One way to enhance mass transfer and reduce fouling in wastewater electrodialysis is stimulation of electroconvective mixing of the solution adjoining membranes by modifying their surfaces. Several samples were prepared by casting the perfluorosulfonic acid (PFSA) polymer film doped with TiO₂ nanoparticles onto the surface of the heterogeneous cation-exchange membrane MK-40. It is found that changes in surface characteristics conditioned by such modification lead to an increase in the limiting current density due to the stimulation of electroconvection, which develops according to the mechanism of electroosmosis of the first kind. The greatest increase in the current compared to the pristine membrane can be obtained by modification with the film being 20 μm thick and containing 3 wt% of TiO₂. The sample containing 6 wt% of TiO₂ provides higher mass transfer in overlimiting current modes due to the development of nonequilibrium electroconvection. A 1.5-fold increase in the thickness of the modifying film reduces the positive effect of introducing TiO₂ nanoparticles due to (1) partial shielding of the nanoparticles on the surface of the modified membrane; (2) a decrease in the tangential component of the electric force, which affects the development of electroconvection.

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.

A non-steady state mathematical model of the separation of a solution of an amino acid (phenylalanine) and a mineral salt (NaCl) by the neutralization dialysis (ND) method in a circulating hydrodynamic mode has been proposed. The model takes into account the characteristics of the membranes (thickness, ion-exchange capacity, electrical conductivity) and the solution (concentration and nature of the components) and the flow rate of the solution in the dialyzer compartments. The new model, unlike the known models, takes into account the transport of phenylalanine cations and anions across membranes and diffusion layers of the ND system. In addition, the model takes into account the ability of an amino acid to undergo protonation/deprotonation reactions. Comparison of the simulation results with experimental data suggests that the model adequately describes the ND of solutions of a phenylalanine–NaCl mixture. It has been shown that, for a given pair of membranes (CSE cation-exchange membrane and ASE anion-exchange membrane, Astom, Japan) and studied concentrations, the pH of the mixed solution remains relatively low throughout the entire process, and the rate of decrease in the electrical conductivity is lower than that for an individual NaCl solution. The loss of phenylalanine in the ND process has been determined according to analysis of the experimental data and simulation results.

Membrane scaling is a serious problem in electrodialysis. A widely used technique for controlling scale deposition in water treatment technologies is the application of antiscalants (AS). The present study reports on gypsum scale inhibition in electrodialysis cell by the two novel ASs: fluorescent-tagged bisphosphonate 1-hydroxy-7-(6-methoxy-1,3-dioxo-1Hbenzo[de]isoquinolin-2(3H)-yl)heptane-1,1-diyl-bis(phosphonic acid), HEDP-F and fluorescein-tagged polyacrylate, PAA-F2 (molecular mass 4000 Da) monitored by chronopotentiometry and fluorescent microscopy. It was found that cation-exchange membrane MK-40 scaling is sufficiently reduced by both ASs, used in 10⁻⁶ mol·dm⁻³ concentrations. PAA-F2 at these concentrations was found to be more efficient than HEDP-F. At the same time, PAA-F2 reveals gypsum crystals’ habit modification, while HEDP-F does not noticeably affect the crystal form of the deposit. The strong auto-luminescence of MK-40 hampers visualization of both PAA-F2 and HEDP-F on the membrane surface. Nevertheless, PAA-F2 is proved to localize partly on the surface of gypsum crystals as a molecular adsorption layer, and to change their crystal habit. Crystal surface coverage by PAA-F2 appears to be nonuniform. Alternatively, HEDP-F localizes on the surface of a deposit tentatively in the form of [Ca-HEDP-F]. The proposed mechanisms of action are formulated and discussed. The application of antiscalants in electrodialysis for membrane scaling mitigation is demonstrated to be very promising.

The relevance of the hemodialysis procedure is increasing worldwide due to the growing number of patients suffering from chronic kidney disease. Taking into account the structure of dialysis polymer membranes is an important aspect in their development to achieve the required performance of hemodialyzers. We propose a new mathematical model of mass transfer that allows hollow-fiber membrane structural parameters to be taken into account in simulating the clearance (CL) of hemodialyzers in a way that does not require difficult to achieve close approximation to the exact geometry of the membrane porous structure. The model was verified by a comparison of calculations with experimental data on $CL$ obtained using a lab-made dialyzer as well as commercially available ones. The simulations by the model show the non-trivial behavior of the dialyzer clearance as a function of membrane porosity ($f_p$) and the arrangement of pores ($\alpha$). The analysis of this behavior allows one to consider two strategies for increasing the $CL$ of the dialyzer by optimizing the polymer membrane structure: (1) creating a membrane with a well-structured pore system (where $\alpha$ → 1) since doubling $\alpha$ at a high enough $f_p$ can lead to an almost tenfold increase in $CL$; (2) increasing the porosity of the membrane characterized by a random arrangement of pores ($\alpha$ → 0), where, at a relatively low $\alpha$, a sharp increase in $CL$ is observed with a small increase in $f_p$ over a certain threshold value.

A non-steady state mathematical model of an amino acid (phenylalanine (Phe)) and mineral salt (NaCl) solution separation by neutralization dialysis (ND) carried out in a batch mode is proposed. The model takes into account the characteristics of membranes (thickness, ion-exchange capacity, and conductivity) and solutions (concentration, composition). As compared to previously developed models, the new one considers the local equilibrium of Phe protolysis reactions in solutions and membranes and the transport of all the phenylalanine forms (zwitterionic, positively and negatively charged) through membranes. A series of experiments on ND demineralization of the NaCl and Phe mixed solution was carried out. In order to minimize Phe losses, the solution pH in the desalination compartment was controlled by changing the concentrations of the solutions in the acid and alkali compartments of the ND cell. The validity of the model was verified by comparison of simulated and experimental time dependencies of solution electrical conductivity and pH, as well as the concentration of Na⁺, Cl⁻ ions, and Phe species in the desalination compartment. Based on the simulation results, the role of Phe transport mechanisms in the losses of this amino acid during ND was discussed. In the experiments carried out, the demineralization rate reached 90%, accompanied by minimal Phe losses of about 16%. Modeling predicts a steep increase in Phe losses when the demineralization rate is higher than 95%. Nevertheless, simulations show that it is possible to achieve a highly demineralized solution (by 99.9%) with Phe losses amounting to 42%.