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.

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.

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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.