Junya Cao, Zhen Meng, Jianfeng Zhang, Qiyu Meng, Wei Meng, Li Wang, Huiyong Wu, Marco Wenzel, Jan J. Weigand, Huizhou Liu, Liangrong Yang
Direct and efficient recovery of lithium from precipitation mother liquor has garnered increasing attention, but challenges remain due to the low concentration of Li + and high Na + excess. To address these issues, we proposed a synergistic extraction system using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) as the extractant and Cyanex 923 as the synergist, which exhibits high selectivity for lithium in industrial mother liquors. In a single-stage extraction, HPMBP-Cyanex 923 achieved 85% Li + extraction with only 4% Na + and K + from a real mother liquor solution containing 1.46 g/L Li +, 67 g/L Na + and 2.57 g/L K + . The total organic carbon (TOC) test showed that HPMBP-Cyanex 923 exhibited significantly lower dissolution loss (220 mg/L) compared to that of the commonly used benzoyl-1,1,1-trifluoroacetone (HBTA, 432 mg/L), indicating superior hydrophobicity, which is essential for a green extraction process. The results demonstrate that 97% Na + in the organic phase can be scrubbed prior to Li + stripping, and much lower acid concentration (0.2 M HCl) is required to strip the lithium due to a lower p K a value of pyrazolone compared to traditional β-diketones. Single-crystal analysis, slope analysis, and DFT calculations revealed the observation of a binuclear structure, [Li 2 (PMBP) 2 (TBPO) 2 ], which could serve as a general structural formula for systems involving pyrazolones and an organophosphorus co-ligand with a short alkyl chain. This work presents a novel lithium extraction system that offers enhanced selectivity and hydrophobicity, along with a lower stripping acid requirement compared to traditional β-diketones. These features make it highly promising for future industrial applications.