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Phosphate recovery from different second streams using electrodialysis (ED) is a promising step to a nutrients circular economy. However, the relatively low ED performance hinders the widespread adoption of this environmentally sound method. The formation of “bonded species” between phosphates and the weakly basic fixed groups (primary and secondary amines) of the anion exchange membrane can be the cause of decrease in current efficiency and increase in energy consumption. ED processing of NaxH(3−x)PO4 alkaline solutions and the use of intense current modes promote the formation of a bipolar junction from negatively charged bound species and positively charged fixed groups. This phenomenon causes a change in the shape of current–voltage curves, increase in resistance, and an enhancement in proton generation during long-term operation of anion-exchange membrane with weakly basic fixed groups. Shielding of primary and secondary amines with a modifier containing quaternary ammonium bases significantly improves ED performance in the recovery of phosphates from NaxH(3−x)PO4 solution with pH 4.5. Indeed, in the limiting and underlimiting current modes, 40% of phosphates are recovered 1.3 times faster, and energy consumption is reduced by 1.9 times in the case of the modified membrane compared to the pristine one. Studies were performed using a new commercial anion exchange membrane CJMA-2.

New processes for recycling valuable materials from used lithium-ion batteries (LIBs) need to be developed. This is critical to both meeting growing global demand and mitigating the electronic waste crisis. In contrast to the use of reagent-based processes, this work shows the results of testing a hybrid electrobaromembrane (EBM) method for the selective separation of Li+ and Co2+ ions. Separation is carried out using a track-etched membrane with a pore diameter of 35 nm, which can create conditions for separation if an electric field and an oppositely directed pressure field are applied simultaneously. It is shown that the efficiency of ion separation for a lithium/cobalt pair can be very high due to the possibility of directing the fluxes of separated ions to opposite sides. The flux of lithium through the membrane is about 0.3 mol/(m2 × h). The presence of coexisting nickel ions in the feed solution does not affect the flux of lithium. It is shown that the EBM separation conditions can be chosen so that only lithium is extracted from the feed solution, while cobalt and nickel remain in it.

The entrance of even a small amount of phosphorus compounds into natural waters leads to global problems that require the use of modern purification technologies. This paper presents the results of testing a hybrid electrobaromembrane (EBM) method for the selective separation of Cl− (always present in phosphorus-containing waters) and H2PO4− anions. Separated ions of the same charge sign move in an electric field through the pores of a nanoporous membrane to the corresponding electrode, while a commensurate counter-convective flow in the pores is created by a pressure drop across the membrane. It has been shown that EBM technology provides high fluxes of ions being separated across the membrane as well as a high selectivity coefficient compared to other membrane methods. During the processing of solution containing 0.05 M NaCl and 0.05 M NaH2PO4, the flux of phosphates through a track-etched membrane can reach 0.29 mol/(m2×h). Another possibility for separation is the EBM extraction of chlorides from the solution. Its flux can reach 0.40 mol/(m2×h) through the track-etched membrane and 0.33 mol/(m2×h) through a porous aluminum membrane. The separation efficiency can be very high by using both the porous anodic alumina membrane with positive fixed charges and the track-etched membrane with negative fixed charges due to the possibility of directing the fluxes of separated ions in opposite sides.

The application of electrodialysis for tartrate stabilization and reagent-free acidity correction of wine and juices is attracting increasing interest. New aliphatic membranes CJMC-3 and CJMA-3 and aromatic membranes CSE and ASE were tested to determine their suitability for use in these electrodialysis processes and to evaluate the fouling of these membranes by wine components for a short (6–8 h) operating time. Using IR spectroscopy, optical indication and measurement of surface contact angles, the chemical composition of the studied membranes, as well as some details about their fouling by wine components, was clarified. The current–voltage charsacteristics, conductivity and water-splitting capacity of the membranes before and after electrodialysis were analyzed. We found that in the case of cation-exchange membranes, complexes of anthocyanins with metal ions penetrate into the bulk (CJMC-3) or are localized on the surface (CSE), depending on the degree of crosslinking of the polymer matrix. Adsorption of wine components by the surface of anion-exchange membranes CJMA-3 and ASE causes an increase in water splitting. Despite fouling under identical conditions of electrodialysis, membrane pair CJMC-3 and CJMA-3 provided 18 ± 1 tartrate recovery with 31 · 10−3 energy consumption, whereas CSE and ASE provided 20 ± 1% tartrate recovery with an energy consumption of 28 · 10−3 Wh, in addition to reducing the conductivity of wine by 20 ± 1%. The casting of aliphatic polyelectrolyte films on the surface of aromatic membranes reduces fouling with a relatively small increase in energy consumption and approximately the same degree of tartrate recovery compared to pristine CSE and ASE.

In spite of wide variety of commercial ion-exchange membranes, their characteristics, in particular, electrical conductivity and counterion permselectivity, are unsatisfactory for some applications, such as electrolyte solution concentration. This study is aimed at obtaining an anion-exchange membrane (AEM) of high performance in concentrated solutions. An AEM is prepared with a polypyrrole (PPy)-based modification of a heterogeneous AEM with quaternary ammonium functional groups. Concentration dependences of the conductivity, diffusion permeability and Cl− transport number in NaCl solutions are measured and simulated using a new version of the microheterogeneous model. The model describes changes in membrane swelling with increasing concentration and the effect of these changes on the transport characteristics. It is assumed that PPy occupies macro- and mesopores of the host membrane where it replaces non-selective electroneutral solution. Increasing conductivity and selectivity are explained by the presence of positively charged PPy groups. It is found that the conductivity of a freshly prepared membrane reaches 20 mS/cm and the chloride transport number > 0.99 in 4 M NaCl. A choice of input parameters allows quantitative agreement between the experimental and simulation results. However, PPy has shown itself to be an unstable material. This article discusses what parameters a membrane can have to show such exceptional characteristics.

The microheterogeneous model makes it possible to describe the main transport properties of ion-exchange membranes using a single set of input parameters. This paper describes an adaptation of the microheterogeneous model for describing the electrical conductivity and diffusion permeability of a track-etched membrane (TEM). Usually, the transport parameters of TEMs are evaluated assuming that ion transfer occurs through the solution filling the membrane pores, which are cylindrical and oriented normally to the membrane surface. The version of the microheterogeneous model developed in this paper takes into account the presence of a loose layer, which forms as an intermediate layer between the pore solution and the membrane bulk material during track etching. It is assumed that this layer can be considered as a “gel phase” in the framework of the microheterogeneous model due to the fixed hydroxyl and carboxyl groups, which imparts ion exchange properties to the loose layer. The qualitative and quantitative agreement between the calculated and experimental concentration dependencies of the conductivity and diffusion permeability is discussed. The role of the model input parameters is described in relation to the structural features of the membrane. In particular, the inclination of the pores relative to the surface and their narrowing in the middle part of the membrane can be important for their properties.

Electrodialysis (ED) is an attractive method of tartrate stabilization of wine due to its rapidity and reagentlessness. At the same time, fouling of ion-exchange membranes by the components of wine materials is still an unsolved problem. The effect of ethanol, polyphenols (mainly anthocyanins and proanthocyanidins) and saccharides (fructose) on the fouling of aliphatic ion-exchange membranes CJMA-6 and CJMC-5 (manufactured by Hefei Chemjoy Polymer Materials Co. Ltd., Hefei, China) was analyzed using model solutions. It was shown that the mechanism and consequences of fouling are different in the absence of an electric field and during electrodialysis. In particular, a layer of colloidal particles is deposited on the surface of the CJMA-6 anion-exchange membrane in underlimiting current modes. Its thickness increases with increasing current density, apparently due to the implementation of a trap mechanism involving tartaric acid anions, as well as protons, which are products of water splitting and “acid dissociation”. A successful attempt was made to clean CJMA-6 in operando by pumping a water-alcohol solution of KCl through the desalination compartment and changing electric field direction. It has been established that such a cleaning process suppresses the subsequent biofouling of ion-exchange membranes. In addition, selective recovery of polyphenols with high antioxidant activity is possible.

A comparative analysis of mass transfer characteristics and energy consumption was carried out for the electrodialysis recovery of PV from of NaH2PO4 solutions and multicomponent (0.045 M NaxH(3−x)PO4, 0.02 M KCl, 0.045 M KOH, 0.028 M CaCl2, and 0.012 M MgCl2, pH 6.0 ± 0.1) solution in conventional continuous current (CC) and pulsed electric field (PEF) modes. The advantages of using PEF in comparison with CC mode are shown to increase the current efficiency and reduce energy consumption, as well as reduce scaling on heterogeneous anion-exchange membranes. It has been shown that PEF contributes to the suppression of the “acid dissociation” phenomenon, which is specific for anion-exchange membranes in phosphate-containing solutions. Pulse and pause lapse 0.1 s–0.1 s and duty cycle 1/2 were found to be optimal among the studied PEF parameters.

The contact angle between a membrane surface and a waterdrop lying on its surface provides important information about the hydrophilicity/hydrophobicity of the membrane. This method is well-developed for solid non-swelling materials. However, ion-exchange membranes (IEMs) are gel-like solids that swell in liquids. When an IEM is exposed to air, its degree of swelling changes rapidly, making it difficult to measure the contact angle. In this paper, we examine the known experience of measuring contact angles and suggest a simple equipment that allows the membrane to remain swollen during measurements. An optimized protocol makes it possible to obtain reliable and reproducible results. Measuring parameters such as drop size, water dosing speed and others are optimized. Contact angle measurements are shown for a large number of commercial membranes. These data are supplemented with values from other surface characteristics from optical and profilometric measurements.

The review describes the place of membrane methods in solving the problem of the recovery and re-use of biogenic elements (nutrients), primarily trivalent nitrogen NIII and pentavalent phosphorus PV, to provide the sustainable development of mankind. Methods for the recovery of NH4+ − NH3 and phosphates from natural sources and waste products of humans and animals, as well as industrial streams, are classified. Particular attention is paid to the possibilities of using membrane processes for the transition to a circular economy in the field of nutrients. The possibilities of different methods, already developed or under development, are evaluated, primarily those that use ion-exchange membranes. Electromembrane methods take a special place including capacitive deionization and electrodialysis applied for recovery, separation, concentration, and reagent-free pH shift of solutions. This review is distinguished by the fact that it summarizes not only the successes, but also the “bottlenecks” of ion-exchange membrane-based processes. Modern views on the mechanisms of NH4+ − NH3 and phosphate transport in ion-exchange membranes in the presence and in the absence of an electric field are discussed. The innovations to enhance the performance of electromembrane separation processes for phosphate and ammonium recovery are considered.

A one-dimensional non-stationary model was developed for a better understanding of the protein fouling formation mechanism during electroacidification of caseinate solution using electrodialysis with bipolar membranes (EDBM) in pulsed electric field (PEF) mode. Four different PEF modes were investigated with pulse–pause durations of 10–10 s, 10–20 s, 10–33 s, 10–50 s. For each current mode 3 different flow rates were considered, corresponding to Reynolds numbers, Re, equal to 187, 374 and 560. The processes are considered in the diffusion boundary layer between the surface of the cation-exchange layer of bipolar membrane and bulk solution of the desalination compartment. The Nernst–Planck and material balance equation systems describe the ion transport. The electroneutrality condition and equilibrium chemical reactions are taken into account. The calculation results using the developed model are in qualitative agreement with the experimental data obtained during the previous experimental part of the study. It is confirmed that both the electrical PEF mode and the flow rate have a significant effect on the thickness (and mass) of the protein fouling during EDBM. Moreover, the choice of the electric current mode has the main impact on the fouling formation rate; an increase in the PEF pause duration leads to a decrease in the amount of fouling. It was shown that an increase in the PEF pause duration from 10 s to 50 s, in combination with an increase in Reynolds number (the flow rate) from 187 to 560, makes it possible to reduce synergistically the mass of protein deposits from 6 to 1.3 mg/cm2, which corresponds to a 78% decrease.

Synthetic ion exchange membranes (IEMs) are made from organic, inorganic, or mixed and composite materials [...]

The efficiency of separation processes using ion exchange membranes (IEMs), especially in the food industry, is significantly limited by the fouling phenomenon, which is the process of the attachment and growth of certain species on the surface and inside the membrane. Pulsed electric field (PEF) mode, which consists in the application of constant current density pulses during a fixed time (Ton) alternated with pause lapses (Toff), has a positive antifouling impact. The aim of this study was to investigate the combined effect of three different relatively high flow rates of feed solution (corresponding to Reynolds numbers of 187, 374 and 560) and various pulse–pause ratios of PEF current regime on protein fouling kinetics during electrodialysis with bipolar membranes (EDBM) of a model caseinate solution. Four different pulse/pause regimes (with Ton/Toff ratios equal to 10 s/10 s, 10 s/20 s, 10 s/33 s and 10 s/50 s) during electrodialysis (ED) treatment were evaluated at a current density of 5 mA/cm2. It was found that increasing the pause duration and caseinate solution flow rate had a positive impact on the minimization of protein fouling occurring on the cationic surface of the bipolar membrane (BPM) during the EDBM. Both a long pause and high flow rate contribute to a more effective decrease in the concentration of protons and caseinate anions at the BPM surface: a very good membrane performance was achieved with 50 s of pause duration of PEF and a flow rate corresponding to Re = 374. A further increase in PEF pause duration (above 50 s) or flow rate (above Re = 374) did not lead to a significant decrease in the amount of fouling.

The application of pulsed electric field (PEF) in electrodialysis has been proven to be efficient for a number of effects: increasing mass transfer rate, mitigation of scaling and fouling, reducing water splitting. Recently, the improvement of the membrane permselectivity for specific counterions was discovered experimentally by the group of Laurent Bazinet (N. Lemay et al. J. Memb. Sci. 604, 117878 (2020)). To better understanding the effect of PEF in electrodialysis, simulations were performed using a non-stationary mathematical model based on the Nernst–Planck and Poisson equations. For the first time, it was not only the condition used when the current density is specified but also the condition when the voltage is set. A membrane and two adjacent diffusion layers are considered. It is shown that when applying the regime used by Lemay et al. (the same current density in conventional continuous current (CC) mode and during the pulses in PEF mode), there is a significant gain in specific permselectivity. It is explained by a reduction in the membrane concentration polarization in PEF mode. In the CC mode of electrodialysis, increasing current density leads to a loss in specific permselectivity: concentration profiles in the diffusion layers and membrane are formed in such a way that ion diffusion reduces the migration flux of the preferentially transferred ion and increases that of the poorly transferred ion. In PEF mode, the concentration profiles are partially restored during the pauses when the current is zero. However, if a different condition is used than the condition applied by Lemay et al., that is, when the same average current density is applied in both the PEF and CC modes, there is no gain in specific permeability. It is shown that within the framework of the applied mathematical model, the specific selectivity depends only on the average current density and does not depend on the mode of its application (CC or PEF mode).

The broad possibilities of electrochemical impedance spectroscopy for assessing the capacitance of interphase boundaries; the resistance and thickness of the foulant layer were shown by the example of AMX-Sb membrane contacted with red wine from one side and 0.02 M sodium chloride solution from the other side. This enabled us to determine to what extent foulants affect the electrical resistance of ion-exchange membranes, the ohmic resistance and the thickness of diffusion layers, the intensity of water splitting, and the electroconvection in under- and over-limiting current modes. It was established that short-term (10 h) contact of the AMX-Sb membrane with wine reduces the water-splitting due to the screening of fixed groups on the membrane surface by wine components. On the contrary, biofouling, which develops upon a longer membrane operation, enhances water splitting, due to the formation of a bipolar structure on the AMX-Sb surface. This bipolar structure is composed of a positively charged surface of anion-exchange membrane and negatively charged outer membranes of microorganisms. Using optical microscopy and microbiological analysis, it was found that more intense biofouling is observed on the AMX-Sb surface, that has not been in contacted with wine.

Fouling is one of the major problems in electrodialysis. The aim of the present work was to investigate the effect of five different solution flow rates (corresponding to Reynolds numbers of 162, 242, 323, 404 and 485) combined with the use of pulsed electric field (PEF) current mode on protein fouling of bipolar membrane (BPM) during electrodialysis with bipolar membranes (EDBM) of skim milk. The application of PEF prevented the fouling formation by proteins on the cationic interface of the BPM almost completely, regardless of the flow rate or Reynolds number. Indeed, under PEF mode of current the weight of protein fouling was negligible in comparison with CC current mode (0.07 ± 0.08 mg/cm2 versus 5.56 ± 2.40 mg/cm2). When a continuous current (CC) mode was applied, Reynolds number equals or higher than 323 corresponded to a minimal value of protein fouling of BPM. This positive effect of both increasing the flow rate and using PEF is due to the facts that during pauses, the solution flow flushes the accumulated protein from the membrane while in the same time there is a decrease in concentration polarization (CP) and consequently decrease in H+ generation at the cationic interface of the BPM, minimizing fouling formation and accumulation.

Recently developed and produced by Hefei Chemjoy Polymer Material Co. Ltd., homogeneous CJMC-3 and CJMC-5 cation-exchange membranes (CJMCED) are characterized. The membrane conductivity in NaCl, Na2SO4, and CaCl2 solutions, permeability in respect to the NaCl and CaCl2 diffusion, transport numbers, current–voltage curves (CVC), and the difference in the pH (ΔpH) of the NaCl solution at the desalination compartment output and input are examined for these membranes in comparison with a well-studied commercial Neosepta CMX cation-exchange membrane produced by Astom Corporation, Japan. It is found that the conductivity, CVC (at relatively low voltages), and water splitting rate (characterized by ΔpH) for both CJMCED membranes are rather close to these characteristics for the CMX membrane. However, the diffusion permeability of the CJMCED membranes is significantly higher than that of the CMX membrane. This is due to the essentially more porous structure of the CJMCED membranes; the latter reduces the counterion permselectivity of these membranes, while allowing much easier transport of large ions, such as anthocyanins present in natural dyes of fruit and berry juices. The new membranes are promising for use in electrodialysis demineralization of brackish water and natural food solutions.

Water splitting (WS) and electroconvection (EC) are the main phenomena affecting ion transfer through ion-exchange membranes in intensive current regimes of electrodialysis. While EC enhances ion transport, WS, in most cases, is an undesirable effect reducing current efficiency and causing precipitation of sparingly soluble compounds. A mathematical description of the transfer of salt ions and H+ (OH−) ions generated in WS is presented. The model is based on the Nernst−Planck and Poisson equations; it takes into account deviation from local electroneutrality in the depleted diffusion boundary layer (DBL). The current transported by water ions is given as a parameter. Numerical and semi-analytical solutions are developed. The analytical solution is found by dividing the depleted DBL into three zones: the electroneutral region, the extended space charge region (SCR), and the quasi-equilibrium zone near the membrane surface. There is an excellent agreement between two solutions when calculating the concentration of all four ions, electric field, and potential drop across the depleted DBL. The treatment of experimental partial current−voltage curves shows that under the same current density, the surface space charge density at the anion-exchange membrane is lower than that at the cation-exchange membrane. This explains the negative effect of WS, which partially suppresses EC and reduces salt ion transfer. The restrictions of the analytical solution, namely, the local chemical equilibrium assumption, are discussed.

Ion-exchange membranes (IEMs) find more and more applications; the success of an application depends on the properties of the membranes selected for its realization. For the first time, the results of a comprehensive characterization of the transport properties of IEMs from three manufactures (Astom, Japan; Shchekinoazot, Russia; and Fujifilm, The Netherlands) are reported. Our own and literature data are presented and analyzed using the microheterogeneous model. Homogeneous Neosepta AMX and CMX (Astom), heterogeneous MA-41 and MK-40 (Shchekinoazot), and AEM Type-I, AEM Type-II, AEM Type-X, as well as CEM Type-I, CEM Type-II, and CEM Type-X produced by the electrospinning method (Fujifim) were studied. The concentration dependencies of the conductivity, diffusion permeability, as well as the real and apparent ion transport numbers in these membranes were measured. The counterion transport number characterizing the membrane permselectivity increases in the following order: CEM Type-I ≅ MA-41 < AEM Type-I < MK-40 < CMX ≅ CEM Type-II ≅ CEM Type-X ≅ AEM Type-II < AMX < AEM Type-X. It is shown that the properties of the AEM Type-I and CEM Type-I membranes are close to those of the heterogeneous MA-41 and MK-40 membranes, while the properties of Fujifilm Type-II and Type-X membranes are close to those of the homogeneous AMX and CMX membranes. This difference is related to the fact that the Type-I membranes have a relatively high parameter f2, the volume fraction of the electroneutral solution filling the intergel spaces. This high value is apparently due to the open-ended pores, formed by the reinforcing fabric filaments of the Type-I membranes, which protrude above the surface of these membranes.

The use of the Nernst–Planck and Poisson (NPP) equations allows computation of the space charge density near solution/electrode or solution/ion-exchange membrane interface. This is important in modelling ion transfer, especially when taking into account electroconvective transport. The most solutions in literature use the condition setting a potential difference in the system (potentiostatic or potentiodynamic mode). However, very often in practice and experiment (such as chronopotentiometry and voltammetry), the galvanostatic/galvanodynamic mode is applied. In this study, a depleted stagnant diffusion layer adjacent to an ion-exchange membrane is considered. In this article, a new boundary condition is proposed, which sets a total current density, i, via an equation expressing the potential gradient as an explicit function of i. The numerical solution of the problem is compared with an approximate solution, which is obtained by a combination of numerical solution in one part of the diffusion layer (including the electroneutral region and the extended space charge region, zone (I) with an analytical solution in the other part (the quasi-equilibrium electric double layer (EDL), zone (II). It is shown that this approach (called the “zonal” model) allows reducing the computational complexity of the problem tens of times without significant loss of accuracy. An additional simplification is introduced by neglecting the thickness of the quasi-equilibrium EDL in comparison to the diffusion layer thickness (the “simplified” model). For the first time, the distributions of concentrations, space charge density and current density along the distance to an ion-exchange membrane surface are computed as functions of time in galvanostatic mode. The calculation of the transition time, τ, for an ion-exchange membrane agree with an experiment from literature. It is suggested that rapid changes of space charge density, and current density with time and distance, could lead to lateral electroosmotic flows delaying depletion of near-surface solution and increasing τ.