Solubility and Modeling of Li₂SO₄·H₂O in Aqueous H₂SO₄–MgSO₄ Solutions for Lithium Extraction from Spodumene

Abstract

Lithium extraction from spodumene (LiAlSi2O6) is of great importance to meet the increasing demand for lithium-ion batteries used in electric energy storage. However, conventional processing of spodumene involves enormous consumption of H2SO4 during the neutralization step. We propose a new flowsheet to avoid wasting H2SO4 by adding a cooling crystallization step to crystallize lithium sulfate as Li2SO4·H2O. To advance the process development, the solubilities of Li2SO4·H2O in the system H2SO4–MgSO4–H2O from 283.15 to 353.15 K were measured experimentally via a dynamic method. Chemical modeling for the solubility was carried out by regressing the mixed solvent electrolyte model parameters with the average absolute relative deviation of less than 2%. The newly built model is capable of calculating the solubility of Li2SO4·H2O in aqueous H2SO4–MgSO4 solutions in wide concentration and temperature ranges. Cooling crystallization of Li2SO4·H2O in concentrated H2SO4 was conducted and its feasibility was proved.