Advertisement

Journal of Sustainable Metallurgy

, Volume 4, Issue 3, pp 395–406 | Cite as

Reduction of Light Rare Earths and a Proposed Process for Nd Electrorecovery Based on Ionic Liquids

  • E. Bourbos
  • I. Giannopoulou
  • A. Karantonis
  • I. Paspaliaris
  • D. Panias
Research Article
  • 60 Downloads

Abstract

Electrodeposition of the rare-earth metals La, Sm, Nd, and Dy from solution in the ionic liquids N-butyl-N-methylpyrrolidinium bistriflimide (BMPTFSI) and trimethyl butylammonium bistriflimide (Me3NBuTFSI) was studied in this work. Both ionic liquids are hydrophobic and present a wide electrochemical window as well as satisfactory ionic conductivity, rendering them promising electrolytes for electroreduction of rare-earth elements. Cyclic voltammetry (CV) performed using a Pt electrode in a three-electrode cell revealed that the rare-earth cations could indeed be reduced to the metallic state in the above-mentioned ionic liquids. Furthermore, electrodeposition of the rare earths was realized on copper substrate under potentiostatic conditions of − 3.1 V versus Ag/0.1 M AgNO3 in acetonitrile at 25 °C for 5 h. Analysis of the electrodeposits by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) revealed that electrodeposition of the rare earths was feasible using these ionic liquids as the electrolytic medium. Finally, with the aim of identifying a sustainable metallurgical process for electrorecovery of rare earths, a two-compartment electrolytic cell was developed and tested for production of neodymium from a Nd(TFSI)3/BMPTFSI electrolyte.

Keywords

Electrodeposition Ionic liquids Pyrrolidinium Rare earths Neodymium 

Notes

Acknowledgements

The research leading to these results has received funding from the European Community’s Seventh Framework Programme ([FP7/2007-2013]) under Grant Agreement No. 309373. This publication reflects only the authors’ views, exempting the Community from any liability. Project web site: www.eurare.eu.

References

  1. 1.
    Ohno H (2005) Electrochemical aspects of ionic liquids. Wiley, New JerseyCrossRefGoogle Scholar
  2. 2.
    Tsuda T, Hussey CL (2009) Electrochemistry of room-temperature ionic liquids and melts. In: White RE (ed) Modern aspects of electrochemistry, No. 45. Springer, New York, pp 63–174CrossRefGoogle Scholar
  3. 3.
    Bockris JO, Reddy A (2002) Modern electrochemistry: Ionics. Kluwer Academic, New York, pp 601–654Google Scholar
  4. 4.
    Ohno H (2008) Physical properties of ionic liquids. In: Endres F, Abbott AP, Mcfarlane DR (eds) Electrodeposition from ionic liquids, 1st edn. Wiley, Weinheim, pp 47–81CrossRefGoogle Scholar
  5. 5.
    Tsuda T, Hussey CL (2007) Electrochemical applications of room temperature ionic liquids. Electrochem Soc Interface 16:42–49Google Scholar
  6. 6.
    Tian G, Li J, Hua Y (2010) Application of ionic liquids in hydrometallurgy of nonferrous metals. Trans Nonferrous Met Soc China 20:513–520CrossRefGoogle Scholar
  7. 7.
    Park J, Jung Y, Kusumah P, Lee J, Kwon K, Kyoung Lee C (2014) Application of ionic liquids in hydrometallurgy. Int J Mol Sci 15:15320–15343CrossRefGoogle Scholar
  8. 8.
    Zoski CG (2007) Handbook of electrochemistry. Elsevier, AmsterdamGoogle Scholar
  9. 9.
    Cui Y, Hua Y, Lin Y (2010) Applications of ionic liquids in electrodeposition of rare earths. J Chongqing Univ 9(4):167–176Google Scholar
  10. 10.
    Ispas A, Bund A (2014) Electrodeposition from ionic liquids. Electrochem Soc Interface 23:47–51CrossRefGoogle Scholar
  11. 11.
    Ispas A, Adolphi B, Bund A, Endres F (2010) On the electrodeposition of tantalum from three different ionic liquids with the bis(trifluoromethyl sulfonyl) amide anion. Phys Chem Chem Phys 12:1793–1803CrossRefGoogle Scholar
  12. 12.
    Jiang T, Chollier Brym MJ, Dubé G, Lasia A, Brisard GM (2006) Electrodeposition of aluminium from ionic liquids: part I electrodeposition and surface morphology of aluminium from aluminium chloride (AlCl3)–1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) ionic liquids. Surf Coat Technol 201:1–9CrossRefGoogle Scholar
  13. 13.
    Tsuda T, Nohira T, Ito Y (2001) Electrodeposition of lanthanum in lanthanum chloride saturated AlCl3-1-ethyl-3-methylimidazolium chloride molten salts. Electrochim Acta 46(12):1891–1897CrossRefGoogle Scholar
  14. 14.
    Tsuda T, Nohira T, Ito Y (2002) Nucleation and surface morphology of aluminum-lanthanum alloy electrodeposited in a LaCl3-saturated AlCl3-EtMeImCl room temperature molten salt. Electrochim Acta 47(17):2817–2822CrossRefGoogle Scholar
  15. 15.
    Lin FM, Hussey CL (1993) An electrochemical and spectroscopic study of cerium in the basic aluminum chloride-1-methyl-ethylimidazolium chloride molten salt. J Electrochem Soc 140(11):3093–3096CrossRefGoogle Scholar
  16. 16.
    Jagadeeswara RC, Venkatesan KA, Nagarajan K, Srinivasan TG, Rao PRV (2010) Electrochemical and thermodynamic properties of europium(III), samarium(III) and cerium(III) in 1-butyl-3-methylimidazolium chloride ionic liquid. J Nucl Mater 399(1):81–86CrossRefGoogle Scholar
  17. 17.
    Glukhov LM, Greish AA, Kustov LM (2010) Electrodeposition of rare earth metals Y, Gd, Yb in ionic liquids. Russ J Phys Chem A 84(1):104–108CrossRefGoogle Scholar
  18. 18.
    Legeai S, Diliberto S, Stein N, Boulanger C, Estager J, Papaiconomou N, Draye M (2008) Room-temperature ionic liquid for lanthanum electrodeposition. Electrochem Commun 10(11):1661–1664CrossRefGoogle Scholar
  19. 19.
    Yamagata M, Katayama Y, Miura T (2006) Electrochemical behavior of samarium, europium and ytterbium in hydrophobic room temperature molten salt systems. J Electrochem Soc 153(1):E5–E9CrossRefGoogle Scholar
  20. 20.
    Rao CJ, Venkatesan KA, Nagarajan K, Srinivasan TG, Rao PRV (2009) Electrochemical behavior of europium (III) in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Electrochim Acta 54(20):4718–4725CrossRefGoogle Scholar
  21. 21.
    Hussey CL, Chou LH (2014) An electrochemical and spectroscopic study of Nd(III) and Pr(III) coordination in the 1-butyl-1methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid containing chloride ion. Inorg Chem 53:5750–5758CrossRefGoogle Scholar
  22. 22.
    Bhatt AI, May I, Volkovich VA, Collison D, Helliwell M, Polovov IB, Lewin RG (2005) Structural characterisation of a lanthanum bistriflimide complex La(N(SO2CF3)3(H2O)3 and an investigation of La, Sm and Eu electrochemistry in a room-temperature ionic liquid, [Me3NnBu]N(SO2(CF3)2. Inorg Chem 44:4934–4940CrossRefGoogle Scholar
  23. 23.
    Chiappe C, Malvaldi M, Melai B, Fantini S, Bardi U, Caporali S (2009) An unusual common ion effect promotes dissolution of metal salts in room-temperature ionic liquids: a strategy to obtain ionic liquids having organic–inorganic mixed cations. Green Chem 12:77–80CrossRefGoogle Scholar
  24. 24.
    Eiden P, Liu Q, Zein El Abedin S, Endres F, Krossing I (2009) An experimental and theoretical study of the aluminium mixtures of AlCl3 with the ionic liquids [BMP]Tf2N and [Emim]Tf2N. Chem Eur J 15:3426–3434CrossRefGoogle Scholar
  25. 25.
    Rocher NM, Izgorodina EI, Rüther T, Forsyth M, McFarlane DR, Rodopoulos T, Horne MD, Bond AM (2009) Aluminium speciation in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures. Chem Eur J 15:3435–3447CrossRefGoogle Scholar
  26. 26.
    Sasaya N, Matsumiya M, Tsunashima K (2015) Solvation and electrochemical analyses of neodymium complexes in TFSA-based ionic liquids dissolving the nitrates synthesized from spent Nd-Fe-B magnets. Polyhedron 85:888–893CrossRefGoogle Scholar
  27. 27.
    Otaa H, Matsumiya M, Sasayaa N, Nishihatab K (2016) Investigation of electrodeposition behavior for Nd(III) in [P2225][TFSA] ionic liquid by EQCM methods with elevated temperatures. Electrochim Acta 222:20–26CrossRefGoogle Scholar

Copyright information

© The Minerals, Metals & Materials Society 2018

Authors and Affiliations

  1. 1.School of Mining and Metallurgical EngineeringNational Technical University of AthensZografouGreece
  2. 2.School of Chemical EngineeringNational Technical University of AthensZografouGreece

Personalised recommendations