Preparing titanium powders by calcium vapor reduction of titanium oxide directly is a new way with short flow sheet and CaTiO3 is the very important intermediate compound in this process. In this paper, the behavior of intermediate CaTiO3 in the reduction process of TiO2 was investigated. The thermodynamic calculation indicated that the Gibbs free energy change of the reaction to produce CaTiO3 by CaO and TiO2 was always negative below 1000 °C; The reaction Gibbs free energy change of the calciothermic reduction of CaTiO3 was lower than that of TiO, which would be the most predominant step from TiO2 to Ti. The experimental results showed that CaTiO3 phase derived from the reaction between TiO2 and the reduction by-product CaO, and the reaction between TiO2 and the decomposition product CaO from the additive of CaCl2 with crystal water as well in the calcium vapor reduction process of titanium oxide. But CaTiO3 could be reduced to Ti much easier than that of TiO2 by calcium vapor.
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