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Ionics

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Electrochemical extraction of titanium from carbon-doped titanium dioxide precursors by electrolysis in chloride molten salt

  • Kun ZhaoEmail author
  • Yaowu Wang
  • Feng Gao
Original Paper
  • 4 Downloads

Abstract

In this paper, a new short process integrating carbochlorination and electrolyzation to produce metallic titanium in molten NaCl–CaCl2 electrolyte was presented. This electrochemical experiment was carried out at 1123 K using carbon-doped TiO2 precursors. The electrolysis process of intermediate produced by carbochlorination of carbon-doped TiO2 precursors was studied. The cathodic product was analyzed using X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and scanning electron microscopy (SEM) after electrolysis. The evolved gas was analyzed by a gas chromatograph equipped with a thermal conductivity detector (GC-TCD). Results showed that Ti powder of 98.7% could be obtained as the final product in the cathode by electrolysis for 5 h at 4.0 V using raw pellets with a C/TiO2 mass ratio of 0.15. Furthermore, the electrochemical process of Ti deposition was comprehensively evaluated by cyclic voltammetry and squarewave voltammetry. The electrode reaction mechanisms and particle evolution principles in molten salt during this electrolysis process were discussed. It indicated that titanium chloride in lower valence (TiCl3) with more productive advantage could exist as an intermediate, and Ti3+ ions were reduced to Ti metal by a two-step mechanism corresponding to the pathway: Ti3+ → Ti2+ → Ti.

Keywords

Titanium Electrolyzation Carbochlorination Molten salts 

Notes

Funding information

This research work was supported by the National Natural Science Foundation of China (grant number 51674076), Science and Technology Program of Chongqing, China (grant number cstc2018jcyjAX0833), and Fuling District Science and Technology Plan Project of Chongqing, China (grant number FLKJ2018BBA3075).

References

  1. 1.
    Weng W, Wang MY, Gong XZ, Wang Z, Wang D, Guo Z (2017) Electrochemical reduction behavior of soluble CaTiO3 in Na3AlF6-AlF3 melt for the preparation of metal titanium. J Electrochem Soc 164:D551–D557CrossRefGoogle Scholar
  2. 2.
    Zhu FX, Qiu KH, Sun ZH (2017) Preparation of titanium from TiCl4 in a molten fluoride-chloride salt. Electrochemistry 85:715–720CrossRefGoogle Scholar
  3. 3.
    Zhao Z, Chen J, Guo S, Tan H, Lin X, Huang W (2017) Influence of α/β interface phase on the tensile properties of laser cladding deposited Ti-6Al-4V titanium alloy. J Mater Sci Technol 33:675–681CrossRefGoogle Scholar
  4. 4.
    Zhao K, Feng NX, Wang YW (2017) Fabrication of Ti-Al intermetallics by a two-stage aluminothermic reduction process using Na2TiF6. Intermetallics 85:156–162CrossRefGoogle Scholar
  5. 5.
    Liang J, Li H, Huo D, Yan H, Reddy RG, Wang L, Wang L (2018) Electrochemical characteristics of TiO2 in NaCl-KCl-NaF molten salt system. Ionics 24:3221–3226CrossRefGoogle Scholar
  6. 6.
    Kado Y, Akihiro K, Tetsuya U (2013) Electrolysis of TiO2 or TiCl2 using bi liquid cathode in molten CaCl2. J Electrochem Soc 160:E139–E142CrossRefGoogle Scholar
  7. 7.
    Kroll W (1940) The production of ductile titanium. Trans Electrochem Soc 78:35–47CrossRefGoogle Scholar
  8. 8.
    Gao F, Nie ZR, Yang DP, Sun B, Liu Y, Gong X, Wang Z (2018) Environmental impacts analysis of titanium sponge production using Kroll process in China. J Clean Prod 174:771–779CrossRefGoogle Scholar
  9. 9.
    Zhang Y, Fang ZZ, Xia Y, Huang Z, Lefler H, Zhang T, Sun P, Free ML, Guo J (2016) A novel chemical pathway for energy efficient production of Ti metal from upgraded titanium slag. Chem Eng J 286:517–527Google Scholar
  10. 10.
    Won CW, Nersisyan HH, Won HI (2010) Titanium powder prepared by a rapid exothermic reaction. Chem Eng J 157:270–275Google Scholar
  11. 11.
    Schwandt C, Fray DJ (2005) Determination of the kinetic pathway in the electrochemical reduction of titanium dioxide in molten calcium chloride. Electrochim Acta 51:66–76Google Scholar
  12. 12.
    Head RB (1961) Electrolytic production of sintered titanium from titanium tetrachloride at a contact cathode. J Electrochem Soc 108:806–809Google Scholar
  13. 13.
    Normore WM, Scobie AG (1956) Electrolysis of titanium tetrachloride to produce titanium. US Patent, No. 2755240Google Scholar
  14. 14.
    Chen GZ, Fray DJ, Farthing TW (2000) Direct electrochemical reduction of titanium dioxide to titanium in molten calcium chloride. Nature 407:361–364Google Scholar
  15. 15.
    Fray DJ, Chen GZ (2004) Reduction of titanium and other metal oxides using electrodeoxidation. Mater Sci Tech-lond 20:295–300Google Scholar
  16. 16.
    Suzuki RO, Ono K, Teranuma K (2003) Calciothermic reduction of titanium oxide and in-situ electrolysis in molten CaCl2. Metall Mater Trans B Process Metall Mater Process Sci 34:287–295Google Scholar
  17. 17.
    Ono K, Suzuki RO (2002) A new concept for producing Ti sponge: calciothermic reduction. JOM 54:59–61Google Scholar
  18. 18.
    Uda T, Okabe TH, Waseda Y (2000) Contactless electrochemical reduction of titanium (II) chloride by aluminum. Metall Mater Trans B Process Metall Mater Process Sci 31:713–721Google Scholar
  19. 19.
    Froes FH (2007) Innovations in titanium technology. Mater Technol 22:101–104Google Scholar
  20. 20.
    Muskat IE, Taylor RH (1939) Treatment of titanium ores. U.S. Patent 2184884Google Scholar
  21. 21.
    Jiao SQ, Zhu HM (2007) Electrolysis of Ti2CO solid solution prepared by TiC and TiO2. J Alloy Compd 438:243–246Google Scholar
  22. 22.
    Dring K, Rosenkilde C (2007) Production of titanium and titanium alloys by electrochemical reduction of oxide precursors. Mater Technol 22:62–65Google Scholar
  23. 23.
    Sun P, Fang ZZ, Zhang Y, Xia Y (2017) Review of the methods for production of spherical Ti and Ti alloy powder. JOM 69:1853–1860Google Scholar
  24. 24.
    Zhao K, Wang YW, Peng JP, di Y, Liu K, Feng N (2016) Formation of Ti or TiC nanopowder from TiO2 and carbon powders by electrolysis in molten NaCl-KCl. RSC Adv 6:8644–8650Google Scholar
  25. 25.
    Rand MJ, Reimert LJ (1964) Electrolytic titanium from TiCl4 I. operation of a reliable laboratory cell. J Electrochem Soc 111:429–434Google Scholar
  26. 26.
    Haarberg GM, Rolland W, Sterten Å et al (1993) Electrodeposition of titanium from chloride melts. J Appl Electrochem 23:217–224Google Scholar
  27. 27.
    Levin EM, Robbins CR, McMurdie HF (1969) Phase diagrams for ceramists. American Ceramic Society, ColumbusGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Material Science and EngineeringYangtze Normal UniversityChongqingChina
  2. 2.School of MetallurgyNortheastern UniversityShenyangChina
  3. 3.School of Chemistry and Chemistry EngineeringYangtze Normal UniversityChongqingChina

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