Mechanism of Selective Extraction and Separation of Vanadium and Aluminum from Oxalic Acid Leachate of Shale: Experimental Investigation and DFT Calculations

Oxalic acid serves as an environmentally benign leaching agent, exhibiting strong reducing and complexing capabilities. In the oxalic acid leachate derived from vanadium-bearing shale, aluminum ions are present as major impurities. Achieving efficient and deep separation of vanadium from aluminum remains a key technical challenge. This study investigates the selective separation of vanadium and aluminum from oxalic acid leaching solutions using solvent extraction with Aliquat 336, supported by density functional theory (DFT) calculations. Experimental results demonstrate that, under optimized conditions, Aliquat 336 enables effective separation of vanadium from aluminum. DFT analysis elucidates the molecular-level interaction mechanism, revealing that the binding affinity of Aliquat 336 for [VO(C2O4)2]2− (ΔG = −287.96 kJ/mol) is significantly stronger than for [Al(C2O4)2]− (ΔG = −186.68 kJ/mol). These results provide a solid thermodynamic basis for the observed selectivity and establish a robust theoretical framework for developing high-efficiency separation processes. This work thus clarifies, for the first time, the mechanistic foundation of vanadium–aluminum separation in oxalic acid systems.