Home Thermodynamic Assessment of TiO2 Reduction to Ti Metal in Molten CaCl2
Article
Licensed
Unlicensed Requires Authentication

Thermodynamic Assessment of TiO2 Reduction to Ti Metal in Molten CaCl2

  • Mallikharjuna R. Bogala and Ramana G. Reddy EMAIL logo
Published/Copyright: April 7, 2016
Become an author with De Gruyter Brill

Abstract

Thermodynamic assessment of electrochemical reduction of TiO2 to Ti metal in CaCl2 molten salt electrolyte is discussed. The conversion of TiO2 to Ti takes place via multi-step reduction process that involves formation of several intermediates or sub-oxides of titanium at different reaction conditions. A complete understanding of these redox chemical reactions, and change in reaction Gibbs energy is very essential for efficient extraction of the Ti metal. This research article discusses the thermodynamic modelling studies on the formation of different titanium sub-oxides and corresponding reaction conditions (change in Gibb’s energy, temperature, and pressure) during TiO2 reduction to Ti metal.

Award Identifier / Grant number: DMR-1310072

Funding statement: The authors are grateful to National Science Foundation (NSF) agency for financial grant (DMR-1310072) in support of current research. The authors also extend thanks to American Cast Iron Pipe Company (ACIPCO) and University of Alabama for the computer research lab facilities.

References

1. Leyens C, Peters M. Titanium and titanium alloys. Weinheim: Wiley-VCH, 2003.Search in Google Scholar

2. Wang K. The use of titanium for medical applications in the USA. Mater Sci Eng A 1996;213:134–7.Search in Google Scholar

3. Cui C, Hu B, Zhao L, Liu S. Titanium alloy production technology, market prospects and industry development. Mater Des 2011;32:1684–91.Search in Google Scholar

4. Seagle SR. The state of the USA titanium industry in 1995. Mater Sci Eng A 1996;213:1–7.Search in Google Scholar

5. Force ER. Geology of titanium-mineral deposits. Geol Soc Am Spec Pap 1991;259(1):1–112.Search in Google Scholar

6. Zhang W, Zhu Z, Cheng CY. A literature review of titanium metallurgical processes. Hydrometallurgy 2011;108:177–88.Search in Google Scholar

7. Jackson M, Dring K. A review of advances in processing and metallurgy of titanium alloys. Mater Sci Technol 2006;22:881–7.Search in Google Scholar

8. Norgate TE, Jahanshahi S, Rankin WJ. Assessing the environmental impact of metal production processes. J Cleaner Prod 2007;15(8):838–48.Search in Google Scholar

9. Nagesh CR, Ramachandran CS. Electrochemical process of titanium extraction. Trans Nonferrous Met Soc China 2007;17:429–33.Search in Google Scholar

10. Fray DJ. Novel methods for the production of titanium. Int Mater Rev 2008;53(6):317–25.Search in Google Scholar

11. Chassaing E, Basile F, Lorthioir G. Electrochemical behaviour of the titanium chlorides in various alkali chloride baths. J Less-Common Met 1979;68:153–8.Search in Google Scholar

12. Lantelme F, Salmi A. Electrochemistry of titanium in NaCl‐KCl mixtures and influence of dissolved fluoride ions. J Electrochem Soc 1995;142:3451–6.Search in Google Scholar

13. Lantelme F, Kuroda K, Barhoun A. Electrochemical and thermodynamic properties of titanium chloride solutions in various alkali chloride mixtures. Electrochim Acta 1998;44:421–31.Search in Google Scholar

14. Janz GJ, Allen CB, Bansal NP, Murphy RM, Tomkins RP. Physical properties data compilations relevant to energy storage. II. Molten salts: data on single and multi-component salt systems. Rensselaer Polytechnic Inst. Troy, NY, USA: Cogswell Lab, 1979.Search in Google Scholar

15. Inman D, White SH. The production of refractory metals by the electrolysis of molten salts; design factors and limitations. J Appl Electrochem. 1978;8:375–90.Search in Google Scholar

16. Fray DJ. Emerging molten salt technologies for metals production. JOM 2001;53:27–31.Search in Google Scholar

17. Chen GZ, Fray DJ, Farthing TW. Direct electrochemical reduction of titanium dioxide to titanium in molten calcium chloride. Nature 2000;407:361–4.Search in Google Scholar

18. Park I, Abiko T, Okabe TH. Production of titanium powder directly from TiO2 in CaCl2 through an electronically mediated reaction (EMR). J Phys Chem Solids 2005;66:410–13.Search in Google Scholar

19. Suzuki RO, Ono K. OS process–thermochemical approach to reduce titanium oxide in the molten CaCl2. In TMS Yazawa international symposium, metallurgical and materials processing: principles and technologies, Vol III: aqueous and electrochemical processing, 2003.Search in Google Scholar

20. Okabe TH, Oda T, Mitsuda Y. Titanium powder production by preform reduction process (PRP). J Alloys Compd 2004;364:156–63.Search in Google Scholar

21. Withers JC, Cardarelli F, Laughlin J, Loutfy RO. Recent improvements for electrowinning titanium metal from composite anodes. International round table on titanium production in molten salts, 2008.Search in Google Scholar

22. Rigby GD, Ratchev IP, Olivares RI, Mukunthan K, Bliznyukov SA, Shook AA. Polar™ titanium–development of the BHP billiton titanium metal production process. Presentation at 21st Annual 2005;1:25–7.Search in Google Scholar

23. Suput M, Delucas R, Pati S, Ye G, Pal U, Powell Iv AC. Solid oxide membrane technology for environmentally sound production of titanium. Miner Process Extr Metall Rev 2008;117:118–22.Search in Google Scholar

24. Mohandas KS, Fray DJ. FFC Cambridge process and removal of oxygen from metal-oxygen systems by molten salt electrolysis: an overview. Trans Indian Inst Met 2004;57:579–92.Search in Google Scholar

25. Bertolini M, Shaw L, England L, Rao K, Deane J, Collins J. The FFC Cambridge process for production of low cost titanium and titanium powders. Key Eng Mater 2010;436:75–83.Search in Google Scholar

26. Ma M, Wang D, Wang W, Hu X, Jin X, Chen GZ. Extraction of titanium from different Titania precursors by the FFC Cambridge process. J Alloys Compd 2006;420:37–45.Search in Google Scholar

27. Rajulu GG, Kumar MG, Babu BH, Rao KS, Nagesh CR. On chemical synthesis of electrochemical reduction of titanium dioxide (TiO2) to titanium metal. Trans Indian Inst Met 2016;1–7 (article in press), http://link.springer.com/journal/12666/onlineFrist/page/2, doi:10.1007/s12666-015-0600-2.Search in Google Scholar

28. Alexander DT, Schwandt C, Fray DJ. The electro-deoxidation of dense titanium dioxide precursors in molten calcium chloride giving a new reaction pathway. Electrochim Acta 2011;56:3286–95.Search in Google Scholar

29. Suzuki RO. Calciothermic reduction of TiO2 and in situ electrolysis of CaO in the molten CaCl2. J Phys Chem Solids 2005;66:461–5.Search in Google Scholar

30. Jacob KT, Hoque SM, Synergistic WY. Use of thermogravimetric and electrochemical techniques for thermodynamic study of TiOx (1.67≤ x ≤2.0) at 1,573 K. Mater Trans JIM 2000;41:681–9.Search in Google Scholar

31. Jacob KT, Abraham KP. Thermodynamic properties of calcium titanates: CaTiO3, Ca4Ti3O10, and Ca3Ti2O7. J Chem Thermodyn 2009;41:816–20.Search in Google Scholar

32. Jacob KT, Gupta S. Phase diagram of the system Ca-Ti-O at 1200 K. Bull Mater Sci 2009; 32(6):611–616.Search in Google Scholar

33. Dring K, Dashwood R, Inman D. Predominance diagrams for electrochemical reduction of titanium oxides in molten CaCl2. J Electrochem Soc 2005;152:D184–90.Search in Google Scholar

34. Bavbande D, Mishra R, Juneja J. Studies on the kinetics of synthesis of TiC by calciothermic reduction of TiO2 in presence of carbon. J Therm Anal Calorim 2004;78:775–80.Search in Google Scholar

35. Outotec HSC Chemistry, Pori, Finland. Available at: http://www.hsc-chemistry.com. Accessed:09/09/2015.Search in Google Scholar

36. The FactSage system. Available at: http://www.factsage.com. Accessed on 01/06/2016.Search in Google Scholar

Received: 2016-2-13
Accepted: 2016-2-16
Published Online: 2016-4-7
Published in Print: 2016-3-1

©2016 by De Gruyter

Downloaded on 13.10.2025 from https://www.degruyterbrill.com/document/doi/10.1515/jmsp-2016-0003/html
Scroll to top button