Efficient Recovery of Valeric Acid Using Phosphonium-Based Ionic Liquids

This study explores the application of phosphonium-based ionic liquids (ILs) for the efficient separation of valeric acid (VA) through reactive liquid-liquid extraction. Two hydrophobic quaternary phosphine ILs, trihexyl(tetradecyl)phosphonium decanoate (C103) and trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (C104), were evaluated in combination with heptane as a diluent. Extraction efficiency was experimentally determined at different levels of extraction process factors in terms of aqueous phase pH (3-6), IL concentration (0-120 g/L), and process temperature (25-60 °C). For each IL, extraction efficiency was predicted using a response surface regression model, and the process factors were optimized based on the desirability function approach. Both ILs effectively extracted VA, with optimal mean values of extraction efficiency of 98.61% for C103 and 99.24% for C104 under optimal conditions (pH of 3.8 and 4, respectively, IL concentration of 60 g/L, and temperature of 25 °C). Mechanistic analysis revealed that VA extraction occurs through the formation of IL-acid complexes, involving hydrogen bonding between the non-dissociated acid and the IL anion. Depending on the extractant concentration, 1:1 and 2:1 acid-to-IL stoichiometric ratios were observed. These findings highlight the potential of phosphonium-based ILs, particularly in a heptane-diluted system, as high-performance extractants for carboxylic acid separation.