Selective Separation of Lithium, Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors

Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202216011. doi: 10.1002/anie.202216011. Epub 2023 Jan 31.

Abstract

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li+ from Ca2+ , Mg2+ , Na+ and K+ . The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li+ at pH 6.0 was 94 % when Mg2+ and Ca2+ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

Keywords: 4-Phosphoryl Pyrazolone Ligands; Ca/Mg/Li Separation; Di- and Trinuclear Complexes; Separation Science; pH-Regulated Receptors.