Abstract
A concept for calciothermic direct reduction of titanium dioxide in molten CaCl2 is proposed and experimentally tested. This production process consists of a single cell, where both the thermochemical reaction of the calciothermic reduction and the electrochemical reaction for recovery of the reducing agent, Ca, coexist in the same molten CaCl2 bath. A few molar percentages of Ca dissolve in the melt, which gives the media a strong reducing power. Using a carbon anode and a Ti basket-type cathode in which anatase-type TiO2 powder was filled, a metallic titanium sponge containing 2000 ppm oxygen was produced after 10.8 ks at 1173 K in the CaCl2 bath. The optimum concentration of CaO in the molten CaCl2 was 0.5 to 1 mol pct, to shorten the operating time and to achieve a lower oxygen content in Ti.
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W. Kroll: Trans. Electrochem. Soc., 1940, vol. 78, pp. 35–47.
K. Ono: Titanium Jpn., 2000, vol. 48 (1), pp. 13–15.
K. Ono and R.O. Suzuki: Proc. Symp. on Emerging Technologies for Metals Extraction, EPD Congr. 2001, 2001 TMS Annual Meeting, New Orleans, LA, P.R. Taylor, ed., TMS, Warrendale, PA, 2001, pp. 79–88.
K. Ono and R.O. Suzuki: Mater. Jpn., 2002, vol. 41 (1), pp. 28–31.
K. Ono and R.O. Suzuki: JOM Mem. J. Min. Met. Mater. Soc., 2002, vol. 54 (2), pp. 59–61.
K. Ono and R.O. Suzuki: Titanium Jpn., 2002, vol. 50 (2), pp. 105–08.
R.O. Suzuki and S. Inoue: Metall. Mater. Trans. B, 2003, vol. 34B, pp. 277–85.
R.O. Suzuki and K. Ono: Proc. 13th Int. Symp. on Molten Salt, H.C. Delong, R.W. Bradshaw, M. Matsunaga, G.R. Stafford, and P.C. Trulove, eds., The Electrochemical Society, Penningston, NJ, 2002, pp. 810–21.
A. Roine: HSC Chemistry for Windows, ver. 4.1, Outokump Research Oy, Pori, Finland, 2000.
H. Okamoto: Desk Handbook Phase Diagrams for Binary Alloys, ASM INTERNATIONAL, Materials Park, OH, 2000.
O. Kubaschewski and W.A. Dench: J. Inst. Met., 1953, vol. 82, pp. 87–91.
K. Ono, T.H. Okabe, M. Ogawa, and R.O. Suzuki: Tetsu-to-Hagané, 1990, vol. 76 (4), pp. 568–75.
W. Kroll: Z. Anorg. Allgem. Chem., 1937, vol. 234, pp. 42–50.
S. Miyazaki, T. Oishi, and K. Ono: Proc. 5th. World Conf. on Titanium, Munich, Germany, Sept. 10–14, 1984, G. Lütjering, U. Zwicker, and W. Bunk, eds., Deutsche Geselschaft für Metallk., Oberursel, Germany, 1985, pp. 2657–63.
K. Ono and S. Miyazaki: J. Jpn. Inst. Met., 1985, vol. 49 (10), pp. 871–75.
R.O. Suzuki, M. Ogawa, T. Oishi, and K. Ono: Proc. 6th World Conf. on Titanium 1988, Cannes, France, 1988, Soc. Franc. Metall., Paris, 1989, vol. II, pp. 701–06.
T.H. Okabe, R.O. Suzuki, T. Oishi, and K. Ono: Mater: Trans. JIM, 1991, vol. 32 (5), pp. 485–88.
H. Niiyama, Y. Tajima, F. Tsukihashi, and N. Sano: J. Less-Common Met., 1991, vol. 169, pp. 209–16.
I. Obinata, Y. Takeuchi, and S. Saikawa: Trans. ASM, 1960, vol. 52, pp. 1072–83.
P.P. Alexander: U.S. Patent 2.038.402, 1936; U.S. Patent 2.043.363, 1936; and U.S. Patent 2.082.134, 1937.
B. Neumann, C. Kröger, and H. Jüttner: Z. Elektrochem., 1935, vol. 41 (10), pp. 725–36.
W.D. Threadgill: J. Electrochem. Soc., 1965, vol. 112 (6), pp. 632–33.
D.A. Wenz, I. Johnson, and R.D. Wolson: J. Chem. Eng. Data, 1969, vol. 14 (2), pp. 250–52.
G.S. Perry and L.G. MacDonald: J. Nucl. Mater., 1985, vol. 130, pp. 234–41.
T. Ohshima, R.O. Suzuki, T. Yagura, and K. Ono: Proc. 2000 Powder Metallurgy World Congr., Kyoto, Japan, Nov. 13–18, 2000, K. Kosuge and H. Nagai, eds., Japan Society Powder and Powder Metallurgy, Tokyo, 2001, pp. 532–35.
W.Z. Wade and T. Wolf: J. Nucl. Sci. Technol., 1969, vol. 6, pp. 402–07.
R.A. Sharma: J. Met., 1987, vol. 2, pp. 33–37.
R.A. Sharma and R.N. Seefruth: J. Electrochem. Soc., 1988, vol. 135 (1), pp. 66–71.
R.A. Sharma and R.N. Seefruth: Metall. Trans. B, 1989, vol. 20B (6), pp. 805–13.
Metals Databook, Japan Institute of Metals ed., 2nd ed., Maruzen, Tokyo, 1984, pp. 9, 15, 34, and 68.
Y.S. Touloukian, R.K. Kirby, R.E. Taylor, and T.Y.R. Lee: Thermal Expansion, Nonmetallic Solid, IFI/Plenum, New York, NY, 1977, pp. 49 and 392–97.
D.T. Peterson and J.A. Hinkebein: J. Phys. Chem., 1959, vol. 63, pp. 1360–63.
R.A. Sharma: J. Phys. Chem., 1970, vol. 74 (22), pp. 3896–900.
V. Dosaj, C. Aksaranan, and D.R. Morris: J. Chem. Soc. Faraday Trans., 1975, vol. 71, pp. 1083–98.
H. Fischbach: Steel Res., 1985, vol. 56 (7), pp. 365–68.
L.-I. Staffansson and D. Sichen: Scand. J. Metall., 1992, vol. 21, pp. 165–71.
A.I. Zaitsev and B.M. Mogutnov: Metall. Mater. Trans., B, 2001, vol. 32B, pp. 305–11.
K.M. Axler and G.L. DePoorter: Mater. Sci. Forum, 1991, vol. 73–75, pp. 19–24.
P.D. Ferro, B. Mishra, D.L. Olson, and W.A. Averill: Waste Management, 1997, vol. 17, pp. 451–61.
P.D. Ferro, B. Mishra, D.L. Olson, and W.A. Averill: Trans. Ind. Inst. Met., 1998, vol. 51, pp. 69–77.
P.D. Ferro, B. Mishra, and W.A. Averill: in Light Metals 1991, E.L. Rooy, ed., TMS, Warrendale, PA, 1990, pp. 1197–1203.
G.J. Kipouros and R.A. Sharma: J. Electrochem. Soc., 1990, vol. 137, pp. 3333–38.
M. Kunitomi: J. Chem. Soc. Jpn., Pure Chem. Sec., 1950, vol. 71, pp. 40–43.
R. Lorenz: Trans. Am. Electrochem. Soc., 1904, vol. 6, pp. 160–61.
H.-H. Emons and D. Richter: Z. Anorg. Allg. Chem., 1965, vol. 339, pp. 91–98.
A.S. Dworkin, H.R. Bronstein, and M.A. Bredig: J. Phys. Chem., 1966, vol. 70 (7), pp. 2384–88.
T.H. Okabe, R.O. Suzuki, T. Oishi, and K. Ono: Tetsu-to-Hagané, 1991, vol. 77 (1), pp. 93–99.
T.H. Okabe, T. Oishi, and K. Ono: J. Alloys Compounds, 1992, vol. 184, pp. 43–56.
T.H. Okabe, M. Nakamura, T. Ueki, T. Oishi, and K. Ono: Bull. Jpn. Inst. Met., 1992, vol. 31 (4), pp. 315–17.
T.H. Okabe, T.N. Deura, T. Oishi, K. Ono, and D.R. Sadoway: J. Alloys Compounds, 1996, vol. 237, pp. 150–54.
R.O. Suzuki, M. Aizawa, and K. Ono: J. Alloys Compounds, 1999, vol. 288, pp. 173–82.
T.H. Okabe, M. Nakamura, T. Oishi, and K. Ono: Metall. Trans. B, 1993, vol. 24B, pp. 449–56.
K. Hirota, T.H. Okabe, F. Saito, Y. Waseda, and K.T. Jacob: J. Alloys Compounds, 1999, vol. 282, pp. 101–08.
M. Maeda and A. McLean: ISS Trans., 1987, vol. 8, pp. 23–27.
M.E. Sibert, Q.H. McKenna, M.A. Steinberg, and E. Wainer: J. Electrochem. Soc., 1955, vol. 102 (5), pp. 252–62.
S. Takeuchi and O. Watanabe: J. Jpn. Inst. Met., 1964, vol. 28 (9), pp. 549–54.
T. Oki and H. Inoue: Mem. Fac. Eng., Nagoya Univ., 1967, vol. 19 (1), pp. 164–66.
G.Z. Chen, D.J. Fray, and T.W. Farthing: Nature, 2000, vol. 407, pp. 361–64.
G.Z. Chen, D.J. Fray, and T.W. Farthing: Metall. Mater. Trans. B, 2001, vol. 32B (6), pp. 1041–52.
D.J. Fray: JOM Mem. J. Min. Met. Mater. Soc., 2001, vol. 53 (10), pp. 26–31.
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Suzuki, R.O., Ono, K. & Teranuma, K. Calciothermic reduction of titanium oxide and in-situ electrolysis in molten CaCl2 . Metall Mater Trans B 34, 287–295 (2003). https://doi.org/10.1007/s11663-003-0074-1
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DOI: https://doi.org/10.1007/s11663-003-0074-1