Technological Indicators of the Cathodic Process in the Regeneration of Used Sulfo-Acid Solutions for Etching Steel

Abstract

The current state of regeneration of sulfate solutions was analyzed, it was established that the existing physico-chemical methods do not solve the problem of regeneration of sulfuric acid, but only neutralize it, for transfer according to the standards of the MPC to neutralization and into the sewage system with subsequent disposal. It has been confirmed that it is advisable to carry out the regeneration by an electrochemical method using a three-chamber electrolyzer, when the solution is fed into the middle chamber, the concentration of regenerated sulfuric acid increases to 180-200 g/l, with simultaneous iron deposition, with a current yield of 65-70%. This method reduces waste and allows switching to a closed cycle on sulfuric acid. It was found that in the process of digestion, the concentration of sulfuric acid decreases from 2.0 to 0.5 mol·dm-3, and the concentration of iron (II) sulfate increases accordingly. Under the conditions of a decrease in the concentration of sulfuric acid, its chemical activity also decreases when interacting with iron oxides and hydroxides. To increase the reactivity of pickling solutions, an increase in the temperature of the entire process is used. The kinetic regularity of combined cathodic processes in model solutions of iron (II) sulfate with sulfuric acid was established. Platinum, copper and carbon steel were used as cathode material. The choice of the cathode material was based on the different electrochemical properties of these selected metals with respect to the hydrogen reaction. The main process at the platinum cathode is hydrogen release in a wide range of current densities. At current densities greater than 0.1 A/cm2, a sharp increase in potential was observed due to the incorporation of Fe2+ into the composition of the cathode-electrolyte interface, but Fe2+ reduction potentials were not reached. When replacing the cathode material from platinum to carbon steel, a significant inhibition of hydrogen release was observed, which made it possible to reach the potentials for the simultaneous reduction of hydrogen and iron, however, the maximum current of the rectilinear section of the electrochemical process with electrochemical control was reduced from 10 at 20 0C to 3 times at 80 0C. The use of a copper cathode made it possible to reveal the influence of the hydrogen reaction on the course of Fe2+ reduction. The release of hydrogen at the copper cathode was accompanied by a significant inhibition of the hydrogen ion discharge. When using an iron cathode, electrochemical desorption is the limiting stage, which leads to the existence of layers of adsorbed hydrogen firmly attached to the surface of the iron cathode. A comparative analysis of the voltage-current dependences for the final investigated temperatures indicates a significant effect of an increase in temperature from 20 0C to 80 0C by approximately 120-150 mV. The cathodic process at 20 0C takes place in the mode of increased kinetics for both combined processes. At 80 0С, rectilinear sections of electrochemical control of the cathodic process appear on the voltage–voltage dependences, at Fe2+ concentrations of 1.0 and 1.5 mol/dm3. These areas range from 20 to 60 mA/cm2. The concentration of iron ions and the temperature of electrolysis have a significant effect on the process of electrochemical reduction of Fe2+, which was confirmed experimentally. Since the target process in the electrochemical regeneration of spent pickling solutions is the regeneration of sulfuric acid itself, and not the removal of Fe2+ from this solution, the cathodic mode of operation of the electrode unit was determined according to the technological indicators of the anodic process.