Membranes — Open Access Journal

Anaerobic treatment processes have achieved popularity in treating palm oil mill effluent due to its high treatability and biogas generation. The use of externally submerged membranes with anaerobic reactors promotes the retention of the biomass in the reactor. This study was conducted in thermophilic conditions with the Polytetrafluoroethylene hollow fiber (PTFE-HF) membrane which was operated at 55 °C. The reactor was operated at Organic Loading Rates (OLR) of 2, 3, 4, 6, 8, and 10 kg Chemical Oxygen Demand (COD)/m³·d to investigate the treatment performance and the membrane operation. The efficiency of the COD removal achieved by the system was between 93–98%. The highest methane yield achieved was 0.56 m³ CH₄/kg COD_r. The reactor mixed liquor volatile suspended solids (MLVSS) was maintained between 11.1 g/L to 20.9 g/L. A dead-end mode PTFE hollow fiber microfiltration was operated with the constant flux of 3 LMH (L/m²·h) in permeate recirculation mode to separate the clear final effluent and retain the biomass in the reactor. Membrane fouling was one of the limiting factors in the membrane bioreactor application. In this study, organic fouling was observed to be 93% of the total membrane fouling. Full article

The transport of small gases (H₂, CO₂, N₂, O₂) through a series of novel membranes based on necklace-shaped inorganic polymers ([email protected]), in which a polyhedral oligomeric silsesquioxane (POSS) cage unit and soft chains of oligo-dimethyl siloxane (DMS) were alternately connected, was investigated. The influence of the DMS chain length and crosslinking density of the [email protected] on membrane properties were studied. The membranes revealed characteristic structure-property relation towards both glass transition and gases transport. Specifically, clear dependence of properties from the length of DMS units (or overall siloxane content) was revealed. Gas transport properties, when compared to state-of-art polydimethylsiloxane and commercial silicone rubber, demonstrated significantly higher selectivity of [email protected] for carbon dioxide (in CO₂/N₂), hydrogen (in H₂/N₂) and oxygen (in O₂/N₂) but lowered permeability, proportional to the amount of POSS in the material. With a precise control over mechanical and thermal properties compared to conventional silicone rubbers, described materials could be considered as materials of choice in niche gas separation or other applications. Full article

This work investigated changes in the biochemical parameters of multilayer membrane structures, emerging at their modification with multiwalled carbon nanotubes (MWCNTs). The structures were represented by polyelectrolyte microcapsules (PMCs) containing glucose oxidase (GOx). PMCs were made using sodium polystyrene sulfonate (polyanion) and poly(allylamine hydrochloride) (polycation). Three compositions were considered: with MWCNTs incorporated between polyelectrolyte layers; with MWCNTs inserted into the hollow of the microcapsule; and with MWCNTs incorporated simultaneously into the hollow and between polyelectrolyte layers. The impedance spectra showed modifications using MWCNTs to cause a significant decrease in the PMC active resistance from 2560 to 25 kOhm. The cyclic current–voltage curves featured a current rise at modifications of multilayer MWCNT structures. A PMC-based composition was the basis of a receptor element of an amperometric biosensor. The sensitivity of glucose detection by the biosensor was 0.30 and 0.05 μA/mM for PMCs/MWCNTs/GOx and PMCs/GOx compositions, respectively. The biosensor was insensitive to the presence of ethanol or citric acid in the sample. Polyelectrolyte microcapsules based on a multilayer membrane incorporating the enzyme and MWCNTs can be efficient in developing biosensors and microbial fuel cells. Full article

Increasing water demand coupled with projected climate change puts the Southwestern United States at the highest risk of water sustainability by 2050. Membrane distillation offers a unique opportunity to utilize the substantial, but largely untapped geothermal brackish groundwater for desalination to lessen the stress. Two types of hydrophobic, microporous hollow fiber membranes (HFMs), including polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), were evaluated for their effectiveness in direct contact membrane distillation (DCMD). Water flux and salt rejection were measured as a function of module packing density and length in lab-scale systems. The PVDF HFMs generally exhibited higher water flux than the PTFE HFMs possibly due to thinner membrane wall and higher porosity. As the packing density or module length increased, water flux declined. The water production rate per module, however, increased due to the larger membrane surface area. A pilot-scale DCMD system was deployed to the 2nd largest geothermally-heated greenhouse in the United States for field testing over a duration of about 22 days. The results demonstrated the robustness of the DCMD system in the face of environmental fluctuation at the facility. Full article

Novel selective polymeric thin-film composite membranes (TFCMs) for applications at elevated temperatures were developed. Thin selective layers of the polyimides Matrimid 5218^® and 6FDA-6FpDA were cast on a developed polybenzimidazole (PBI) porous support prepared by a phase inversion process. The TFCM properties were investigated with different gases in a wide temperature range, including temperatures up to 270 °C. The membranes showed very high thermal stability and performed well at the elevated temperatures. The development of highly thermally resistant polymeric membranes such as these TFCMs opens opportunities for application in high-temperature integrated processes, such as catalytic membrane reactors for the water-gas shift reaction in order to maximize H₂ yield. Full article

Solid electrolytes for Li transport have been prepared by melt-compounding in one single step. Electrolytes are composed of polyvinylidene fluoride–hexafluoropropylene (PVDF–HFP) with PYR13TFSI on its own or with varying concentration of LiTFSI. While the extrusion of PVDF–HFP with PYR13TFSI is possible up to relatively high liquid fractions, the compatibility of PVDF–HFP with LiTFSI/PYR13TFSI solutions is much lower. An organo-modified sepiolite with D-α-tocopherol polyethylene glycol 1000 succinate (TPGS-S) can be used to enhance the compatibility of these blends and allows to prepare homogeneous PYR13TFSI/LiTFSI/PVDF–HFP electrolytes with controlled microphase separations by melt-compounding. The structure and morphology of the electrolytes has been studied by FTIR, differential scanning calorimetry (DSC), SEM, and AFM. Their mechanical properties have been studied by classical strain–stress experiments. Finally, ionic conductivity has been studied in the −50 to 90 °C temperature range and in diffusivity at 25 °C by PFG-NMR. These electrolytes prove to have a microphase-separated morphology and ionic conductivity which depends mainly on their composition, and a mechanical behavior typical of common thermoplastic polymers, which makes them very easy to handle. Then, in this solvent-free and scalable fashion, it is possible to prepare electrolytes like those prepared by solvent casting, but in few minutes instead of several hours or days, without solvent evaporation steps, and with ionic conductivities, which are very similar for the same compositions, above 0.1 mS·cm⁻¹ at 25 °C. In addition, some of the electrolytes have been prepared with high concentration of Li ion, what has allowed the anion exchange Li transport mechanism to contribute significantly to the overall Li diffusivity, making D_Li become similar and even clearly greater than D_TFSI. Full article

CsH₂PO₄ is a proton conductor pertaining to the acid salts group and shows a phase transition from monoclinic to cubic phase at 232 ± 2 °C under high-steam atmospheres (>30%). This cubic phase gives rise to the so-called superprotonic conductivity. In this work, the influence of the partial substitution of Cs by Ba and Rb, as well as the partial substitution of P by W, Mo, and S in CsH₂PO₄ on the phase transition temperature and electrochemical properties is studied. Among the tested materials, the partial substitution by Rb led to the highest conductivity at high temperature. Furthermore, Ba and S-substituted salts exhibited the highest conductivity at low temperatures. CsH₂PO₄ was used as electrolyte in a fully-assembled fuel cell demonstrating the applicability of the material at high pressures and the possibility to use other materials (Cu and ZnO) instead of Pt as electrode electrocatalyst. Finally, an electrolyzer cell composed of CsH₂PO₄ as electrolyte, Cu and ZnO as cathode and Pt and Ag as anode was evaluated, obtaining a stable production of H₂ at 250 °C. Full article

In cross-flow membrane filtration, fouling results from material deposit which clogs the membrane inner surface. This hinders filtration, which experiences the so-called limiting flux. Among the models proposed by the literature, we retain a simple one: a steady-state reversible fouling is modelled with the use of a single additional parameter, i.e., $N_d$, the ratio of the critical concentration for deposition to the feed concentration at inlet. To focus on fouling, viscous pressure drop and osmotic (counter-)pressure have been chosen low. It results in a minimal model of fouling. Solved thoroughly with the numerical means appropriate to enforce the nonlinear coupling between permeation and concentration polarization, the model delivers novel information. It first shows that permeation is utterly governed by solute transfer, the relevant non-dimensional quantities being hence limited to $N_d$ and $P{e}_{in}$, the transverse Péclet number. Furthermore, when the role played by $N_d$ and moderate $P{e}_{in}$ (say $P{e}_{in}<40$) is investigated, all results can be interpreted with the use of a single non-dimensional parameter, $F_l$, the so-called fouling number, which simply reads $F_l\equiv P{e}_{in}{N}_d^{-1}$. Now rendered possible, the overall fit of the numerical data allows us to put forward analytical final expressions, which involve all the physical parameters and allow us to retrieve the experimental trends. Full article

In the present study, a submerged ceramic membrane bioreactor was used to effectively treat industrial wastewater. The outcome of membrane coatings on the efficacy of the membrane was investigated using a silicon carbide (SiC) coating. The flux data obtained from the study were fitted into two mathematical models, namely, the standard pore blocking model (SPBM) and the complete pore plugging model (CPPM) in order to determine the fouling mechanism. It was observed that the SPBM fit with a minimum coefficient of regression of 0.95, suggesting that particles retained on the pore walls were smaller than the average size of membrane pores. An increase in dissolved oxygen (DO) of up to 225% was noted. The significant improvement of the water quality in terms of DO, chemical oxygen demand (COD) and turbidity of coated membrane emphasizes the fact that the membrane coating increases the efficacy of water treatment in membrane bioreactors. Full article

Silicalite-1 membranes with high pervaporation performance were prepared successfully on a silica-particle-coated tubular silica support using a gel-free steam-assisted conversion (SAC) method. The effects of the silica-particle layer formed on the top surface of the silica support and the physical properties of the silica particles themselves on the membrane-formation process were investigated. The silica particles coated served as the additional silica source for growing the silicalite-1 seed crystal layer into the silicalite-1 membrane. As a result, it was possible to form a dense and continuous membrane even under gel-free conditions. Furthermore, it was found that the properties of the silica particles, such as their primary particle diameter, had a determining effect on their solubility during the steam treatment, that is, on the supply rate of the silica source. The silicalite-1 membrane obtained using the spherical-silica-particle-coated support had an approximately 9-μm-thick separation layer and showed very high pervaporation performance, exhibiting a separation factor of 105 and a flux of 3.72 kg m⁻² h⁻¹ for a 10 wt % ethanol/water mixture at 323 K. Thus, the gel-free SAC method can be used with a silica support coated with silica particles to readily prepare high-performance membranes without producing any chemical waste. Full article

Spent sulfite liquor is an abundant but currently less used wastewater stream from the pulp and paper industry. The recovery of lignin from this resource would provide an inexpensive raw material for the manufacture of fuels and fine chemicals. Here we investigated the suitability of ceramic hollow-fiber membranes for the concentration of spent sulfite liquor as an alternative to common membrane technologies. We tested three ceramic hollow-fiber membranes (3, 8, and 30 nm) in different membrane processes (fed-batch and total recycle mode) and compared their performance with the widely-used tubular membrane geometry. We also evaluated backflushing as a strategy to reduce membrane fouling during filtration. The juxtaposition of the two membrane geometries revealed that wall shear stress is the most important process parameter for the assessment of membrane performance according to permeate flux. The higher the wall shear stress, the higher the permeate flux. Due to the smaller inner diameter of the hollow-fiber membranes, higher wall shear stress can be achieved more easily. Backflushing had no effect on the permeate flux during the concentration experiments. Full article

Swimming pool water was treated using an ultrafiltration process using ceramic and polymer membranes for comparison. It was determined that the efficiency of the process depended on the type of membrane used. The polymer membrane decreased the absorbance and concentration of combined chlorine in the pool water to a greater extent than the ceramic membrane. In the case of a ceramic membrane, the concentration of combined chlorine in the permeate exceeded the limit values. During the ultrafiltration process, the permeate flux decreased, causing the blockage of membrane pores. The extent of this phenomenon was similar for both tested membranes. In the case of the ceramic membrane, flushing it with water could significantly restore its initial performance. For both tested membranes, a high regeneration efficiency was observed during chemical treatment with an alkaline solution. SEM photos of the polymer membrane showed low resistance of this polymer to the chlorine present in the swimming pool water. Full article

Semipermeable membranes play critical roles in many natural and engineering systems. The osmotic pressure is found experimentally much less effective than the hydraulic pressure to drive water through the membrane, which is commonly attributed to the internal concentration polarization (ICP) in the porous layer of the membrane. In this study, it has been shown that a necessary condition for the osmotic pressure to be effective is water continuity across the entire membrane thickness under negative pressure, i.e., the water inside the membrane remains in a metastable state. However, the metastable state of water cannot be maintained indefinitely, and cavitation will undoubtedly occur in the osmotically driven processes. Collapse of the water metastable state was suggested for the first time to be a more important and fundamental reason for the low water fluxes in the osmotically driven membrane processes. Full article

Nowadays, block copolymers hold great promise for the design of novel membranes to be applied for the membrane gas separation. In this regard, microporous block copolymers based on a macroinitiator with an anionic nature, such as potassium-substituted block copolymers of propylene oxide and ethylene oxide (PPEG) and 2,4-toluene diisocyanate (TDI), were obtained and investigated as effective gas separation membranes. The key element of the macromolecular structure that determines the supramolecular organization of the studied polymers is the coplanar blocks of polyisocyanates with an acetal nature (O-polyisocyanate). In the present research, the influence of the content of peripheral polyoxyethylene (POE) blocks in PPEG on the supramolecular structure processes and gas transport characteristics of the obtained polymers based on PPEG and TDI was investigated. According to the study of polymers if the POE block content is 15 wt %, the polyoxypropylene segments are located in the internal cavity of voids formed by O-polyisocyanate blocks. When the POE block content is 30 wt %, the flexible chain component forms its own microphase outside the segregation zone of the rigid O-polyisocyanate blocks. The permeability for polar molecules, such as ammonia or hydrogen sulfide, significantly exceeds the permeability values obtained for non-polar molecules He, N₂ and CH₄. A relatively high permeability is also observed for carbon dioxide. At the same time, the content of POE blocks has a small effect on the permeability for all studied gases. The diffusion coefficient increases with an increase in the POE block content in PPEG for all studied gases. Full article

Polymers of intrinsic microporosity (PIMs) are a promising membrane material for gas separation, because of their high free volume and micro-cavity size distribution. This is countered by PIMs-based membranes being highly susceptible to physical aging, which dramatically reduces their permselectivity over extended periods of time. Supercritical carbon dioxide is known to plasticize and partially solubilise polymers, altering the underlying membrane morphology, and hence impacting the gas separation properties. This investigation reports on the change in PIM-1 membranes after being exposed to supercritical CO₂ for two- and eight-hour intervals, followed by two depressurization protocols, a rapid depressurization and a slow depressurization. The exposure times enables the impact contact time with supercritical CO₂ has on the membrane morphology to be investigated, as well as the subsequent depressurization event. The density of the post supercritical CO₂ exposed membranes, irrespective of exposure time and depressurization, were greater than the untreated membrane. This indicated that supercritical CO₂ had solubilised the polymer chain, enabling PIM-1 to rearrange and contract the free volume micro-cavities present. As a consequence, the permeabilities of He, CH₄, O₂ and CO₂ were all reduced for the supercritical CO₂-treated membranes compared to the original membrane, while N₂ permeability remained unchanged. Importantly, the physical aging properties of the supercritical CO₂-treated membranes altered, with only minor reductions in N₂, CH₄ and O₂ permeabilities observed over extended periods of time. In contrast, He and CO₂ permeabilities experienced similar physical aging in the supercritical treated membranes to that of the original membrane. This was interpreted as the supercritical CO₂ treatment enabling micro-cavity contraction to favour the smaller CO₂ molecule, due to size exclusion of the larger N₂, CH₄ and O₂ molecules. Therefore, physical aging of the treated membranes only had minor impact on N₂, CH₄ and O₂ permeability; while the smaller He and CO₂ gases experience greater permeability loss. This result implies that supercritical CO₂ exposure has potential to limit physical aging performance loss in PIM-1 based membranes for O₂/N₂ separation. Full article

Plenty of fresh water resources are still inaccessible for human use. Calamities such as pollution, climate change, and global warming pose serious threats to the fresh water system. Although many naturally and synthetically grown materials have been taken up to resolve these issues, there is still plenty of room for enhancements in technology and material perspectives to maximize resources and to minimize harm. Considering the challenges related to the purification of water, materials in the form of nanofiber membranes and nanomaterials have made tremendous contributions to water purification and filtration. Nanofiber membranes made of synthetic polymer nanofibers, ceramic membranes etc., metal oxides in various morphologies, and carbonaceous materials were explored in relation to waste removal from water. In this review, we have discussed a few key materials that have shown effectiveness in removing pollutants from waste water, enabling solutions to existing problems in obtaining clean drinking water. Full article

Flow-through electrodialysis membrane cells are widely used in water purification and the processing of agricultural products (milk, wine, etc.). In the research and operating practice of such systems, a significant place is occupied by a galvanodynamic (or galvanostatic) mode. 2D mathematical modelling of ion transfer in the galvanodynamic mode requires solving the problem of setting the average current density equal to a certain value, while the current density distribution in the system is uneven. This article develops a 2D mathematical model of the overlimiting transfer enhanced by electroconvection in a flow-through electrodialysis cell in the galvanodynamic mode. The model is based on the system of Navier–Stokes, Nernst–Planck, Poisson equations and equations for the electric current stream function. To set the electric mode we use a boundary condition, relating the electric field strength and current density. This approach allows us to describe the formation of the extended space charge region and development of electroconvection at overlimiting currents. For the first time, chronopotentiograms and current–voltage characteristics of the membrane systems are calculated for the galvanodynamic mode taking into account the forced flow and development of electroconvection. The behaviors of the calculated chronopotentiograms and current–voltage characteristic coincide qualitatively with experimental data. The effects of the electrolyte concentration, forced flow velocity and channel size on the mass transfer at overlimiting currents are estimated. Full article

Pervaporation has been applied for tetrahydrofuran (THF) dehydration with novel composite membranes advanced by a thin selective layer composed of chitosan (CS) modified by copolymerization with vinyl monomers, acrylonitrile (AN) and styrene, in order to improve the chemical and mechanical stability of CS-based membranes. Composite membranes were developed by depositing a thin selective layer composed of CS copolymers onto a commercially-available porous support based on aromatic polysulfonamide (UPM-20^®). The topography and morphology of the obtained materials were studied by atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Thermal properties and stability were determined by coupled evolved gas analysis (EGA-MS). Transport properties were estimated in pervaporation dehydration of THF. The effect of operating parameters for the pervaporation dehydration of THF such as feed compositions and temperatures (295, 308 and 323 K) was evaluated. It was shown that CS modification with different vinyl monomers led to a difference in physical and transport properties. The composite membrane with the thin selective layer based on CS-PAN copolymer demonstrated optimal transport properties and exhibited the highest water content in the permeate with a reasonably high permeation flux. Full article

Direct contact membrane distillation (DCMD) is a membrane distillation (MD) configuration where feed and distillate directly contact with a hydrophobic membrane. Depending on its operating conditions, the hydraulic pressures of the feed and distillate may be different, leading to adverse effects on the performance of the DCMD process. Nevertheless, little information is available on how hydraulic pressure affects the efficiency of DCMD. Accordingly, this paper investigates the effect of external hydraulic pressure on the process efficiency of DCMD. Gas permeabilities of MD membranes were measured to analyze the effect of membrane compaction by external pressure. Mass transfer coefficients were calculated using experimental data to quantitatively explain the pressure effect. Experiments were also carried out using a laboratory-scale DCMD set-up. After applying the pressure, the cross-sections and surfaces of the membranes were examined using a scanning electron microscope (SEM). Results showed that the membrane structural parameters such as porosity and thickness were changed under relatively high pressure conditions (>30 kPa), leading to reduction in flux. The mass transfer coefficients were also significantly influenced by the hydraulic pressure. Moreover, local wetting of the membranes were observed even below the liquid entry pressure (LEP), which decreased the rejection of salts. These results suggest that the control of hydraulic pressure is important for efficient operation of DCMD process. Full article