Opposite selectivities of tri‐n‐butyl phosphate (TBP) and Cyanex 923 in solvent extraction of lithium and magnesium

The synergic solvent extraction system of tri-n-butyl phosphate (TBP) and FeCl3 (or ionic liquids, ILs) has been extensively studied for selective extraction of Li from Mg-containing brines. However, Cyanex 923 (C923), which extracts many metals stronger than TBP, has not yet been examined for Li/Mg separation. Here, we report on the unexpected observation that the C923/FeCl3 system has opposite Li/Mg selectivity compared to the TBP/FeCl3 system. Detailed investigations show that the opposite selectivity of the C923/FeCl3 (or IL) system is due to three factors: (1) the strong extraction of Fe by C923 leads to a low concentration of [FeCl4]- in the system, which is essential for Li extraction; (2) C923 in combination with an IL extracts Mg strongly by an ion-pair mechanism; (3) most importantly, C923 extracts Mg by solvation, resulting in an insufficient concentration of C923 for Li extraction. The unexpected poor Li/Mg selectivity of C923 highlights the irreplaceable role of TBP in the selective recovery of Li.