Chemistry:FFC Cambridge process
The FFC Cambridge process is an electrochemical method for producing Titanium (Ti) from titanium oxide by electrolysis in molten calcium salts.[1]
History
A process for electrochemical production of titanium was described in a 1904 German patent.[2][3][1] In solution of molten CaCl2, titanium dioxide (TiO2) has been reduced electrolytically to the metal.[4]
The FFC Cambridge process was developed by George Chen, Derek Fray, and Thomas Farthing between 1996 and 1997 at the University of Cambridge. (The name FFC derives from the first letters of the last names of the inventors).[5] The intellectual property relating to the technology has been acquired by Metalysis, (Sheffield, UK).[citation needed]
Process
The process typically takes place between 900 and 1100 °C, with an anode (typically carbon) and a cathode (oxide being reduced) in a solution of molten CaCl2. Depending on the nature of the oxide it will exist at a particular potential relative to the anode, which is dependent on the quantity of CaO present in CaCl2.
Cathode reaction mechanism
The electrocalciothermic reduction mechanism may be represented by the following sequence of reactions, where "M" represents a metal to be reduced (typically titanium).
- (1) MOx+ x Ca → M + x CaO
When this reaction takes place on its own, it is referred to as the "calciothermic reduction" (or, more generally, an example of metallothermic reduction). For example, if the cathode was primarily made from TiO then calciothermic reduction would appear as:
- TiO + Ca → Ti + CaO
Whilst the cathode reaction can be written as above it is in fact a gradual removal of oxygen from the oxide. For example, it has been shown that TiO2 does not simply reduce to Ti. It, in fact, reduces through the lower oxides (Ti3O5, Ti2O3, TiO etc.) to Ti.
The calcium oxide produced is then electrolyzed:
- (2a) x CaO → x Ca2+ + x O2−
- (2b) x Ca2+ + 2x e− → x Ca
and
- (2c) x O2− → x/2 O2 + 2x e−
Reaction (2b) describes the production of Ca metal from Ca2+ ions within the salt, at the cathode. The Ca would then proceed to reduce the cathode.
The net result of reactions (1) and (2) is simply the reduction of the oxide into metal plus oxygen:
- (3) MOx→ M + x/2 O2
Anode reaction mechanism
The use of molten CaCl2 is important because this molten salt can dissolve and transport the "O2−" ions to the anode to be discharged. The anode reaction depends on the material of the anode. Depending on the system it is possible to produce either CO or CO2 or a mixture at the carbon anode:
- C + 2O2− → CO2 +4 e−
- C + O2− → CO + 2 e−
However, if an inert anode is used, such as that of high density SnO2, the discharge of the O2− ions leads to the evolution of oxygen gas. However the use of an inert anode has disadvantages. Firstly, when the concentration of CaO is low, Cl2 evolution at the anode becomes more favourable. In addition, when compared to a carbon anode, more energy is required to achieve the same reduced phase at the cathode. Inert anodes suffer from stability issues.
- 2O2− → O2 + 4 e−
See also
References
- ↑ 1.0 1.1 Takeda, O.; Ouchi, T.; Okabe, T. H. (2020). "Recent Progress in Titanium Extraction and Recycling". Metall. Mater. Trans. B 51 (4): 1315–1328. doi:10.1007/s11663-020-01898-6.
- ↑ Borchers W., W. Hupperts, W., DRP 150557 "Verfahren der Gewinnung von Titan aus seinen Sauerstoffverbindungen auf elektrolytischem Wege". dpma.de
- ↑ Rideal, Eric Keightley (1919). Industrial Electrometallurgy, Including Electrolytic and Electrothermal Processes. D. Van Nostrand co.. p. 137. https://archive.org/details/industrialelect00ridegoog.
- ↑ Oki, T.; Inoue, H. (1967). Mem. Fac. Eng., Nagoya Univ. 19: 164–66.
- ↑ Fray, D. J.; Chen, G. Z.; Farthing, T. W. (2000). "Direct Electrochemical Reduction of Titanium Dioxide to Titanium in Molten Calcium Chloride". Nature 407 (6802): 361–4. doi:10.1038/35030069. PMID 11014188. Bibcode: 2000Natur.407..361C.
Further reading
- R. Bhagat; M. Jackson; D. Inman; R. Dashwood (2008). "Production of Ti-Mo Alloys from Mixed Oxide Precursors via the FFC Cambridge Process". J. Electrochem. Soc. 155 (6): E63–69. doi:10.1149/1.2904454.
- R. Bhagat; M. Jackson; D. Inman; R. Dashwood (2009). "Production of Ti-W Alloys from Mixed Oxide Precursors via the FFC Cambridge Process". J. Electrochem. Soc. 156 (1): E1–7. doi:10.1149/1.2999340. http://wrap.warwick.ac.uk/28972/.
- Ryosuke O. Suzuki (February–April 2005). "Calciothermic reduction of TiO2 and in situ electrolysis of CaO in the molten CaCl2". Journal of Physics and Chemistry of Solids 66 (2–4): 461–465. doi:10.1016/j.jpcs.2004.06.041. Bibcode: 2005JPCS...66..461S.
- Il Park; Takashi Abiko; Toru H. Okabe (February–April 2005). "Production of titanium powder directly from TiO2 in CaCl2 through an electronically mediated reaction (EMR)". Journal of Physics and Chemistry of Solids 66 (2–4): 410–413. doi:10.1016/j.jpcs.2004.06.052. Bibcode: 2005JPCS...66..410P.
- X. Ge; X. Wang; S. Seetharaman (2009). "Copper extraction from copper ore by electro-reduction in molten CaCl2–NaCl". Electrochimica Acta 54 (18): 4397–4402. doi:10.1016/j.electacta.2009.03.015.
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