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通过对TiO_2碳热还原进行热力学计算,得出真空碳热还原技术能降低反应温度。采用X射线衍射以及电阻测量装置考察了TiO_2真空碳热还原过程,并将最终还原产物制备成可溶性TiO阳极进行电解。结果表明:在还原温度为1200℃,还原时间2 h,TiO_2与碳摩尔比为1:3的条件下,可以得到电阻率较低(小于0.03Ω·m)的低价氧化钛。整个还原过程TiO_2遵循逐级还原理论,反应产物会经历TiO_2→Ti_6O_(11)→Ti_4O_7→Ti_3O_5→Ti_2O_3→TiO的还原过程。最终将还原产物TiO与C混合制备成阳极,石墨为阴极时,850℃在CaCl_2-KCl熔盐体系中电解2 h后可生成TiC;相同实验条件下,TiO与C按配比压制成阳极,铁为阴极,中间以泡沫陶瓷材料相隔,产物则为金属钛及钛铁合金。
Through the thermodynamic calculation of the carbothermal reduction of TiO 2, it is concluded that the vacuum carbothermal reduction technology can reduce the reaction temperature. X-ray diffraction and electrical resistance measurement were used to investigate the vacuum carbothermal reduction process of TiO 2. The final reduced product was prepared as a soluble TiO anode for electrolysis. The results show that low titania with low resistivity (less than 0.03Ω · m) can be obtained under the conditions of a reduction temperature of 1200 ℃, a reduction time of 2 h and a molar ratio of TiO_2 to carbon of 1: 3. The whole process of reduction follows the gradual reduction theory, and the reaction products undergo the reduction of TiO 2 → Ti 6 O 11 → Ti 4 O 7 → Ti 3 O 5 → Ti 2 O 3 → TiO. Finally, TiO 2 and C were mixed to prepare an anode. When graphite was used as cathode, TiC could be formed after electrolysis at 850 ℃ for 2 h in CaCl 2 -KCl molten salt system. Under the same experimental conditions, For the cathode, the middle of the foam ceramic material separated by the product is titanium metal and titanium alloy.