Waste and Biomass Valorization

, Volume 10, Issue 4, pp 1029–1035 | Cite as

Characteristics of Nb and Ta in V–Cu Residue from the Purification Process of TiCl4

  • Hannian Gu
  • Ning WangEmail author
  • Yongqiong Yang
Short Communication


Titanium tetrachloride is produced through the chlorination of a variety of titanium bearing ores. The chlorination step can produce a variety of metal chloride impurities, such as iron chlorides and vanadium chlorides. The technological process of removal vanadium with copper wires is widely used in China. In the process of removal vanadium, a solid and liquid mixture will be discharged as waste. V–Cu residue is a kind of solid waste filtered from the solid and liquid mixture generated in the purification process. V–Cu residue samples from Zunyi, Guizhou, China, were investigated using X-ray fluorescence spectroscopy, inductively coupled plasma optical emission spectrometry, X-ray diffraction, and scanning electron microscope. The results showed that this waste residue contained Ti (29%), Cu (9.87%), Cl (8.83%), V (5.77%), and an amount of niobium and tantalum. Mainly mineral phases were composed of vanadium niobium oxides, titanium niobium oxides, titanium oxides, and eriochalcite. Ti and V mainly existed in the form of oxides, as dense clumps, and were accompanied by a small amount of Nb. Cu in the V–Cu residue mainly existed in the form of chlorides, adsorbing on the surface of the Ti–V–Nb oxides.


Niobium and tantalum V–Cu residue Characteristics Enrichment mechanism Titanium 



The work is financially supported by the National Natural Science Foundation of China (Grant No. 41402039), Guizhou Provincial Science and Technology Foundation ([2016]1155) and Doctoral Program Foundation of Guizhou Normal University.


  1. 1.
    Clabaugh, W.S., Leslie, R.T., Gilchrist, R.: Preparation of titanium tetrachloride of high purity. J. Res. Nat. Bur. Stand. 55(5), 261–264 (1955)CrossRefGoogle Scholar
  2. 2.
    Bonsack, J.P.: Entrained-flow chlorination of ilmenite to produce titanium tetrachloride and metallic iron. Metall. Trans. B 23(3), 261–266 (1992)CrossRefGoogle Scholar
  3. 3.
    Xu, C., Yuan, Z., Wang, X.: Preparation of TiCl4 with the titanium slag containing magnesia and calcia in a combined fluidized bed. Chin. J. Chem. Eng. 14(3), 281–288 (2006)CrossRefGoogle Scholar
  4. 4.
    Helberg, L.E.: The purification of titanium tetrachloride: a history. EPD Congr. 1, 503–509 (2011)Google Scholar
  5. 5.
    Evdokimov, V.I., Krenev, V.A.: Magnesium reduction of titanium tetrachloride. Inorg. Mater. 38(5), 490–493 (2002)CrossRefGoogle Scholar
  6. 6.
    Roy, P.K., Bhatt, A., Rajagopal, C.: Quantitative risk assessment for accidental release of titanium tetrachloride in a titanium sponge production plant. J. Hazard. Mater. A 102, 167–186 (2003)CrossRefGoogle Scholar
  7. 7.
    Lynch, D.C.: Conversion of VOCl3 to VOCl2 in liquid TiCl4. Metall. Mater. Trans. B 33(1), 142–146 (2002)MathSciNetCrossRefGoogle Scholar
  8. 8.
    Xiong, S., Yuan, Z., Yin, Z., Yan, W.: Removal of the vanadium impurities from crude TiCl4 with high content of vanadium using a mixture of Al power and white mineral oil. Hydrometallurgy 119–120, 16–22 (2012)CrossRefGoogle Scholar
  9. 9.
    Wang, X., Zhang, L., Shang, G., Zhang, G., Yuan, J., Gong, S.: Processing copper-vanadium precipitate formed from crude TiCl4 in titania and titanium sponge production. Hydrometallurgy 99, 259–262 (2009)CrossRefGoogle Scholar
  10. 10.
    Li, D.: Process of removal of vanadium from titanium tetrachloride with copper wire in China. Titan. Ind. Prog. 5, 12–14 (1996) (in Chinese)Google Scholar
  11. 11.
    Wang, M., Wang, X., Ye, P.: Recovery of vanadium from the precipitate obtained by purifying the wash water formed in refining crude TiCl4. Hydrometallurgy 110, 40–43 (2011)CrossRefGoogle Scholar
  12. 12.
    Wang, N., Gu, H., Jiang, Y., Fu, Y., Tian, Y.: Study on niobium-tantalum resources in waste from the process of refining titanium tetrachloride by copper wires. Sci. Technol. Eng. 10(31), 7728–7730 (2010) (in Chinese)Google Scholar
  13. 13.
    Zhang, L., Wang, X., Yuan, J., Gong, S.: New purification technique of wastewater in removing vanadium from raw TiCl4 with copper wire. Chin. J. Nonferrous Met. 18(6), 1159–1163 (2008) (in Chinese)Google Scholar
  14. 14.
    Liu, B., Wang, N., Yuan, J., Huang, Y., Chen, J., Tian, Y.: Comprehensive utilization of waste in titanium tetrachloride refining. Environ. Prot. Chem. Ind. 29(1), 58–61 (2009) (in Chinese)Google Scholar
  15. 15.
    Sun, Y., Wang, N., Yuan, J., Tian, Y., Li, H.: Recycle experiment and analysis of the waste brought in the process of removing vanadium by copper wires in titanium sponge. Acta Mineral. Sin. 29(1), 124–128 (2009) (in Chinese)Google Scholar
  16. 16.
    Parker, R.L., Fleischer, M.: Geochemistry of niobium and tantalum. Geol. Surv. Prof. Pap. 612, 1–43 (1968)Google Scholar
  17. 17.
    Deblonde, G.J.-P., Weigel, V., Bellier, Q., Houdard, R., Delvallée, F., Bélair, S., Beltrami, D.: Selective recovery of niobium and tantalum from low-grade concentrates using a simple and fluoride-free process. Sep. Purif. Technol. 162, 180–187 (2016)CrossRefGoogle Scholar
  18. 18.
    Wang, X., Zheng, S., Xu, H., Zhang, Y.: Processing copper-vanadium precipitate formed from crude TiCl4 in titania and titanium sponge production. Hydrometallurgy 98, 219–223 (2009)CrossRefGoogle Scholar
  19. 19.
    Gaballah, I., Allain, E., Djona, M.: Extraction of tantalum and niobium from tin slags by chlorination and carbochlorination. Metall. Mater. Trans. B 28(3), 359–369 (1997)CrossRefGoogle Scholar
  20. 20.
    Shen, H., Forssberg, E.: An overview of recovery of metals from slags. Waste Manage. 23, 933–949 (2003)CrossRefGoogle Scholar
  21. 21.
    Kosemura, S., Fukasawa, E., Ampo, S., Shiraki, T., Sannone, T.: Technology trend of titanium sponge and ingot production. Nippon Steel Tech. Rep. 85, 31–35 (2002)Google Scholar

Copyright information

© Springer Science+Business Media B.V. 2017

Authors and Affiliations

  1. 1.Key Laboratory of High-temperature and High-pressure Study of the Earth’s Interior, Institute of GeochemistryChinese Academy of SciencesGuiyangPeople’s Republic of China
  2. 2.School of Geographic and Environmental SciencesGuizhou Normal UniversityGuiyangPeople’s Republic of China

Personalised recommendations