Carbothermic And Magnesiothermic Reduction Of Titanium Dioxide ? A Thermodynamic Analysis

The stability diagram of the ternary system Ti-C-O is drawn in the present work for four temperatures, 1473 K, 1573 K, 1673 K and 1873 K, showing the stability fields of TiC, Ti, TiO, Ti2O3 and TiO2. An analysis of the system reveals that it is not possible to produce Ti in a carbon-saturated system; instead, the stable product is TiC. However, Ti can be an equilibrium product in a carbon-unsaturated system at prohibitively low values of pCO and pCO2; for example, at 1873 K, these limiting values are: pCO = 10-6.76 atm and pCO2 = 10-13.36 atm, which, when exceeded, produce TiC and TiO respectively. The magnesiothermic reduction is examined through the stability diagram (log pO2 vs. 1/T) of the system Ti-Mg-O, drawn for a number of pMg values, presenting the pairwise stability fields such as Mg(l) + Ti(s), Mg(v) + Ti(s), MgO(s) + Ti(s), etc. The diagram shows that magnesium reduction of TiO to Ti is possible only at T < 1641 K with pMg = 1 atm and only at T < 1569 K with pMg = 0.5 atm. An experimental scheme for Mg vapor reduction of TiO2 is proposed in which an argon stream is passed over a Mg(liquid) evaporator at temperature T1 (say, 1234 K); the resulting Ar-Mg mixture at 1 atm is subsequently flown over a bed of TiO2 at temperature T2. A thermodynamic analysis establishes that complete reduction to Ti is possible and that the best results are obtained when T1 = T2.