METALS RECOVERY FROM SPENT Zn-MnO2 BATTERIES BY HYDROMETALLURGY

A hydrometallurgical process for recycling spent Zn-MnO2 batteries was developed, involving leaching with sulfuric acid, purification by precipitation and metals separation for further recovery. Leaching of zinc oxide was easily attained while for manganese oxide was rather difficult depending on temperature and acid concentration. At 90oC and with the liquid/solid ratio of 20 L/kg, more than 95% of zinc is recovered in 30 minutes with 0.5M H2SO4. To attain similar recovery for manganese, higher levels of acid concentration and time are needed (e.g 0.7 M and 2 hours). After leaching a purification step is necessary to remove iron co-dissolved through Fe(III) precipitation. Separation of zinc from manganese by solvent extraction with 1M DEHPA follows in the process route. The countercurrent multistage separation diagram developed allows the production of a zinc electrolyte with 120 g/L Zn and 0.005 g/L Mn, and a raffinate with 16 g/L Mn and 0.013 g/L Zn. Introduction The recycling of spent Zn-MnO2 batteries is carried out by dedicated recyclers using several process alternatives [1]. Most of the running processes use pyrometallurgical technologies [2] based on zinc distillation. Alternative treatments by hydrometallurgy have been reported [3-5] but its application is scarce. In order to contribute to the development of alternative solutions, a process for recycling batteries based on Zn-MnO2 systems has been studied. The process is based on the hydrometallurgical treatment of spent batteries in sulfuric acid media (Figure 1). The process starts with the physical processing by shredding using cutting grinders, where the batteries are opened and size reduced, allowing the liberation of the interior electrode particles or pastes. The fines can be then separated and the coarse material containing the steel scrap can be treated to remove the remaining aggregate electrode. The final scrap also contains some plastics and other non-metal materials and can be further valorized. The chemical treatment is carried out by leaching of the zinc and manganese oxides with sulfuric acid with formation of soluble metal sulfates. Some iron also dissolves and a purification step is thus necessary to remove iron from solution by oxidation/precipitation. The resulting leach liquor rich in Zn and Mn is processed by solvent extraction with di(2-ethylhexyl) phosphoric acid DEHPA, where zinc is selectively extracted against manganese, leading to a pure manganese raffinate for recovery as a salt or precipitate (e.g. manganese sulfate or oxide/hydroxide). The organic extract containing zinc is stripped with an acidic electrolyte and