Selective Leaching of Rare Earth Elements from Ion-Adsorption Rare Earth Tailings: A Synergy between CeO₂ Reduction and Fe/Mn Stabilization

The increasing demand for rare earth elements (REEs) motivates the development of novel strategies for cost-effective REE recovery from secondary sources, especially rare earth tailings. The biggest challenges in recovering REEs from ion-adsorption rare earth tailings are incomplete extraction of cerium (Ce) and the coleaching of iron (Fe) and manganese (Mn). Here, a synergistic process between reduction and stabilization was proposed by innovatively using elemental sulfur (S) as reductant for converting insoluble CeO₂ into soluble Ce₂(SO₄)₃ and transforming Fe and Mn oxides into inert FeFe₂O₄ and MnFe₂O₄ spinel minerals. After the calcination at 400 °C, 97.0% of Ce can be dissolved using a diluted sulfuric acid, along with only 3.67% of Fe and 23.3% of Mn leached out. Thermodynamic analysis reveals that CeO₂ was indirectly reduced by the intermediates MnSO₄ and FeS in the system. Density functional theory calculations indicated that Fe­(II) and Mn­(II) shared similar outer electron arrangements and coordination environments, favoring Mn­(II) over Ce­(III) as a replacement for Fe­(II) in the FeO₆ octahedral structure of FeFe₂O₄. Further investigation on the leaching process suggested that 0.5 mol L^–1 H₂SO₄ is sufficient for the recovery of REEs (97.0%). This research provides a promising strategy to selectively recover REEs from mining tailings or secondary sources via controlling the mineral phase transformation.