Separation of tantalum and niobium by solvent extraction

Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.Niobium (Nb) and tantalum (Ta) are found in the same group (VB) of the periodic table of elements and therefore have similar chemical properties, which is the reason why they are difficult to separate. They are usually found together in various minerals of which the most important are columbite ((Fe, Mn, Mg)(Nb, Ta)2O6) and tantalite ((Fe, Mn)(Nb, Ta)2O6). Several methods have been used to separate Nb and Ta. Most methods use very high concentrations of hydrofluoric acid (HF) and sulphuric acid (H2SO4) as the aqueous phase, tributyl phosphate (TBP) as the extractant and methyl isobutyl ketone (MIBK) as the organic phase. High extraction can be achieved, but the reagents used are hazardous. With the increasing demand of both pure Ta and Nb, as well as stricter environmental requirements, a need exists to develop a more efficient and safer technique to separate Ta and Nb. In this project the focus was on the solvent extraction (SX) of Ta and Nb with the possible application in a membrane-based solvent extraction (MBSX) process. For this purpose, eight different extractants were investigated, namely the cation exchangers di-iso-octyl-phosphinic acid (PA) and di-(2-ethylhexyl)-phosphoric acid (D2EHPA), the neutral solvating extractant 2-thenoyl-trifluoro- acetone (TTA), and the anion exchangers Alamine 336, Aliquat 336, 1-octanol, 2-octanol and 3-octanol. The extractant to metal ratio was varied from 0.1:1 to 10:1, while cyclohexane was used as diluent and 3% v/v 1-octanol was used as modifier for the organic phase. In addition, four different acids, hydrochloric acid (HCl), nitric acid (HNO3), sulphuric (H2SO4) and perchloric acid (HClO4), were used at different concentrations to determine the best combination for extraction. First, fluoride salts of Ta and Nb (Ta(Nb)F5) were tested and the optimum results showed that the highest extraction was obtained with PA and D2EHPA, irrespective of the type of acid used. Similarly, irrespective of the acid used, extraction with PA and D2EHPA increased with increasing acid concentration, followed by Alamine 336, Aliquat 336 and then TTA and the octanols. Extraction values of 97% Ta at 15 mol/dm3 and 85% Nb between 12 and 15 mol/dm3 were obtained. Although extraction of both Ta and Nb was achieved with all the acids tested, only H2SO4 showed sufficient separation (log D = 3) of the two metals in the 0 to 2 mol/dm3 acid range and 15 mol/dm3 for PA and D2EHPA, respectively. Precipitation, probably due to hydrolysis of the metals, occurred in the absence of acid when using Alamine 336, Aliquat 336 and TTA. The octanols showed the least amount of extraction of Ta and Nb, irrespective of the acid investigated. The optimum extraction was achieved with an E/M ratio of 3:1 of PA and D2EHPA as the extractant and 10 mol/dm3 H2SO4 in the aqueous phase. The NH4Ta(Nb)F6 salt solution was investigated using the optimum conditions for maximum extraction obtained from the Ta(Nb)F5 experiments, i.e. 4 mol/dm3 H2SO4 with an E/M ratio above 3:1 for the extractant PA and 4 mol/dm3 H2SO4 with an E/M ratio of 20:1 for the extractant D2EHPA. Kinetic equilibrium for PA was reached after 10 minutes and for D2EHPA after 20 minutes. The highest extraction of Ta (100%) above 3 mol/dm3 H2SO4 and Nb (54%) at 8 mol/dm3 with the highest separation factor of 4.7 with PA was achieved, followed by the 100% extraction of Ta above 5 mol/dm3 and 40% Nb at 10 mol/dm3 with the highest separation factor of 4.9 in D2EHPA. Although the aim of this study was the extraction and separation of Ta and Nb, the recovery or back extraction of the metals from the organic phase, as well as the membrane-based solvent extraction (MBSX) was briefly investigated. From the preliminary results obtained it became apparent that further research into the different aspects, including the type of stripping agent used, stripping agent concentration, effect of Ta to Nb ratio and different sources of Ta and Nb is needed to obtain the optimum conditions for the MBSX process and the subsequent recovery of Ta and Nb.Master