Deblonde Gauthier J-P, Chagnes Alexandre, Roux Marie-Aude, Weigel Valérie, Cote Gérard
PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, 11 rue Pierre et Marie Curie, 75005 Paris, France.
Eramet Research, Hydrometallurgy department, F-78193 Trappes, France.
Dalton Trans. 2016 Dec 6;45(48):19351-19360. doi: 10.1039/c6dt03873e.
Solvent extraction of Nb(v) from alkaline aqueous media using quaternary ammonium solutions, especially Aliquat® 336 diluted in an aliphatic diluent, was investigated. The hexaniobate ions (HNbO) were extracted into the organic phase with very high yields at room temperature and within a few minutes, affording easy access to organic solutions of hexaniobates. Several parameters were found to influence the extraction of HNbO including the nature and concentration of alkali cations, confirming subtle effects previously described for polyoxoniobates such as ion-pairing with alkali ions. The extraction of HNbO with Aliquat® 336 is also influenced if competing anions are present in the aqueous phase (NO, Cl, CO, SO and CO) and varies with the pH mainly due to the competitive extraction of hydroxide ions at high pH. The co-extraction of sodium ions with HNbO was observed as well as the co-extraction of water molecules, suggesting a self-association of the extractant. The proposed liquid-liquid extraction generic system paves the way for innovative niobium (and potentially tantalum) hydrometallurgical processes and it may also afford more direct routes for exploring the chemistry of hexaniobates in organic solvents.
研究了使用季铵溶液,特别是稀释在脂肪族稀释剂中的Aliquat® 336,从碱性水介质中溶剂萃取铌(V)。在室温下几分钟内,六铌酸根离子(HNbO)以非常高的产率被萃取到有机相中,从而易于获得六铌酸盐的有机溶液。发现几个参数会影响HNbO的萃取,包括碱金属阳离子的性质和浓度,证实了先前对聚氧铌酸盐所描述的微妙效应,如与碱金属离子的离子对作用。如果水相中存在竞争性阴离子(NO、Cl、CO、SO和CO),Aliquat® 336对HNbO的萃取也会受到影响,并且主要由于在高pH下氢氧根离子的竞争性萃取,萃取率会随pH值变化。观察到钠离子与HNbO的共萃取以及水分子的共萃取,这表明萃取剂存在自缔合现象。所提出的液 - 液萃取通用体系为创新的铌(以及潜在的钽)湿法冶金工艺铺平了道路,并且它还可能为探索六铌酸盐在有机溶剂中的化学性质提供更直接的途径。