Investigating Exchange Efficiencies of Sodium and Magnesium to Access Lithium from β-Spodumene and Li-Stuffed β-Quartz (γ-Spodumene)

Abstract

After the high-temperature pretreatment of α-spodumene to induce a phase transition to β-spodumene, a derivative of the silica polymorph keatite, often coexisting with metastable Li-stuffed β-quartz (γ-spodumene), the conventional approach to access lithium is through ion exchange with hydrogen using concentrated sulfuric acid, which presents drawbacks associated with the production of low-value leaching residues. As sodium and magnesium can produce more interesting aluminosilicate byproducts, this study investigates Na+ ↔ Li+ and Mg2+ ↔ 2 Li+ substitution efficiencies in β-spodumene and β-quartz. Thermal annealing at 850 °C of the LiAlSi2O6 silica derivatives mixed with an equimolar proportion of Na endmember glass of equivalent stoichiometry (NaAlSi2O6) indicates that sodium incorporation in β-quartz is limited, whereas the main constraint for not attaining complete growth to a Na0.5Li0.5AlSi2O6 β-spodumene solid solution is co-crystallization of minor nepheline. For similar experiments in the equimolar LiAlSi2O6-Mg0.5AlSi2O6 system, the efficient substitution of Mg for Li is observed in both β-spodumene and β-quartz, consistent with the alkaline earth having an ionic radius closer to lithium than sodium. Ion exchange at lower temperatures was also evaluated by exposing coexisting β-spodumene and β-quartz to molten salts. In NaNO3 at 320 °C, sodium for lithium exchange reaches ≈90% in β-spodumene but less than ≈2% in β-quartz, suggesting that to be an efficient lithium recovery route, the formation of β-quartz during the conversion of α-spodumene needs to be minimized. At 525 °C in a molten MgCl2/KCl medium, although full LiAlSi2O6-Mg0.5AlSi2O6 solid solution is observed in β-quartz, structural constraints restrict the incorporation of magnesium in β-spodumene to a Li0.2Mg0.4AlSi2O6 stoichiometry, limiting lithium recovery to 80%.

Keywords

• α-spodumene
• β-spodumene_ss
• keatite_ss
• γ-spodumene
• β-quartz_ss