DOI QR코드

DOI QR Code

Separation of Tungsten and Vanadium from Alkaline Solution with adding CaCl2

알칼리 용액 중 CaCl2 첨가에 의한 텅스텐과 바나듐의 분리

  • Moon, Gyeonghye (Strategic Mineral Utilization Research Department, Korea Institute of Geoscience and Resources) ;
  • Choi, In-hyeok (Strategic Mineral Utilization Research Department, Korea Institute of Geoscience and Resources) ;
  • Park, Kyungho (Strategic Mineral Utilization Research Department, Korea Institute of Geoscience and Resources) ;
  • Kang, Hee-Nam (Strategic Mineral Utilization Research Department, Korea Institute of Geoscience and Resources) ;
  • Kang, Jungshin (Strategic Mineral Utilization Research Department, Korea Institute of Geoscience and Resources) ;
  • Lee, Jin-Young (Strategic Mineral Utilization Research Department, Korea Institute of Geoscience and Resources)
  • 문경혜 (한국지질자원연구원 DMR융합연구단) ;
  • 최인혁 (한국지질자원연구원 DMR융합연구단) ;
  • 박경호 (한국지질자원연구원 DMR융합연구단) ;
  • 강희남 (한국지질자원연구원 DMR융합연구단) ;
  • 강정신 (한국지질자원연구원 DMR융합연구단) ;
  • 이진영 (한국지질자원연구원 DMR융합연구단)
  • Received : 2017.05.23
  • Accepted : 2017.07.21
  • Published : 2017.08.31

Abstract

As a fundamental study for the separation of vanadium and tungsten from the leaching solution obtained from the soda roasting and water leaching process of spent SCR (Selective Catalytic Reduction) catalyst was carried out. The precipitation behaviors of vanadium and tungsten using the artificial solution (V: $1g{\cdot}L^{-1}$, W: $10g{\cdot}L^{-1}$) was investigated depending on temperature, NaOH concentration and the amount of $CaCl_2$ (aq.) added. V (aq.) was selectively precipitated at lower temperature than 293 K while tungsten also was precipitated at higher temperature. Precipitation rate of V and W was decreased by the increasing concentration of NaOH. On the other hand, excess Ca addition induced the increase of precipitation rate for V and W due to the formation of $Ca(OH)_2$ following the pH decline. The response surface methodology was employed to optimize the selective precipitation. Vanadium of 99.5% and tungsten of 0.0% was precipitated at $0.5mol{\cdot}L^{-1}$ of aqueous NaOH and 1 equivalent ratio of $CaCl_2$ at 293 K.

SCR 폐촉매의 소다배소-수침출 용액으로부터 바나듐과 텅스텐을 분리하기 위한 기초연구를 수행하였다. 침출용액을 모사한 바나듐 $1g{\cdot}L^{-1}$, 텅스텐 $10g{\cdot}L^{-1}$ 합성 알칼리 용액에 NaOH 농도와 $CaCl_2$ 첨가량에 따른 바나듐과 텅스텐의 침전거동을 조사하였다. 또한 이를 바탕으로 반응표면법을 통해 바나듐과 텅스텐의 칼슘 침전에 의한 분리 최적조건을 구하였다. 그 결과 칼슘 침전물로의 반응속도 차이에 기인하여 용액의 온도가 낮으면 바나듐만 선택적으로 침전되었고, 온도가 높아지면 텅스텐 또한 침전되었다. 바나듐과 텅스텐은 NaOH 농도가 높아짐에 따라 침전율이 낮아지며 또한 과량의 칼슘 첨가는 용액의 pH를 낮추어 바나듐과 텅스텐의 침전반응을 촉진시켰다. 반응표면법 분석결과 바나듐과 텅스텐의 분리의 최적조건은 293 K에서 $0.5mol{\cdot}L^{-1}$ NaOH, $CaCl_2$ 1 당량 이며, 이 때 바나듐과 텅스텐의 침전율은 각각 99.5%와 0.0%를 나타냈다.

Keywords

References

  1. Hong-Yoon Kang, 2015 : Review and prospect of the remanufacturing industry of Korea, REWAN 2015.
  2. Dong Wook Kwon and Sung Chang Hong, 2016 : Selective catalytic reduction (SCR) technology trends for the nitrogen oxide removal of exhaust gas, Korea Industrial Chemistry News, 19(5), pp12-24.
  3. Korea Institute of Geoscience and Mineral Resources, 2016 : Technical development on the process for commercialization of rare metal recovery from the spent deNOx catalyst and the spent automobile catalyst, R&D/GT-11-C- 01-230-0
  4. Adrian Marberger, et al. 2015 : Surface coverage optimization of $V_2O_5/WO_3-TiO_2$ SCR catalysts by variation of the V loading and by aging, Catal. Vol.5, pp1704-1720. https://doi.org/10.3390/catal5041704
  5. Korea Envionment Instutute, 2011 : Study on institutional and technical supporting plans to activate resource recirculation of rare metals of waste metal resources.
  6. Kyung Ho Park and Seong Wong Hong, 1992 : Extraction of vanadium from the metamorphic black schists in the Okchen basin by NaCl roasting, J. of Korean Institute of Mineral and Energy Resources Engineers, 29(5), pp301-315.
  7. Kyung-Ho Park, 1992 : A study on the leaching of vanadium and nickel from heavy oil fly ash, J. of Korean Inst. of Resources Recycling, 1(1), pp29-36.
  8. Kyung-Ho Park, et al., 2004 : Leaching behaviour of vanadium from orimulsion ash, J. of Korean Inst. of Resources Recycling, 13(4), pp32-38.
  9. V. Dimitrijevic, M. Dimitrijevic and D. Milanovic, 2004 : Recovery of tungsten from low-grade scheelite concentrate by soda ash roast-leach method, J. of Mining and Metallurgy, 40A(1), pp75-89.
  10. Jong-Dae Lee, Yeung-Hyo Park and Tae-Jin Lee, 2003 : Tungsten recovery from the hard metal scrap and quality enhancement technology development of recovered tungsten with using a catalyst, Prospectives of Industrial Chemistry, 3, pp3-7.
  11. Hye-Rim Kim, Jin-Young Lee and Joon-Soo Kim, 2012 : Leaching of vanadium and tungsten from spent SCR catalysts for De-NOx by soda roasting and water leaching method, J. of Korean Inst. of Resources Recycling, 21(6), pp65-73. https://doi.org/10.7844/KIRR.2012.21.6.65
  12. J.H. Pee, et al., 2015 : Extraction factor of pure ammonium paratungstate from tungsten scraps, Archives of Metallurgy and Materials, 60(2), pp1403-1405. https://doi.org/10.1515/amm-2015-0141
  13. Hye-Rim Kim, 2013 : Recovery of valuable metals from spent SCR catalysts for de-NOx by soda roasting and solvent extraction, University of Science and Technology, Master Thesis.
  14. L. Luo, et al., 2003 : A novel process for recovery of tungsten and vanadium from a leach solution of tungsten alloy scrap, Mineral Engineering, 16, pp665-670. https://doi.org/10.1016/S0892-6875(03)00103-1
  15. Li Luo, et al., 2004 : Recovery of tungsten and vanadium from tungsten alloy scrap, Hydrometallurgy, 72, pp 1-8. https://doi.org/10.1016/S0304-386X(03)00121-X
  16. Thi Hong Nguyen and Man Seung Lee, 2014 : Separation of vanadium and tungsten from sodium molybdate solution by solvent extraction, Industrial & Engineering Chemistry Research, 53, pp8608-8614. https://doi.org/10.1021/ie500486y
  17. Douglas C. Montgomery, 2005 : Design and analysis of experiments, pp 405-407, 6th Edition, John Wiley & Sons, INC.
  18. Minitab version 16, 2010, Minitab statistical software.
  19. Allen J. Bard, Roger Parsons and Joseph Jordan, 1985 : Standard potentials in aqueous solution, pp507-515, Marcel Dekker, INC.
  20. Li Honggui, Yang Jiangao and Li Kun, 2010 : Tungsten metallurgy, pp58-59, www.csupress.com.cn (in Chinese)
  21. Li He, Liu Xu-heng and He Li-hua, 2014 : Thermodynamic study on vanadium precipitation with calcium salt, CNKI, Vol. 42, No. 1.
  22. Richard Marvin and George B. Magin, Jr. 1959 : Geological survey professional paper 320_Synthesis of calcium vanadate minerals and related compounds, pp103-107, United states government printing office, Washington
  23. A Handbook for Extractive Metallurgy of Nonferrous Metals, 1999 : Rare high melting point metal, pp33, Metallurgical Industry Press, Beijing