Advances in Lithium Extraction from Spodumene: Alternatives to Sulfuric Acid Digestion

Conventional lithium extraction from spodumene via sulfuric acid roasting can achieve up to 98% recovery but suffers from high energy use, acidic residues, and purification complexity. This review evaluates alternative methods for both α- and β-spodumene, aiming for improved sustainability. For α-spodumene, Na2SO4–CaO salt roasting achieved >95% recovery at 900 ◦C via water leaching. Sodium carbonate roasting–NaOH leaching and mechanical activation–Na2SO4 roasting reached 95.9% and ~92%, respectively. High-pressure NaOH leaching reached 95.8%, while alkaline decomposition–acid leaching yielded 53.2–84.1%. Microwave-assisted calcination achieved up to 97% recovery, and fluoride-based roasting gave 93–98% but raised environmental concerns. Bioleaching is eco-friendly but slow, with <3.5% recovery. For β-spodumene, high-pressure leaching using sodium carbonate (>94%), sodium sulfate (90.7%–93.3%), sodium chloride (~93%), and nitric acid (~95%) provided high recoveries. Atmospheric leaching with HF and H3PO4 yielded ~90% and ~40%, respectively, while carbonic acid leaching reached 75% after multiple stages. Chlorination roasting achieved near-complete recovery. The Metso-Outotec high-pressure sodium carbonate leaching process is set for industrial-scale implementation at the Keliber project in 2025, confirming its scalability.