This work discusses the applicability of polyaniline-modified cation exchange membranes for the separation of monovalent/divalent cations by electrodialysis. A novel method of membrane modification directly in the electrodialysis unit is used to prepare permselective membranes. Complex characterization of the membranes before and after modification allows revealing the influence of membrane matrix on the modification efficiency. The characterization of the membranes includes determination of the diffusion permeability, specific conductivity and current–voltage curves in HCl, NaCl and CaCl₂ solutions, as well as transport-structural parameters of the extended three-wire model. The characterization results are used to predict the influence of the modification on membrane permselectivity. The competitive mass transfer of singly and doubly charged cations in the electrodialysis process is investigated in underlimiting and overlimiting currents. Electrodialysis desalination of a solution containing Na⁺/Ca²⁺ or H⁺/Ca²⁺ cations shows that the modification leads to an increase in membrane permselectivity to single-charged cations due to the repulsion of Ca²⁺ ions from the positively charged membrane surface. The permselectivity of the polyaniline-modified perfluorinated membrane to H⁺ in the mixture of H⁺/Ca²⁺ cations is observed in all current regimes.

Profiled ion-exchange membranes are promising for improving the parameters of reverse electrodialysis due to the reduction of pumping power and electrical resistance. The smooth commercial heterogeneous cation-exchange MK-40 and anion-exchange MA-41 membranes were chosen as the initial membranes. Profiled membranes with three different types of surface profiles were obtained by hot pressing the initial membranes. The bilayer membranes were made on the basis of single-layer profiled membranes by casting MF-4SK film on the profiled surfaces. The diffusion permeability of all types of single-layer and bilayer profiled membranes was higher than of the initial ones due to the appearance of large defects on their surface during pressing. The conductivity of the profiled membrane was lower in the diluted solution and higher in the concentrated solution than of the initial one for all samples except for the bilayer anion-exchange membrane. The conductivity of that sample was lower than that of the initial anion-exchange MA-41 membrane over the entire range of studied concentrations. The counter-ion transport numbers for all studied membranes were calculated based on the concentration dependences of conductivity and diffusion permeability of the membrane by the microheterogeneous model. The selectivity of single layer and bilayer profiled membranes became lower after their profiling due to the increase of the solution phases of membranes. The asymmetry of the current-voltage curves for all single-layer and bilayer profiled membranes was found. The application of the single layer and bilayer profiled membranes in reverse electrodialysis did not lead to an increase in power density.

The paper shows the possibility of using a microheterogeneous model to estimate the transport numbers of counterions through ion-exchange membranes. It is possible to calculate the open-circuit potential and power density of the reverse electrodialyzer using the data obtained. Eight samples of heterogeneous ion-exchange membranes were studied, two samples for each of the following types of membranes: Ralex CM, Ralex AMH, MK-40, and MA-41. Samples in each pair differed in the year of production and storage conditions. In the work, these samples were named “batch 1” and “batch 2”. According to the microheterogeneous model, to calculate the transport numbers of counterions, it is necessary to use the concentration dependence of the electrical conductivity and diffusion permeability. The electrolyte used was a sodium chloride solution with a concentration range corresponding to the conditional composition of river water and the salinity of the Black Sea. During the research, it was found that samples of Ralex membranes of different batches have similar characteristics over the entire range of investigated concentrations. The calculated values of the transfer numbers for membranes of different batches differ insignificantly: ±0.01 for Ralex AMH in 1 M NaCl. For MK-40 and MA-41 membranes, a significant scatter of characteristics was found, especially in concentrated solutions. As a result, in 1 M NaCl, the transport numbers differ by ±0.05 for MK-40 and ±0.1 for MA-41. The value of the open circuit potential for the Ralex membrane pair showed that the experimental values of the potential are slightly lower than the theoretical ones. At the same time, the maximum calculated power density is higher than the experimental values. The maximum power density achieved in the experiment on reverse electrodialysis was 0.22 W/m², which is in good agreement with the known literature data for heterogeneous membranes. The discrepancy between the experimental and theoretical data may be the difference in the characteristics of the membranes used in the reverse electrodialysis process from the tested samples and does not consider the shadow effect of the spacer in the channels of the electrodialyzer.