Processing of spinel-bearing compounds for zinc extraction

Abstract

This thesis studies the zinc extraction from spinels through hydro and pyrometallurgical processing. Two zinc-bearing spinels are covered: zinc ferrite ZnO·Fe2O3 to a limited extent and gahnite ZnO·Al2O3 as the main subject, compounds which are found naturally on the Earth’s crust as well as in industrial residues from the zinc industry, steel industry and others. Zinc ferrite contains 27 % of Zn and 33 % as ZnO; resource recovery from ferrite has been studied already in the past. On the other hand, the processing of gahnite, containing 35 % of Zn and 44 % as ZnO, is studied more extensively since research in the field of extractive metallurgy is effectively non-existent. Hence, the main objective of the present thesis is finding routes of treatment for this spinel. Zinc ferrite was produced synthetically at the CiTG/3mE labs by mixing equimolar amounts of ZnO and Fe2O3 at 1100 °C. Gahnite was produced by an analog method, a mixture of equimolar amounts of ZnO and Al2O3. The first approach was hydrometallurgical. Atmospheric hot acid leaching (4 M, 95 °C, 120 min, L/S 40) was performed with H2SO4, HCl and HNO3, resulting in a non-detected dissolution of the compound. Pressure leaching (90 min, L/S 40) was carried out in an autoclave with H2SO4 and HNO3, resulting in a low (2.9 %; 0.75 M, 140 °C, 3.6 bar) and a moderate extraction (22.2 %; 4.0 M, 250 °C, 39.7 bar) respectively. The second approach was pyrometallurgical processing (60 min dwell, 10 °C/min heating rate), divided into two sub-routes. A series of carbothermic tests (1:1.25 stoichiometric ratio) successfully led to a full reduction of the spinel at 1300 °C (99.90 % extraction of zinc). Aluminothermic tests (1.5:2 stoichiometric ratio) successfully resulted in a 99.98 % zinc extraction at 1200 °C. The mix of gahnite and ferrite with carbon at 1300 °C produced a 99.65 % extraction of the metal. Addition of ZnO to the previous mixture resulted in a 100 % extraction, at 1300 °C. Further experiments with gahnite at 1200 °C by adding SiO2, first with carbon and later with aluminium, resulted in a moderate 23.14 % and a low 4.69 % extraction correspondingly. Trials with CaO at 1400 °C created a glass residue and a slag, in each case. It is thus possible to establish the zinc extraction from gahnite ZnO·Al2O3 as follows: Route / Zinc extraction Atmospheric acidic leaching / Non-detected Pressure leaching / Low – Moderate Reduction with aluminium and silica / Low Reduction with carbon and silica / Moderate Carbothermic reduction / Full Aluminothermic reduction / Full