Preferential extraction of hafnium over zirconium with D2EHPA through selective complexation of organic acids

  • Jialin Zhao
  • Tao Yang
  • Hao Zhang
  • Guoxin Sun
  • Yu CuiEmail author


Nuclear grade zirconium and hafnium are important materials in nuclear power plants, which are usually produced with solvent extraction and separation technology. In this paper, the preferential extracting hafnium was successfully achieved by the selective complexation of the selected organic acids. Hydrochloric acid concentration, organic acid concentration, D2EHPA concentration were investigated to explore the optimum extraction conditions. Increasing acidity and extractant concentration was not conducive to the separation of zirconium and hafnium, while organic acid could effectively improve the separation factor, which was verified by ATR-FTIR spectroscopy. The largest separation factor, 9.936, for hafnium over zirconium was obtained.


Zirconium Hafnium Solvent extraction D2EHPA Hydrochloric acid Organic acid 



This work was supported by the National Natural Science Foundation of China (21876062) and the Natural Science Foundation of Shandong Province (ZR2017LB005).


  1. 1.
    Banda R, Min SH, Lee MS (2013) Selective extraction of Hf(IV) over Zr(IV) from aqueous H2SO4 solutions by solvent extraction with acidic organophosphorous based extractants. J Chem Technol Biotechnol 89(11):1712–1719CrossRefGoogle Scholar
  2. 2.
    Wang LY, Lee MS (2016) Solvent extraction reaction of hafnium (IV) from strong sulfuric acid solutions with D2EHPA and PC 88A. Sep Sci Technol 51(5):759–766CrossRefGoogle Scholar
  3. 3.
    Banda R, Lee HY, Lee MS (2013) Separation of Zr and Hf from strong hydrochloric acid solution by solvent extraction with TEHA. J Radioanal Nucl Chem 295(2):1537–1543CrossRefGoogle Scholar
  4. 4.
    Wang LY, Lee MS (2016) A review on the aqueous chemistry of Zr (IV) and Hf(IV) and their separation by solvent extraction. J Ind Eng Chem 39:1–9CrossRefGoogle Scholar
  5. 5.
    Yang XJ, Fane AG, Pin C (2002) Separation of zirconium and hafnium using hollow fibers: part I. Supported liquid membranes. Chem Eng J 88(1–3):37–44CrossRefGoogle Scholar
  6. 6.
    Xu ZG, Wang LJ, Wu M, Xu YL, Chi R, Li PH, Zhao J (2016) Separation of zirconium and hafnium by solvent extraction using mixture of DIBK and P204. Hydrometallurgy 165:275–281CrossRefGoogle Scholar
  7. 7.
    Wang LY, Lee HY, Lee MS (2015) Solvent extraction separation of Zr and Hf from nitric acid solutions by PC88A and its mixture with other extractants. Met Mater Int 21(1):166–172CrossRefGoogle Scholar
  8. 8.
    Nayl AA, El-Nadi YA, Daoud JA (2009) Extraction and separation of Zr(IV) and Hf(IV) from nitrate medium by some Cyanex extractants. Sep Sci Technol 44(12):2956–2970CrossRefGoogle Scholar
  9. 9.
    Benadict Rakesh K, Suresh A, Sivaraman N, Aswal VK, Vasudeva Rao PR (2016) Extraction and third phase formation behaviour of tri-iso-amyl phosphate and tri-n-butyl phosphate with Zr(IV) and Hf(IV): a comparative study. J Radioanal Nucl Chem 309(3):1037–1048CrossRefGoogle Scholar
  10. 10.
    Taghizadeh M, Ghanadi M, Zolfonoun E (2011) Separation of zirconium and hafnium by solvent extraction using mixture of TBP and Cyanex 923. J Nucl Mater 412(3):334–337CrossRefGoogle Scholar
  11. 11.
    Banda R, Lee MS (2015) Solvent extraction for the separation of Zr and Hf from aqueous solutions. Sep Purif Rev 44(3):199–215CrossRefGoogle Scholar
  12. 12.
    Xu ZG, Zhao J, Wang LJ, Xu YL, Chi RA, Li PH, Jin X (2016) Kinetics for extraction of zirconium and hafnium in DIBK-P350 system. J Radioanal Nucl Chem 309(2):701–707Google Scholar
  13. 13.
    Mishra PK, Chakravortty V, Dash KC, Das NR, Bhattacharyya SN (1989) Extraction of zirconium(IV) from HCl solutions by mixtures of Aliquat-336 and Alamine-336 with TBP. J Radioanal Nucl Chem 134(2):259–264CrossRefGoogle Scholar
  14. 14.
    Banda R, Lee HY, Lee MS (2013) Separation of Zr from Hf in acidic chloride solutions by using TOPO and its mixture with other extractants. J Radioanal Nucl Chem 298(1):259–264CrossRefGoogle Scholar
  15. 15.
    Reddy BR, Kumar JR, Reddy AV (2004) Solvent extraction of zirconium(IV) from acidic chloride solutions using the thiosubstituted organophosphorus acids Cyanex 301 and 302. J Chem Technol Biotechnol 79(11):1301–1307CrossRefGoogle Scholar
  16. 16.
    Reddy BR, Kumar JR, Raja KP, Reddy AV (2004) Solvent extraction of Hf(IV) from acidic chloride solutions using Cyanex 302. Miner Eng 17(7–8):939–942CrossRefGoogle Scholar
  17. 17.
    Lee HY, Kim SG, Oh JK (2004) Stoichiometric relation for extraction of zirconium and hafnium from acidic chloride solutions with Versatic acid 10. Hydrometallurgy 73(1–2):91–97CrossRefGoogle Scholar
  18. 18.
    Banda R, Lee HY, Lee MS (2012) Separation of Zr from Hf in hydrochloric acid solution using amine-based extractants. Ind Eng Chem Res 51(28):9652–9660CrossRefGoogle Scholar
  19. 19.
    Wang LY, Lee HY, Lee MS (2015) 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(10):1289–1295CrossRefGoogle Scholar
  20. 20.
    Saleh AS (2012) Solvent extraction of Zr(IV) and Hf(IV) with N, N, N′-N′-tetraoctyldiglycolamide. J Radioanal Nucl Chem 292(3):1109–1114CrossRefGoogle Scholar
  21. 21.
    Xu ZG, Wang LJ, Wu YK, Chi RA, Zhang L, Wu M (2012) Solvent extraction of hafnium from thiocyanic acid medium in DIBK-TBP mixed system. Trans Nonferrous Met Soc China 22(7):1760–1765CrossRefGoogle Scholar
  22. 22.
    Krishna GG, Reddy RS, Raghunath P, Bhanuprakash K, Kantam ML, Choudary BM (2004) A computational study of ligand interactions with hafnium and zirconium metal complexes in the liquid-liquid extraction process. J Phys Chem B 108(19):6112–6120CrossRefGoogle Scholar
  23. 23.
    Chen S, Zhang ZF, Kuang ST, Li YL, Huang XW, Liao WP (2017) Separation of zirconium from hafnium in sulfate medium using solvent extraction with a new reagent BEAP. Hydrometallurgy 169:607–611CrossRefGoogle Scholar
  24. 24.
    Lee MS, Banda R, Min SH (2015) Separation of Hf(IV)–Zr(IV) in H2SO4 solutions using solvent extraction with D2EHPA or Cyanex 272 at different reagent and metal ion concentrations. Hydrometallurgy 152:84–90CrossRefGoogle Scholar
  25. 25.
    Reddy BR, Kumar JR, Reddy AV (2004) Solvent extraction of tetravalent hafnium from acidic chloride solutions using 2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester(PC-88A). Miner Eng 17(4):553–556CrossRefGoogle Scholar
  26. 26.
    Conradie EW, Van Der Westhuizen DJ, Nel JT, Krieg HM (2018) The hafnium-selective extraction fom a zirconium(hafnium) heptafluoride ammonium solution using organophosphorus-based extractants. Solvent Extr Ion Exch 36(7):658–673CrossRefGoogle Scholar
  27. 27.
    Vermaak V, Krieg HM, De Beer L, Van der Westhuizen D (2018) Mechanistic study of hafnium and zirconium extraction with organophosphorus extractants. Solvent Extr Ion Exch 36(2):150–161CrossRefGoogle Scholar
  28. 28.
    Das NR, Nandi B, Bhattacharyya SN (1981) Sequential separation of hafnium, zirconium and niobium from sulphuric acid medium using di(2-ethylhexyl)phosphoric acid as an extractant. Int J Appl Radiat Isot 32(4):205–209CrossRefGoogle Scholar
  29. 29.
    Ryabchikov DI, Marov IN, Ermakov AN, Belyaeva VK (1964) Stability of some inorganic and organic complex compounds of zirconium and hafnium. J Inorg Nucl Chem 26(6):965–980CrossRefGoogle Scholar
  30. 30.
    Singhal A, Toth LM, Lin JS, Affholter K (1996) Zirconium(IV) tetramer/octamer hydrolysis equilibrium in aqueous hydrochloric acid solution. J Am Chem Soc 118(46):11529–11534CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  • Jialin Zhao
    • 1
  • Tao Yang
    • 1
  • Hao Zhang
    • 1
  • Guoxin Sun
    • 1
  • Yu Cui
    • 1
    Email author
  1. 1.School of Chemistry and Chemical Engineering, Institute for Smart Materials and EngineeringUniversity of JinanJinanPeople’s Republic of China

Personalised recommendations