Gas-Liquid Hollow Fiber Membrane Contactors for Different Applications

Gas-liquid membrane contactors that were based on hollow fiber membranes are the example of highly effective hybrid separation processes in the field of membrane technology. Membranes provide a fixed and well-determined interface for gas/liquid mass transfer without dispensing one phase into another while their structure (hollow fiber) offers very large surface area per apparatus volume resulted in the compactness and modularity of separation equipment. In many cases, stated benefits are complemented with high separation selectivity typical for absorption technology. Since hollow fiber membrane contactors are agreed to be one of the most perspective methods for CO2 capture technologies, the major reviews are devoted to research activities within this field. This review is focused on the research works carried out so far on the applications of membrane contactors for other gas-liquid separation tasks, such as water deoxygenation/ozonation, air humidity control, ethylene/ethane separation, etc. A wide range of materials, membranes, and liquid solvents for membrane contactor processes are considered. Special attention is given to current studies on the capture of acid gases (H2S, SO2) from different mixtures. The examples of pilot-scale and semi-industrial implementation of membrane contactors are given

Effect of molecular weight of polyacrylic acid (PAA) on polyethersulfone membrane structure and performance

The novel method of modification of polyethersulfone (PES) ultrafiltration membranes is proposed. This method involves the use of aqueous solutions of polyacrylic acid (PAA) of different molecular weights (Mn=5.1×103 g·mol–1, Mn=490×103 g·mol–1) as a coagulant in non-solvent induced phase inversion process (NIPS). Addition of PAA (0.05–1.5 wt%) to the coagulation bath leads to marked changes in permeability and hydrophilicity of the surface of membrane selective layer. When the coagulation bath contains 0.5 wt% of PAA (Mn=5.1×103 g·mol–1) the rejection coefficient for polyvinulpyrrolidone (PVP К-30, Mn=40 kDa) decreases from 95% (for pristine PES membrane) to 80% (for membrane modified by PAA) and pure water flux (PWF) increases from 55 to 150 l·m-2·h-1. The presence of 0.1 wt% PAA (Mn=490×103 g·mol–1) in the coagulation bath results in an increase in PWF up to 220 l·m-2·h-1 and a decrease in rejection coefficient down to 35%. Water contact angles of the surface of the selective layer of modified membranes decreased down to 33o, for membranes, modified with PAA of higher molecular weights, and down to 43o for for membranes, modified by PAA with lower molecular weight (Mn=5.1×103 g·mol–1). The presence of PAA on the surface of PES membranes is confirmed by the FTIR spectroscopy. The membranes obtained by using PAA solution were pH-sensitive and pH-reversible, while the PWF of the initial membranes did not respond to the pH of feed solution. The SEM analysis of the structure of the membranes reveals marked difference in the morphology along cross section between the pristine and modified membranes. The suppression of macrovoids formation in the supporting layer of membrane with an increase in the concentration of PAA in the coagulation bath was noted. Fouling resistance behavior was studied using bovine serum albumin (BSA) solution in phosphate buffer. It was found that PAA addition to the coagulation bath enhances the fouling resistance of the modified membranes. The best fouling resistance with respect to BSA fouling is observed for the membranes with maximum hydrophilicity.This work was supported by the Belarusian Republican Foundation for Fundamental Research, Grant No. X18MС-018 and STINT Grant no. IB 2017-7377

Simulation of Convection–Diffusion Transport in a Laminar Flow Past a Row of Parallel Absorbing Fibers

A numerical simulation of the laminar flow field and convection⁻diffusion mass transfer in a regular system of parallel fully absorbing fibers for the range of Reynolds numbers up to Re = 300 is performed. An isolated row of equidistant circular fibers arranged normally to the external flow is considered as the simplest model for a hollow-fiber membrane contactor. The drag forces acting on the fibers with dependence on Re and on the ratio of the fiber diameter to the distance between the fiber axes, as well as the fiber Sherwood number versus Re and the Schmidt number, Sc, are calculated. A nonlinear regression formula is proposed for calculating the fiber drag force versus Re in a wide range of the interfiber distances. It is shown that the Natanson formula for the fiber Sherwood number as a function of the fiber drag force, Re, and Sc, which was originally derived in the limit of high Peclet numbers, is applicable for small and intermediate Reynolds numbers; intermediate and large Peclet numbers, where Pe = Re × Sc; and for sparse and moderately dense rows of fibers

Correlation between membrane surface properties, polymer nature and fouling in skim milk ultrafiltration

The fouling of the membranes in skim milk ultrafiltration with the nominal molecular weight cut-off (MWCO) of 100 kDa fabricated from different polymers (polysulfone (PSF), polysulfonamide (PSA), aromatic polyamide (PA), polyacrylonitrile (PAN), cellulose acetate (CA) and regenerated cellulose (RC)) was studied. The membrane structure and physical-chemical properties of the selective layer were analyzed using scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle (θ, °) measurements, free surface energy measurements and bovine serum albumin (BSA) adsorption. Additionally, the flux of the skim milk at the constant product concentration, protein adsorption, resistance of the gel layer of the membranes were determined. It was found that according to the decrease in water contact angle of the membrane selective layers membranes can be arranged in the series as follows: PSF > PSA > PA > PAN > CA > RC. It was revealed that there was no direct correlation between the membrane hydrophilicity and the protein adsorption. It was noted, that the studied membranes featured significantly different hydraulic resistances of the protein gel-layer, which can be considered as a secondary dynamic membrane. Comparison of the parameters – water contact angle and polar component of the free surface energy of the membrane selective layer, and normalized dipole moment of the membrane polymers - with the adsorption values of the proteins during ultrafiltration proves that the protein adsorption to the membrane surface increases with an increase in hydrophobicity and polarity of the membrane. The high protein adsorption by the moderately hydrophilic PAN membrane is due to the contribution of the high normalized dipole moment of the polymer. In the case of the polar RC-100 membrane, the influence of the membrane polarity was shown to be counter-balanced by its high hydrophilicity. The study highlights the impact of the physical-chemical properties and structure of the membrane on the protein gel-layer and thus their importance in membrane fouling control in dairy applications

Modification of PES ultrafiltration membranes by cationic polyelectrolyte Praestol 859: Characterization, performance and application for purification of hemicellulose

Novel approach for membrane modification to improve separation performance and antifouling stability was proposed. It involves using of 0.1–0.3 wt.% aqueous solutions of Praestol 859 (cationic polyelectrolyte based on copolymer of acrylamide and 2-acryloxyethyltrimethylammonium chloride) as coagulants upon membrane preparation via non-solvent induced phase separation. It was shown that the addition of small amounts (0.1–0.3 wt.%) of Praestol 859 into the coagulation bath leads to an increase in membrane pure water flux from 51 up to 68 L m−2 h−1 without decreasing membrane retention. Contact angle for modified membranes decreased from 64° down to 55°. Immobilization of Praestol 859 on the surface of a selective membrane layer was confirmed by FTIR spectroscopy. It was found that the addition of Praestol 859 into the coagulation bath suppressed the macrovoid formation in the membranes supporting layer due to the decrease of “solvent-non-solvent” exchange rate which is attributed to the significant increase of viscosity of the coagulation bath. The separation performance of modified membranes for fractionation of thermomechanical pulp mill process water, for concentration and purification of hemicellulose for further processing was studied. It was found that membrane modification by Praestol 859 leads to 2–6 times increase of flux, increase of fouling recovery ratio and improvement of cleaning efficiency without decreasing membrane rejection with regard to hemicelluloses (91.5–93%) and lignin (21–22%) as reference components

Development of Antifouling Polysulfone Membranes by Synergistic Modification with Two Different Additives in Casting Solution and Coagulation Bath: Synperonic F108 and Polyacrylic Acid

This study deals with the development of antifouling ultrafiltration membranes based on polysulfone (PSF) for wastewater treatment and the concentration and purification of hemicellulose and lignin in the pulp and paper industry. The efficient simple and reproducible technique of PSF membrane modification to increase antifouling performance by simultaneous addition of triblock copolymer polyethylene glycol-polypropylene glycol-polyethylene glycol (Synperonic F108, Mn =14 × 103 g mol−1) to the casting solution and addition of polyacrylic acid (PAA, Mn = 250 × 103 g mol−1) to the coagulation bath is proposed for the first time. The effect of the PAA concentration in the aqueous solution on the PSF/Synperonic F108 membrane structure, surface characteristics, performance, and antifouling stability was investigated. PAA concentrations were varied from 0.35 to 2.0 wt.%. Membrane composition, structure, and topology were investigated by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The addition of PAA into the coagulation bath was revealed to cause the formation of a thicker and denser selective layer with decreasing its pore size and porosity; according to the structural characterization, an interpolymer complex of the two additives was formed on the surface of the PSF membrane. Hydrophilicity of the membrane selective layer surface was shown to increase significantly. The selective layer surface charge was found to become more negative in comparison to the reference membrane. It was shown that PSF/Synperonic F108/PAA membranes are characterized by better antifouling performance in ultrafiltration of humic acid solution and thermomechanical pulp mill (ThMP) process water. Membrane modification with PAA results in higher ThMP process water flux, fouling recovery ratio, and hemicellulose and total lignin rejection compared to the reference PSF/Synperonic F108 membrane. This suggests the possibility of applying the developed membranes for hemicellulose concentration and purification

Modification of Thin Film Composite PVA/PAN Membranes for Pervaporation Using Aluminosilicate Nanoparticles

The effect of the modification of the polyvinyl alcohol (PVA) selective layer of thin film composite (TFC) membranes by aluminosilicate (Al2O3·SiO2) nanoparticles on the structure and pervaporation performance was studied. For the first time, PVA-Al2O3·SiO2/polyacrylonitrile (PAN) thin film nanocomposite (TFN) membranes for pervaporation separation of ethanol/water mixture were developed via the formation of the selective layer in dynamic mode. Selective layers of PVA/PAN and PVA-Al2O3·SiO2/PAN membranes were formed via filtration of PVA aqueous solutions or PVA-Al2O3·SiO2 aqueous dispersions through the ultrafiltration PAN membrane for 10 min at 0.3 MPa in dead-end mode. Average particle size and zeta potential of aluminosilicate nanoparticles in PVA aqueous solution were analyzed using the dynamic light scattering technique. Structure and surface properties of membranes were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. Membrane performance was investigated in pervaporation dehydration of ethanol/water mixtures in the broad concentration range. It was found that flux of TFN membranes decreased with addition of Al2O3·SiO2 nanoparticles into the selective layer due to the increase in selective layer thickness. However, ethanol/water separation factor of TFN membranes was found to be significantly higher compared to the reference TFC membrane in the whole range of studied ethanol/water feed mixtures with different concentrations, which is attributed to the increase in membrane hydrophilicity. It was found that developed PVA-Al2O3·SiO2/PAN TFN membranes were more stable in the dehydration of ethanol in the whole range of investigated concentrations as well as at different temperatures of the feed mixtures (25 °C, 35 °C, 50 °C) compared to the reference membrane which is due to the additional cross-linking of the selective layer by formation hydrogen and donor-acceptor bonds between aluminosilicate nanoparticles and PVA macromolecules

One-Step Preparation of Antifouling Polysulfone Ultrafiltration Membranes via Modification by a Cationic Polyelectrolyte Based on Polyacrylamide

A novel method for one-step preparation of antifouling ultrafiltration membranes via a non-solvent induced phase separation (NIPS) technique is proposed. It involves using aqueous 0.05–0.3 wt.% solutions of cationic polyelectrolyte based on a copolymer of acrylamide and 2-acryloxyethyltrimethylammonium chloride (Praestol 859) as a coagulant in NIPS. A systematic study of the effect of the cationic polyelectrolyte addition to the coagulant on the structure, performance and antifouling stability of polysulfone membranes was carried out. The methods for membrane characterization involved scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), contact angle and zeta-potential measurements and evaluation of the permeability, rejection and antifouling performance in human serum albumin solution and surface water ultrafiltration. It was revealed that in the presence of cationic polyelectrolyte in the coagulation bath, its concentration has a major influence on the rate of “solvent–non-solvent” exchange and thus also on the rate of phase separation which significantly affects membrane structure. The immobilization of cationic polyelectrolyte macromolecules into the selective layer was confirmed by FTIR spectroscopy. It was revealed that polyelectrolyte macromolecules predominately immobilize on the surface of the selective layer and not on the bottom layer. Membrane modification was found to improve the hydrophilicity of the selective layer, to increase surface roughness and to change zeta-potential which yields the substantial improvement of membrane antifouling stability toward natural organic matter and human serum albumin

Synthesis of Aromatic Polyimides Based on 3,4′-Oxydianiline by One-Pot Polycondensation in Molten Benzoic Acid and Their Application as Membrane Materials for Pervaporation

A series of aromatic polyimides based on the asymmetrical diamine 3,4ʹ-oxydianiline and various tetracarboxylic acid dianhydrides, both “rigid” and “flexible” structure, have been synthesized using the original method of one-pot high-temperature catalytic polycondensation in molten benzoic acid. The synthesized polyimides were investigated using fourier-transform infrared (FTIR) and 1H NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis (TMA) and wide-angle X-ray scattering (WAXS). It was found that the synthesized polyimides, depending on the used dianhydride, are characterized by different solubility in organic solvent and molten benzoic acid, molecular weight, glass transition temperature (Tg) from 198 to 270 °C, an amorphous or semi crystalline structure with the degree of crystallinity from 41 to 52%. The influence of the method of synthesis on the formation of the crystalline phase of polyimides was studied, and the obtained results were compared with the literature data. The effect of dianhydride chemical structure on the performance of polyimide in pervaporation more specifically, dehydratation of azeotropic isopropanol solution was investigated and compared with the commercially available polyetherimide Ultem 1000™. Membrane structure was studied using scanning electron microscopy. It was found that polyimide PI-DA is the most effective for separation of 88 wt.% isopropanol/12 wt.% water mixture compared to the polyimide PI-6FDA and commercial polyetherimide Ultem 1000™ demonstrating normalized permeation flux of 2.77 kg µm m−2 h−1 and separation factor of 264 (water content in permeate 97 wt.%)