Supercritical fluid extraction of alkali metal ions using crown ethers with perfluorocarboxylic acid from aqueous solution

S. Mochizuki, N. Wada, R. Smith, H. Inomata
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引用次数: 15

Abstract

The extraction of alkali metal ions from aqueous solution (K+, Na+ : 1.7 × 10–4 mol dm–3) with supercritical CO2 (scCO2) and crown ethers [18-crown-6 (18C6), 15-crown-5 (15C5)] as ligand was investigated at 40 °C and 8.0–18.0 MPa. The recovery for potassium ion was 1–2% with 18C6 and was independent of pressure. Remarkably, the recovery increased to 40–60% in the presence of the additive pentadecafluoro-n-octanoic acid (PFOA), which is probably because PFOA has CO2-philic fluoroalkyl chains, and easily generates counter ions for the metal–ligand complex. In the case of sodium, the recovery was found to be low even with PFOA, which may be related to the cavity size of 18C6. The 15-crown-5 ligand, having the smaller cavity size increased sodium recovery up to 20–40%. These results show that alkali metals can be extracted with scCO2 and crown ether ligands and further that the recovery of the metals can be greatly increased by adding a substance that can supply a CO2-philic counter ion.
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用冠醚和全氟羧酸从水溶液中超临界萃取碱金属离子
以超临界CO2 (scCO2)和冠醚[18-冠-6 (18C6), 15-冠-5 (15C5)]为配体,在40℃,8.0 ~ 18.0 MPa条件下对水溶液(K+, Na+: 1.7 × 10-4 mol dm-3)中碱金属离子的萃取进行了研究。18C6对钾离子的回收率为1-2%,且与压力无关。值得一提的是,在添加剂五氟辛酸(PFOA)的存在下,回收率提高到40-60%,这可能是因为PFOA具有亲co2的氟烷基链,容易生成金属配体配合物的反离子。在钠的情况下,即使添加PFOA,回收率也很低,这可能与18C6的空腔大小有关。15冠-5配体具有较小的腔体尺寸,可使钠的回收率提高20-40%。这些结果表明,用scCO2和冠醚配体可以提取碱金属,并且通过添加一种可以提供亲co2反离子的物质可以大大提高金属的回收率。
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