Pyrite (FeS2) is the primary form of sulfur that occurs within colliery spoil. It is frequently present in base metal sulfide deposits. It is oxidized to ferrous sulfate (FeSO4) and sulfuric acid (H2SO4) when exposed to atmospheric factors. In the desulphurization of coal/mine stone as well as in the extraction of copper from abundant copper pyrite called chalcopyrite, the aim is the dissolution of pyrite. Copper and sulfuric acid are the primary products in the chalcopyrite (CuFeS2) mining industry. A large amount of acidic wastewater is generated during the flue gas pre-treatment system. Thus, this work aims to apply the electrodialysis (ED) membrane process to recovery sulfuric acid from waste acid liquor. Cationic ion exchange was used as a pre-treatment process to remove heavy metals before the ED system. The fate and transport of heavy metals (Zn, Cd, Cu, Pb, Ni, and As) and operational parameters (conductivity, current, pH, etc.) were monitored for the evaluation of the recovery system. The work performed in the relevant industrial environment confirms that the ED process may recover 90% acid from wastewaters of the chalcopyrite mining industry. Additionally, both obtained acid and recovered water have enough quality to be reused in the chalcopyrite industrial processing line. Thus, the ED-based recovery systems may provide environmentally and economically solutions in a circular economy concept.