Leaching of Li-bearing sedimentary claystones using organic acids

Abstract

Sedimentary claystones are a significant Li source. Currently, conventional sulfuric acid leaching is preferred for the extraction of Li from claystone; however, there are certain environmental concerns and selectivity issues. This study evaluated the use of organic acids for leaching Nevada claystone and compared their performance with that of sulfuric acid. Five organic acids: oxalic, ascorbic, citric, malic, and tartaric acids, were tested under identical conditions (1 M acid concentration, 80 °C, 1/10 g/mL solid-to-liquid ratio (S/L)) between 1 and 24 h using three Li-bearing claystone types. Oxalic acid demonstrated excellent Li extraction efficiency, comparable to that of sulfuric acid, leaching over 80% of Li in 1 h and exhibiting high selectivity for Li over Ca in all claystone samples. Ion exchange rather than mineral dissolution has been suggested as the primary mechanism of Li extraction. Analyses of the pregnant leach solution (PLS) and solid residues from 1-h sulfuric and oxalic acid leaching showed results that were tied to ion exchange tendencies, as the silicate frameworks remained intact after leaching. Citric, malic, and tartaric acids showed potential for Li extraction, although their leaching kinetics were slower, requiring longer durations to achieve comparable results. However, ascorbic acid exhibited considerably low Li extraction efficiency across the three claystones. An economic assessment revealed oxalic acid to be the most cost-effective organic acid, with the added benefits of potential recovery and reuse.

Keywords

Lithium / Organic acids / Sulfuric acid / Sedimentary claystone

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