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.

In the present study, the problem of sulfuric acid recycling from spent copper plating solution was solved using a hybrid membrane technology, including diffusion dialysis and electrodialysis. A real solution from the production of copper-coated steel wire, containing 1.45 mol/L of sulfuric acid, 0.67 mol/L of ferrous sulfate and 0.176 mol/L of copper sulfate, was processed. Diffusion dialysis with anion-exchange membranes was used to separate sulfuric acid and salts of heavy metals. Then, purified dilute sulfuric acid was concentrated by electrodialysis. The energy consumption for sulfuric acid electrodialysis concentration at a current density of 400 A/m2 was 162 W·h/mol, with a current efficiency of 16 %. After processing according to the hybrid membrane scheme, the solution contained 1.13 mol/L sulfuric acid, 0.077 mol/L ferrous sulfate and 0.022 mol/L copper sulfate. According to established requirements, the solution of a copper plating bath had to contain from 0.75 to 1.25 M sulfuric acid, 0.16–0.18 M of copper sulfate and ferrous sulfate not more than 0.15 M. The resulting acid solution with a small amount of ferrous sulfate and copper sulfate could be used to prepare a copper plating bath solution.

The reagent-free electromembrane process of removing carbonates, bicarbonates, and carbonic acid from softened natural carbonate water using an electrodialysis synthesizer EDS-01 with a two-cell unit cell formed by a bipolar membrane and a cation-exchange membrane has been studied. MB-2M membranes modified with an ionopolymer containing phosphoric acid groups catalytically active in a water-splitting reaction have been used as bipolar membranes, while heterogeneous membranes Ralex CMH (Mega a.s., Czech Republic) have been used as cation-exchange membranes. The decarbonization process has been carried out in two stages. At the first stage, a reagent-free correction of pH of the solution treated has been carried out. The value of pH in acid compartments has been adjusted to be 2.5-4.0. At the second stage, this solution has been deaerated with air purified from carbon dioxide. For a quantitative description of the process, a previously developed model has been adapted to describe the electrodialysis process with bipolar and cationexchange membranes. It is shown that the electrodiffusion transfer of anions through the cation-exchange membrane and bipolar membrane is practically absent, and the change in the concentrations of carbonate ions, bicarbonates, and carbonic acid is due to the quasi-equilibrium chemical reactions. The deaeration of acidified softened water reduces the total carbon content from 5 to 1 mmol/L. The decarbonization of softened water is accompanied by a decrease in the concentration of sodium cations and total mineralization. With an EDS-01 electrodialysis synthesizer performance of 100 L/h, the specific energy consumption is in the range from 0.16 to 6.12 kW h/m 3 depending on the current density.

This paper shows the possibility of using a microheterogeneous model to describe the properties of ion-exchange membranes and calculate the characteristics of a reverse electrodialyzer from the data obtained. We studied the properties of eight samples of heterogeneous cation exchange membranes (two samples of each type of membrane). The samples differed in the year of issue and storage conditions. It is shown that for heterogeneous ion-exchange membranes MK-40 and MA-41, the samples' properties can differ significantly. The counterions transport numbers calculated within the framework of the microheterogeneous model for Ralex membranes differ insignificantly. The counterion transport number in 1 mol/L sodium chloride solution is 0.96 for Ralex CM and 0.98 ± 0.01 for Ralex AMH. For the MK-40 membrane, the transport number in the same solution is 0.94 ± 0.04, and for the MA-41 membrane, it is 0.85 ± 0.1. The possibility of calculating the transport numbers and predicting the open-circuit voltage based on simple physicochemical measurements allows selecting the best membrane pairs for the reverse electrodialysis process. Comparison of the open-circuit potential value calculated using the obtained transfer numbers with experimental data showed that in the case of using Ralex membranes, the difference between the experimental and calculated values is 2%. The calculated value of the open circuit potential was 0.19 V/membrane pair or 1.69 V for the investigated reverse electrodialyzer with nine pair chambers.

An urgent task is the development of new resource-saving technologies for deep processing of wastes from the hydrometallurgical industry for the purpose of their reuse. Membrane technologies make it possible to create closed technological cycles with the reuse of recovered components in production, which allows solving many environmental problems. At the Abinsk Electric Steel Works Ltd. (Russia), during the production of copper-coated steel wire, a large amount of waste containing sulfuric acid and heavy metal salts is generated. The chemical treatment of such effluents with slaked lime and alkali produces a large amount of sludge, which causes environmental problems and leads to the irreversible loss of sulfuric acid. The problem of separating acids and salts can be solved using diffusion dialysis through anion-exchange membranes, however, to return the acid to the production cycle, the purified acid must be additionally concentrated. In this work, we studied the process of electrodialysis concentration of sulfuric acid using heterogeneous ion-exchange membranes Ralex® CMHPP and Ralex® AMHPP (manufactured by MEGA a.s., Czech Republic) which have a polypropylene reinforcing mesh resistant to acids. The main parameters of the electrodialysis concentration process have been determined – the dependence of the concentration of the regenerated sulfuric acid on the concentration at the inlet to the electrodialysis cell and on the current density, as well as the energy consumption for the process. It is shown that with the help of electrodialysis concentration it is possible to obtain sulfuric acid with a concentration of up to 180 g/L, which makes it possible to return it to the production cycle.