Selective extraction of lithium over alkali and alkaline earth ions by synergistic solvent extraction†

Abstract

Direct lithium extraction (DLE) from natural surface and geothermal brines is very challenging due to the low ratio of lithium to other metals, and the lack of suitable materials that bind lithium with sufficiently high selectivity. In this paper, a synergistic solvent extraction system is described that comprises a liquid ion exchanger (saponified bis(2-ethylhexyl)dithiophosphoric acid) and a lithium-selective ligand (2,9-dibutyl-1,10-phenanthroline) in an aliphatic diluent. The extraction mechanism was investigated and was confirmed to involve the binding of lithium to the selective ligand, while the liquid ion exchanger facilitates the transfer of metal ions from the aqueous to the organic phase. The variables influencing the selectivity for lithium were also determined. The selectivity improved greatly in highly concentrated salt solutions with low concentrations of lithium, rendering the process ideal for the sequestration of lithium from natural brines. Stripping could be achieved with stoichiometric amounts of hydrochloric acid. Applying the system to a synthetic geothermal brine, an extraction percentage of 68% was obtained in a single stage, with separation factors of 620 ± 20 for lithium over sodium, 3100 ± 200 for lithium over potassium, 596 ± 9 for lithium over magnesium and 2290 ± 80 for lithium over calcium.