Resources Recycling (자원리싸이클링)

The Korean Institute of Resources Recycling (한국자원리싸이클링학회)
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A Study on the Separation of Cerium from Rare Earth Precipitates Recovered from Waste NiMH Battery

폐니켈수소전지에서 회수된 희토류복합 침전분말로부터 세륨 회수에 대한 연구

  • Kim, Boram (Advanced Materials and Processing Center, Institute for Advanced Engineering (IAE)) ;
  • Ahn, Nak-Kyoon (Materials Science and Chemical Engineering Center, Institute for Advanced Engineering (IAE)) ;
  • Lee, Sang-Woo (KMC) ;
  • Kim, Dae-Weon (Advanced Materials and Processing Center, Institute for Advanced Engineering (IAE))
  • 김보람 (고등기술연구원 신소재공정센터) ;
  • 안낙균 (고등기술연구원 융합소재연구센터) ;
  • 이상우 ((주)케이엠씨) ;
  • 김대원 (고등기술연구원 신소재공정센터)
  • Received : 2019.09.25
  • Accepted : 2019.11.13
  • Published : 2019.12.31
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Abstract

In order to recover the cerium contained in the spent nickel metal hydride batteries (NiMH battery), the recovered rare earth complex precipitates from NIMH were converted into rare earth hydroxides through ion exchange reaction to react with NaOH aqueous solution at a reaction temperature of 70 ℃, for 4 hours. Rare earth hydroxides were oxidized by injecting air at 80 ℃ for 4 hours to oxidize Ce3+ to Ce4+. The oxidation rate of cerium was confirmed to be about 25 % through XPS, and the oxidized powder was separated from the rest of the rare earth using the difference in solubility in dilute sulfuric acid. The finally recovered powder has a crystal phase of cerium hydroxide (Ce(OH)4). The cerium purity of the final product was about 94.6 %, and the recovery rate was 97.3 %.

폐니켈수소전지에 함유되어 있는 세륨을 회수하기 위하여 침출 및 침전을 통해 회수한 희토류복합 침전분말을 수산화나트륨(NaOH) 수용액에 반응온도 70 ℃ 및 반응시간 4시간의 조건에서 이온치환반응을 통하여 희토류 수산화물로 변환시켰다. 이후 희토류 수산화물은 반응온도 80 ℃에서 반응시간 4시간의 조건에서 공기를 주입하며 산화반응을 통해 세륨을 Ce3+에서 Ce4+로 전환시켰다. 세륨의 산화율은 XPS 분석을 통해 약 25 %로 확인하였으며, 산화반응이 완료된 분말은 묽은 황산에 대한 용해도 차이를 이용하여 세륨과 나머지 희토류를 분리하였다. 최종적으로 회수된 분말은 XRD 분석을 통해 수산화세륨(Ce(OH)4)의 결정상을 확인하였으며, 이때 세륨의 순도는 약 94.6 %, 회수율은 97.3 %를 나타내었다.

Keywords

References

  1. Korea Battery Recycling Association, Recycling Performance, http://www.kbra.net/, August 01, 2019.
  2. Bertuol, D. A., Bernardes, A. M., and Tenorio, J. A. S., 2006 : Spent NiMH batteries: characterization and metal recovery through mechanical processing, Journal of Power Sources, 160(2), pp.1465-1470. https://doi.org/10.1016/j.jpowsour.2006.02.091
  3. Bertuol, D. A., Bernardes, A. M., and Tenorio, J. A. S., 2009 : Spent NiMH batteries-The role of selective precipitation in the recovery of valuable metals, Journal of Power Sources, 193(2), pp.914-923. https://doi.org/10.1016/j.jpowsour.2009.05.014
  4. Innocenzi, Valentina and Francesco Veglio., 2012 : Recovery of rare earths and base metals from spent nickelmetal hydride batteries by sequential sulphuric acid leaching and selective precipitations, Journal of Power Sources, 211, pp.184-191. https://doi.org/10.1016/j.jpowsour.2012.03.064
  5. Pietrelli, L., Bellomo, B., Fontana, D., et al., 2005 : Characterization and leaching of NiCd and NiMH spent batteries for the recovery of metals, Waste Management, 25(2), pp.221-226. https://doi.org/10.1016/j.wasman.2004.12.013
  6. Pietrelli, L., Bellomo, B., Fontana, D., et al., 2002 : Rare earths recovery from NiMH spent batteries, Hydrometallurgy, 66(1-3), pp.135-139. https://doi.org/10.1016/S0304-386X(02)00107-X
  7. Innocenzi, V. and Veglio, F., 2012 : Recovery of rare earths and base metals from spent nickel-metal hydride batteries by sequential sulphuric acid leaching and selective precipitations, Journal of Power Sources, 211, pp.184-191. https://doi.org/10.1016/j.jpowsour.2012.03.064
  8. Gasser, M. S. and Aly, M. I., 2013 : Separation and recovery of rare earth elements from spent nickel-metal-hydride batteries using synthetic adsorbent, International Journal of Mineral Processing, 121, pp.31-38. https://doi.org/10.1016/j.minpro.2013.02.012
  9. Yun, X. I. A., Liansheng, X., Jiying, T. I. A. N. et al., 2015 : Recovery of rare earths from acid leach solutions of spent nickel-metal hydride batteries using solvent extraction, Journal of Rare Earths, 33(12), pp.1348-1354. https://doi.org/10.1016/s1002-0721(14)60568-8
  10. Ahn, N. K., Kim, D. W., and Yang, D. H., 2018 : A Study on Recovery of Rare Earth and Acid Leaching for Wet Recycling of Waste NiMH Batteries, Journal of the Korean Institute of Resources Recycling, 27(1), pp.22-30. https://doi.org/10.7844/kirr.2018.27.1.22
  11. Ahn, N. K., Kim, D. W., Shim, H. W. et al., 2018 : A study on recovery of rare earth oxide powders from waste NiMH batteries, Journal of the Korean Crystal Growth and Crystal Technology, 28(2), pp.85-90. https://doi.org/10.6111/JKCGCT.2018.28.2.085
  12. Kim, D. W., Ahn, N. K., Shim, H. W. et al., 2018 : A Study on the Preparation of Rare Earth Oxide Powder for Rare Earth Precipitates Recovered from Spent Ni-MH Batteries, Journal of Korean Powder Metallurgy Institute, 25(3), pp.213-219. https://doi.org/10.4150/KPMI.2018.25.3.213
  13. Yoon, H. S., Kim, C. J., Eom, H. C. et al., 2005 : Separation of cerium hydroxide from wasted cerium polishing powders by the aeration and acidity-controlling method, Journal of the Korean Institute of Resources Recycling, 14(6), pp.3-9.
  14. Preisler, E. J., Marsh, O. J., Beach, R. A. et al., 2001 : Stability of cerium oxide on silicon studied by x-ray photoelectron spectroscopy, Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena, 19(4), pp.1611-1618. https://doi.org/10.1116/1.1387464
  15. Zhang, J., Ju, X., Wu, Z. Y. et al., 2001 : Structural characteristics of cerium oxide nanocrystals prepared by the microemulsion method, Chemistry of materials, 13(11), pp.4192-4197. https://doi.org/10.1021/cm010235p
  16. Aramaki, K., 2002 : Self-healing mechanism of an organosiloxane polymer film containing sodium silicate and cerium (III) nitrate for corrosion of scratched zinc surface in 0.5 M NaCl, Corrosion Science, 44(7), pp.1621-1632. https://doi.org/10.1016/S0010-938X(01)00171-8
  17. Paparazzo, E., 2011 : On the curve-fitting of XPS Ce(3d) spectra of cerium oxides, Materials Research Bulletin, 46(2), pp.323-326. https://doi.org/10.1016/j.materresbull.2010.11.009
  18. Ansari, A. A. and Kaushik, A., 2010 : Synthesis and optical properties of nanostructured $Ce(OH)_4$, Journal of Semiconductors, 31(3), pp.1-4.