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The synergistic solvent extraction effect of europium and yttrium using the hexanoic acid -crown ether system

Hexanoic acid - crown ether system을 이용한 europium과 yttrium의 용매추출효과의 향상

  • Sim, Dea-Seon (Korea Research Institutue of Chemical Technology) ;
  • Han, Hye-Rim (Korea Research Institutue of Chemical Technology) ;
  • Kim, Se-Mi (Korea Research Institutue of Chemical Technology) ;
  • Kim, Jeong-Hoon (Korea Research Institutue of Chemical Technology) ;
  • Kim, Young-Wun (Korea Research Institutue of Chemical Technology) ;
  • Jeong, Noh-Hee (Department of Industrial Engineering Chemistry, Chungbuk National University) ;
  • Kang, Ho-Cheol (Korea Research Institutue of Chemical Technology)
  • Received : 2015.03.05
  • Accepted : 2015.03.25
  • Published : 2015.03.30

Abstract

The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded $MLR_3{\cdot}3RH$ form when added the crown ether.

용매추출법에서 희토류 금속을 효과적으로 분리하기 위해 추출제만 사용하는 것이 아니라 crown ether와 같은 첨가제를 이용하는 연구를 하였다. Host-guest 화합물인 macrocyclic ligand는 금속과 착화물을 형성하는데, 이 때 crown ether의 cavity 크기와 비슷한 크기의 금속 이온들과 안정한 착화물을 형성한다. 이전 연구에서 europium과 yttrium을 분리하기 위해 여러 사슬 길이의 지방산 추출제를 이용한 추출실험을 행하였었다. 이를 토대로 분리효율이 좋지 않았던 hexanoic acid에 크기가 다른 crown ether (18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether)를 첨가하여 분리효과가 증가하는 것을 연구하였다. hexanoic acid의 농도별로 분리효율을 본 후 가장 분리 효율이 좋은 농도에서 crown ether를 종류와 농도를 다르게 하여 첨가하였다. 그 결과 0.05 M hexanoic acid에서 분리능이 1.72으로 가장 높게 나타났고, crown ether를 첨가하였을 시 분리능이 0.002 M 15-crown-5 ether에서 가장 높게 나왔으며 기존의 분리능보다 2배 이상 더 높았다. 또한 crown ether를 첨가하였을 때 두 금속이 $MLR_3{\cdot}3RH$의 형태로 추출되는 것도 확인 할 수 있었다.

Keywords

References

  1. Y. Masuda, Y. Zhang, C. Yan, and B. Li,, Studies on the extraction and separation of lanthanide ions with a synergistic extraction system combined with 1,4,10,13-tetrathia-7,16-diazacyclooctadecane and lauric acid, Talanta, 46, 203-213 (1998). https://doi.org/10.1016/S0039-9140(97)00275-0
  2. Y. Jiang, A. Shibayama, K. Liu, and T. Fujita, A hydrometallurgical process for extraction of lanthanum, yttrium and gadolinium from spent optical glass, Hydrometallurgy, 76, 1-9 (2005). https://doi.org/10.1016/j.hydromet.2004.06.010
  3. R. Shimizu, K. Sawada, K. Enokida, and Y. Yamamoto, Supercritical fluid extraction of rare earth elements from luminescent material in waste fluorescent lamps, supercritical fluids, 33, 235-241 (2005). https://doi.org/10.1016/j.supflu.2004.08.004
  4. A.M.Y Jaber, and A.-E. Al-Naser, Liquid-liquid extraction of some lanthanide metal ions by polyoxyalkylene systems, Talanta, 44, 1719-1728 (1997). https://doi.org/10.1016/S0039-9140(97)00033-7
  5. T. C. Owens, and M. Smutz, Extraction of some heavier lanthanides in acidic chloride solutions by di(2-ethylhexyl) phosphoric acid, Inorg. Nucl. Chem., 30, 1617-1633 (1968). https://doi.org/10.1016/0022-1902(68)80301-X
  6. K. E. Lalntz, and E. Tachikawa, Extraction of Lanthanides from Acidic Solution Using Tributyl Phosphate Modified Supercritical Carbon Dioxide, Anal. Chem., 66, 2190-2193 (1994). https://doi.org/10.1021/ac00085a040
  7. W. C. Butts, and C. V. Banks, Solvent Extraction and Gas Chromatography of the Rare Earth Mixed-Ligand Complexes of Hexafluoroacetylacetone and Tri-n-butylphosphate, Anal. Chem., 42, 133-136 (1970). https://doi.org/10.1021/ac60283a013
  8. T. Cecconie, and H. Freiser, Extraction of tervalent lanthanides as hydroxide complexes with tri-n-octylphosphine oxide, Anal. Chem., 62, 622-625 (1990). https://doi.org/10.1021/ac00205a016
  9. A. A. Zamani, and M. R. Yaftian, Solvent extraction of thorium, lanthanum and europium ions by bis(2-ethylhexyl) phosphoric acid using 2-nitrobenzo-18-crown-6 as ion size selective masking agent, Sep. Purif. Technol., (40), 115-121 (2004).
  10. X. Sun, J. Wang, D. Li, and H. Li, Synergistic extraction of rare earths by mixture of bis(2,4,4-trimethylpentyl) phosphinic acid and Sec-nonylphenoxy acetic acid, Sep. Purif. Technol., 50, 30-34 (2006). https://doi.org/10.1016/j.seppur.2005.11.004
  11. F. Bunns, and R. Dumitrescu, Simultaneous Extraction of Rare Earth Elements and Uranium from Phosphoric Acid, Hydrometallurgy, 28, 331-336 (1992). https://doi.org/10.1016/0304-386X(92)90038-2
  12. R. W. Rinehart, Spectrophotometric Determination of Some Rare Earths and Yttrium with Alizarin Red S, Anal. Chem., 26, 1820-1822 (1954). https://doi.org/10.1021/ac60095a039
  13. Q. Z. Zhai, Simultaneous determination of lanthanum and cerium in mixed rare earths with p-acetylarsenazo by spectrophotometry, Talanta, 41, 703-706 (1994). https://doi.org/10.1016/0039-9140(94)80052-9
  14. T. S. Urbanski, C. Abbruzzese, P. Fornari, and R. Massidda, The extraction of cerium (III) and lanthanum (III) with Kelex 100 from chloride solutions, Hydrometallurgy, 25, 185-195(1990). https://doi.org/10.1016/0304-386X(90)90038-4
  15. C. Abbruzzese, P. Fornari, R. Massidda, and T. S. Urbanski, Solvent extraction of lanthanum (III) and cerium (III) from aqueous chloride solutions by LIX 70, Hydrometallurgy, 28, 179-190 (1990).
  16. S. Tong, X. Zhao, N. Song, Q. Jia, W. Zhou, and W. Liao, Solvent extraction study of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid with Cyanex301 or Cyanex302, Hydrometallurgy, 100, 15-19 (2009). https://doi.org/10.1016/j.hydromet.2009.09.006
  17. S. Radhika, B. N. Kumar, M. L. Kantam, and B. R. Reddy, Liquid-liquid extraction and separation possibilities of heavy and light rare-earths from phosphoric acid solutions with acidic organophosphorus reagents, Sep. Purif. Technol., 75, 295-302 (2010). https://doi.org/10.1016/j.seppur.2010.08.018
  18. T. Harada, M. Smutz, and R. G. Bautista, Characterization of iron and rare-earth polymers of di(2-ethylhexyl)phosphoric acid, J. Chem. Eng. Data, 17, 203-204 (1972). https://doi.org/10.1021/je60053a052
  19. M. H. Mallah, F. Shemirani, and M. G. Maragheh, Use of dispersive liquid-liquid microextraction for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium, J. Radioanal. Nucl. Chem., 278, 97-102 (2008). https://doi.org/10.1007/s10967-007-7220-1
  20. C. J. Pedersen, Cyclic polyethers and their complexes with metal salts, J. Am. Chem. Soc., 89, 7017-7036 (1967). https://doi.org/10.1021/ja01002a035
  21. M. Atanassova, Crown ethers as synergistic agents in the solvent extraction of trivalent lanthanoids with 8-hydroxyquinoline, J. Serb. Chem. Soc., 73, 29-39 (2008). https://doi.org/10.2298/JSC0801029A
  22. M. Hiraoka, crown compounds: Their characteristics and Applications; Elsevier Scientific Publishing Co.: New York (1992).
  23. L. F. Lindoy, The chemistry of Macrocyclic Ligand Complexes; Cambridge University Press: Cambrige, U.K. (1989).
  24. A. H. Bond, M. L. Dietz, and R. Chiarizia, Incorporating Size Selectivity into Synergistic Solvent Extraction: A Review of Crown Ether-Containing Systems, Ind. Eng. Chem. Res., 39, 3442-3464 (2000). https://doi.org/10.1021/ie000356j
  25. K. M. Bang, H. J. Ryu, M. B. Choi, and H. C. Kang, Extraction of Yttrium and Europium with Fatty Acids as Extractants, Appl. Chem. Eng., 21, 509-513 (2010).
  26. K. M. Bang, E. S. Lee, H. S. Been, J. H. Kim, Y. W. Kim, G. T. Lim, and H. C. Kang, Separation of Lanthanum and Cerium by Solvent Extraction Using Tetradecanoic Acid as a Extractant, J. Korea Soc. Waste Manage., 29, 231-238 (2012).
  27. K. Nakagawa, S. Okada, Y. Inoue, A. Tai, and T. Hakushi., Solvent extraction of lanthanoid picrates with crown ethers: preferential sandwich complexation and unique cation selectivities, Anal. Chem., 60, 2527-2531 (1988). https://doi.org/10.1021/ac00173a019
  28. H. Imura, and H. Mito, Selective extraction of light lanthanides(III) with 18-crown-6 and perfluorooctanoate, J. Radioanal. Nucl. Chem., 189, 229-235 (1995). https://doi.org/10.1007/BF02042601
  29. Y. Meguro, Y. Kitatsuji, T. Kimura, and Z. Yoshida, Steric effect of $\beta$-diketone +18-crown-6 ether/ 1,2-dichloroethane, J. Alloys Compd., 271, 790-793 (1998).
  30. M. Atanassova, and I. L. Dukov : Synergistic Solvent Extraction of Trivalent Lanthanoids with Mixtures of 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone and Crown Ethers, Acta Chim. Slov., 53, 457-463 (2006).

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