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.
Keywords: acid recovery; concentration; diffusion dialysis; electrodialysis; ion-exchange membrane; separation of acids and salts.