Abstract
A solvent extraction method has been employed to extract and separate zirconium and hafnium from the nitric acid medium using Cyanex-272 and its mixture with TBP in kerosene. The effects of the experimental parameters such as contact time between phases, aging time, nitric acid concentration, Cyanex-272 and TBP concentration on the metals separation, and various stripping agents on the metals back extraction from the loaded organic phase have been investigated. The maximum separation factor of 16 was obtained in the single extraction system with 1% (v/v) Cyanex-272 from 2.5 M HNO3 solution. The combination of Cyanex-272 with TBP exhibited a significant synergistic effect for Zr extraction and the antagonistic effect for Hf extraction. The proposed novel synergistic mixture consisting of 0.5% (v/v) Cyanex-272 and 20% (v/v) TBP in kerosene offered the maximum separation factor of 99.7 from 2.5 M HNO3 solution. By applying a slope method, the extracted zirconium species were proposed to be ZrO(NO3)2·2Cyanex272·2TBP in the organic phase. Among the investigated stripping agents, 4 M H2SO4 solution showed the best efficiency for the stripping of zirconium and hafnium from the loaded mixture of Cyanex-272 and TBP with separation factor of 10.1.
References
1. Nielsen, R., Wah, T., Albany, A.: Ullmann’s encyclopedia of industrial chemistry, Teledyne Wah Chang, Albany (2003), p. 697.Search in Google Scholar
2. Hure, J., Rastoix, M., Saint-James, R.: Données relatives aux équilibres chimiques régissant la séparation zirconium-hafnium: IIéme et IIIéme parties. Anal. Chim. Acta 25, 118 (1961).10.1016/S0003-2670(01)81530-0Search in Google Scholar
3. Biswas, R., Hayat, M.: Solvent extraction of zirconium (IV) from chloride media by D2EHPA in kerosene. Hydrometallurgy 63, 149 (2002).10.1016/S0304-386X(01)00220-1Search in Google Scholar
4. Nandi, B., Das, N. R., Bhattacharyya, S. N.: Solvent extraction of zirconium and hafnium. Solvent Extr. Ion Exch. 1, 141 (1983).10.1080/07366298308918397Search in Google Scholar
5. Gupta, B., Malik. P, Mudhar, N.: Extraction and recovery of zirconium from zircon using Cyanex 923. Solvent Extr. Ion Exch. 23, 345 (2005).10.1081/SEI-200050005Search in Google Scholar
6. Reddy, B. R., Kumar, J. R., Reddy, A. V.: Liquid-liquid extraction of tetravalent zirconium from acidic chloride solutions using Cyanex 272. Anal. Sci. 20, 501 (2004).10.2116/analsci.20.501Search in Google Scholar PubMed
7. Reddy, B. R., Kumar, J. R., Reddy, A.V., Priya, D. N.: Solvent extraction of zirconium (IV) from acidic chloride solutions using 2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (PC-88A). Hydrometallurgy 72, 303 (2004).10.1016/j.hydromet.2003.07.002Search in Google Scholar
8. Saberyan, K., Meysami, A. H., Rashchi, F., Zolfonoun, E.: Proposal of a new Hf (IV)/Zr (IV) separation system by the solvent extraction method. Chin. J. Chem. 26, 2067 (2008).10.1002/cjoc.200890369Search in Google Scholar
9. Reddy, K. J., Reddy, A. V., Shaibu, B., Reddy, M.: Enhanced extraction and separation of zirconium (IV) and hafnium (IV) with 3-phenyl-4-benzoyl-5-isoxazolone in presence of various neutral organophosphorus extractants. Radiochim. Acta 95, 289 (2007).10.1524/ract.2007.95.5.289Search in Google Scholar
10. Wang, L. Y., Lee, H. Y., Lee, M. S.: Solvent extraction of zirconium and hafnium from hydrochloric acid solutions using acidic organophosphorus extractants and their mixtures with TOPO. Mater. Trans. 54, 1460 (2013).10.2320/matertrans.M2013150Search in Google Scholar
11. Wang, L., Lee, H., Lee, M.: Solvent extraction separation of Zr and Hf from nitric acid solutions by PC 88A and its mixture with other extractants. Met. Mater. Int. 21, 166 (2015).10.1007/s12540-015-1020-xSearch in Google Scholar
12. Wang, L., Lee, H., Lee, M.: Solvent extractive separation of zirconium and hafnium from hydrochloric acid solutions by organophosphorous extractants and their mixtures with other types of extractants. Chem. Eng. Commun. 202, 1289 (2015).10.1080/00986445.2014.921621Search in Google Scholar
13. Wang, L. Y., Lee, M. S.: Separation of zirconium and hafnium from nitric acid solutions with LIX 63, PC 88A and their mixture by solvent extraction. Hydrometallurgy 150, 153 (2014).10.1016/j.hydromet.2014.10.009Search in Google Scholar
14. Taghizadeh, M., Ghasemzadeh, R., Ashrafizadeh, S., Saberyan, K., Maragheh, M. G.: Determination of optimum process conditions for the extraction and separation of zirconium and hafnium by solvent extraction. Hydrometallurgy 90, 115 (2008).10.1016/j.hydromet.2007.10.002Search in Google Scholar
15. Taghizadeh, M., Ghasemzadeh, R., Ashrafizadeh, S., Ghannadi, M.: Stoichiometric relation for extraction of zirconium and hafnium from acidic nitrate solutions with Cyanex-272. Hydrometallurgy 96, 77 (2009).10.1016/j.hydromet.2008.08.006Search in Google Scholar
16. Tian, M., Mu, F., Jia, Q., Quan, X., Liao, W.: Solvent extraction studies of zinc (II) and cadmium (II) from a chloride medium with mixtures of neutral organophosphorus extractants and amine extractants. J. Chem. Eng. Data 56, 2225 (2011).10.1021/je101245dSearch in Google Scholar
17. Flett, D.: New reagents or new ways with old reagents. J. Chem. Tec. Biotechnol. 74, 99 (1999).10.1002/(SICI)1097-4660(199902)74:2<99::AID-JCTB4>3.0.CO;2-SSearch in Google Scholar
18. Patil, A. B., Pathak, P., Shinde, V. S., Alyapyshev, M. Y., Babain, V. A., Mohapatra, P. K.: A novel dipicolinamide-dicarbollide synergistic solvent system for actinide extraction. Radiochim. Acta 102, 481 (2014).10.1515/ract-2013-2128Search in Google Scholar
19. Duan, H., Wang, S., Yang, X., Yuan, X., Zhang, Q., Huang, Z., Guo, H.: Simultaneous separation of copper from nickel in ammoniacal solutions using supported liquid membrane containing synergistic mixture of M5640 and TRPO. Chem. Eng. Res. Des. 117, 460 (2017).10.1016/j.cherd.2016.11.003Search in Google Scholar
20. Xiong, P., Zhang, Y., Huang, J., Bao, S., Yang, X., Shen, C.: High-efficient and selective extraction of vanadium (V) with N235-P507 synergistic extraction system. Chem. Eng. Res. Des. 120, 284 (2017).10.1016/j.cherd.2017.02.027Search in Google Scholar
21. Taghizadeh, M., Ghanadi, M., Zolfonoun, E.: Separation of zirconium and hafnium by solvent extraction using mixture of TBP and Cyanex 923. J. Nucl. Mater. 412, 334 (2011).10.1016/j.jnucmat.2011.03.033Search in Google Scholar
22. Banda, R., Lee, H. Y., Lee, M. S.: Separation of Zr from Hf in acidic chloride solutions by using TOPO and its mixture with other extractants. J. Radioanal. Nucl. Chem. 298, 259 (2013).10.1007/s10967-012-2349-ySearch in Google Scholar
23. Xu, G., Wang, W., Wu, J., Li, B., Wu, G., Shi, N.: Chemistry of nuclear fuels extraction. At. Energy Sci. Technol. 7, 487 (1963).Search in Google Scholar
24. Sato, T., Watanabe, H.: The extraction of zirconium (IV) from hydrochloric acid solutions by tricapryl methyl ammonium chloride. Anal. Chim. Acta 49, 463 (1970).10.1016/S0003-2670(00)86822-1Search in Google Scholar
25. Wang, L. Y., Lee, M. S.: A review on the aqueous chemistry of Zr (IV) and Hf (IV) and their separation by solvent extraction. J. Ind. Eng. Chem. 39, 1 (2016).10.1016/j.jiec.2016.06.004Search in Google Scholar
26. Ning, P., Cao, H., Zhang, Y.: Selective extraction and deep removal of tungsten from sodium molybdate solution by primary amine N1923. Sep. Purif. Technol. 70, 27 (2009).10.1016/j.seppur.2009.08.006Search in Google Scholar
27. Singhal, A., Toth, L., Lin, J., Affholter, K.: Zirconium (IV) tetramer/octamer hydrolysis equilibrium in aqueous hydrochloric acid solution. J. Am. Chem. Soc. 118, 11529 (1996).10.1021/ja9602399Search in Google Scholar
28. Mukherji, A. K.: Analytical Chemistry of Zirconium and Hafnium: International Series of Monographs in Analytical Chemistry, Pergamon Press Ltd., Headington Hill Hall, Oxford (1970).Search in Google Scholar
29. Shabana, R., Hafez, F.: Studies on the extraction behaviour of zirconium from mixed aqueous media with TBP. J. Radioanal. Nucl. Chem. 29, 99 (1976).10.1007/BF02516894Search in Google Scholar
30. Alcock, K., Bedford, F., Hardwick, W., McKay, H.: Tri-n-butyl phosphate as an extracting solvent for inorganic nitrates-I: Zirconium nitrate. J. Inorg. Nucl. Chem. 4, 100 (1957).10.1016/0022-1902(57)80091-8Search in Google Scholar
31. Nayl, A., El-Nadi, Y., Daoud, J.: Extraction and separation of Zr (IV) and Hf (IV) from nitrate medium by some CYANEX extractants. Sep. Sci. Technol. 44, 2956 (2009).10.1080/01496390903014169Search in Google Scholar
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