Selective separation of light and heavy rare earth elements from acidic mine waters by integration of chelating ion exchange and ligand impregnated resin

Abstract

This study addresses the potential of sourcing Critical Raw Materials (CRMs) using Acidic Mine Waters (AMWs) as a secondary resource. AMWs, often viewed as waste, contain valuable metals like zinc and copper, as well as critical metals like magnesium and cobalt. Moreover, recent studies also reported the presence of Rare Earth Elements (REEs) at concentrations (mg/L) that make their extraction both technically and economically viable. The research focuses on a circular process to recover these metals from AMWs, specifically from the Aznalcóllar open-pit mine, which contains 216 mg/L of Al, 47 mg/L of Fe, 547 mg/L of Zn, and 18.56 mg/L of REEs. The proposed method involves pre-treating the AMW to remove Fe and Al, achieving removals of over 99.9 % and 90 %, respectively, at pH 4.5. Following this, transition metals like Zn, Cd, and Cu were removed as sulphides with a removal efficiency exceeding 99 %. This pre-treatment step reduced the concentration of competing metals in the ion-exchange process, thereby enhancing the recovery and purity of REEs. To separate heavy and light REEs, two types of resins in series were used: an impregnated resin (TP272) and a chelating resin (S930), which can be regenerated using sulphuric acid (H2SO4). The final recovery of REEs as oxalates was achieved using oxalic acid and ammonia at pH 1, with further optimization of the elution process to minimize ammonia consumption and undesired precipitation of other oxalates. Finally, REE oxalates with purities exceeding 90 % were obtained. This research demonstrates a sustainable method for efficiently recovering valuable REEs from AMWs, while also addressing environmental concerns related to hazardous sludge generation.