 %. Moreover, the recently proposed Sample Preparation Metric of Sustainability (SPMS) was employed to evaluate the greenness of the sample preparation technique resulting in a score of 8.0, which is highly satisfactory according to the concepts of green analytical chemistry.

Preparation of high-performance PVDF hollow fiber microporous membranes via the c-TIPS process with water-insoluble solvent as the second solvent

Triethyl phosphate (TEP) is a promising solvent for the c-TIPS process given its high boiling point and water miscibility. However, casting solutions containing high TEP concentration generally trigger gelation, giving a dense outer surface in PVDF membrane. In this work, we fabricated PVDF hollow fiber membranes with a porous outer surface and excellent mechanical strength via a complex thermally induced phase separation (c-TIPS) method and applied them in the DCMD process. A water-insoluble solvent, dibasic ester solvents (DBEs), was used as the second solvent to modulate the phase separation process of the PVDF/TEP system. The mass transfer between the coagulation bath and the DBEs solvent was analyzed. It could decrease the polymer-solvent interactions and the rate of solvent efflux in the coagulation bath, contributing to the development of a porous membrane structure. When the weight ratio of TEP/DMA was 1, the optimized PVDF hollow fiber membrane exhibited a tensile strength of 8.34 MPa, an average pore diameter of 0.14 μm, giving the permeate flux of 18.56 ± 2.5 kg m−2 h−1 in DCMD and excellent operational stability when subjected to high brine concentration. Thus, the fabrication method shows a promising potential for tailoring the surface porosity and bulk structure. The PVDF membranes developed in this study demonstrate potential for use in membrane distillation and related applications.

Exploring Electrochemistry: A Self-Designed Experiment by Students for Electrochemical Impedance Spectroscopy Measurement of Hollow Fiber Membranes

Exploring Electrochemistry: A Self-Designed Experiment by Students for Electrochemical Impedance Spectroscopy Measurement of Hollow Fiber Membranes

Effect of microwave treatment on morphological and separation characteristics of polysulfone hemodialysis hollow fiber membranes

Effect of microwave treatment on morphological and separation characteristics of polysulfone hemodialysis hollow fiber membranes

Insights on influence of polymer molecular weight on gas sorption, transport and plasticization in glassy 6FDA-DAM polyimide membranes

It is well-known that spinning of defect-free asymmetric polyimide hollow fibers is promoted by using high polymer molecular weight. On the other hand, effects of polymer molecular weight on microstructure and separation performance of dense film 6FDA-based polyimide membranes relevant to sheath layers of composite membranes are less well-explored. In this work, gas sorption, diffusion and permeation of CO2, N2 and CH4 for 6FDA-DAM dense films are considered for 45 kDa and 176 kDa weight average molecular weights. Such molecular weights are relevant for practical hollow fiber spinning of membranes. Earlier results for polystyrene samples show similar trends in dual mode sorption model results like those noted here for the 6FDA-DAM polyimide case; however, effects on permeation like those considered here were not addressed for the polystyrene case. Here we also address actual pure and mixed gas CO2 and CH4 permeation and show higher free volumes, higher gas permeability but lower 50:50 CO2/CH4 selectivity associated with the higher molecular weight sample. Analysis using the self-consistent dual-mode sorption and transport models help understand the observed trends. Our results suggest denser packing of polymer segments exists in the Henry's law environment of the low molecular weight sample. Moreover, the higher polymer segmental packing in the Henry's law environment suppresses CO2 plasticization with a dual-mode microstructure controlling separation performance and plasticization behavior for this important member of the 6FDA polyimide family. We show evidence of effects of charge transfer complexes as possible main features in these trends. These dense film results help guide future work on dense sheath layers on composite hollow fiber membranes.

Mass transfer of bilirubin and bovine serum albumin in hollow fiber membrane module of artificial liver

Understanding the mass transfer behaviors in hollow fiber membrane module of artificial liver is important for improving toxin removal efficiency. A three-dimensional numerical model was established to study the mass transfer of small molecule bilirubin and macromolecule bovine serum albumin (BSA) in the hollow fiber membrane module. Effects of tube-side flow rate, shell-side flow rate, and hollow fiber length on the mass transfer of bilirubin and BSA were discussed. The simulation results showed that the clearance of bilirubin was significantly affected by both convective and diffusive solute transport, while the clearance of macromolecule BSA was dominated by convective solute transport. The clearance rates of bilirubin and BSA increasd with the increase of tube-side flow rate and hollow fiber length. With the increase of shell-side flow rate, the clearance rate of bilirubin first rose rapidly, then slowly rose to an asymptotic value, while the clearance rate of BSA gradually decreased. The results can provide help for designing structures of hollow fiber membrane module and operation parameters of clinical treatment.

Investigation on the synthesis conditions of poly(4-methyl-1-pentene) hollow fiber membrane with high gas permeability and strong tensile strength

Investigation on the synthesis conditions of poly(4-methyl-1-pentene) hollow fiber membrane with high gas permeability and strong tensile strength

Performance enhancement of hollow fiber membrane contactors for CO2 absorption using MEA-based functionalized nanofluids

Performance enhancement of hollow fiber membrane contactors for CO2 absorption using MEA-based functionalized nanofluids