制备四氯化钛过程中加碳氯化反应热力学

Thermodynamics on the reaction of carbochlorination of titania for getting titanium tetrachloride

反应热力学对研究二氧化钛加碳氯化反应具有指导作用。运用HSC软件通过计算对二氧化钛加碳氯化的CO／CO2比值、配碳比等进行了讨论,结果表明低温下加碳氯化反应的相关产物为CO2,而高温下为CO。产物TiCl4含量在整个温度范围内保持稳定。当配碳比较高时,碳的反应不完全,存在过量;较低时,不利于TiO2的完全反应。通过对工业TiCl4生产CO／CO2 比值研究,发现CO／CO2比值不完全与平衡态下的CO／CO2比值一致。同时对低价钛氧化物的生成进行了探讨,计算表明在温度低于1 100℃时不会生成低价钛氧化物。通过以上研究为进一步优化加碳氯化反应提供了依据。

Thermodynamics provides reasonable direction for researching on the reaction of carbochlorination of titania. Several influencing factors of carboehlorination of titania in chloride process are discussed by computation with HSC, a computational chemistry software, which include CO/CO2 ratio, carbon added ratio and so on. The thermodynamic equilibrium calculation of the reaction system shows that main resultant connected with carbon is CO2 at low temperature but CO is at high temperature. Concentration of product TiCl4 is constant in whole domain of temperature. When carbon added ratio is a little higher than needed, the reaction of carbon isn＇t full, therefore the quantities of carbon is excessive, when that is a little lower, it is disadvantage for the reaction of TiO2. CO/CO2 ratio of industrial production of TiCl4 is talked over particularly, it is found that CO/CO2 ratio of industrial production of TiCl4 is＇t in accord with that of equation state. Presence of low valent titanium oxides is also discussed by computation, it is unbelieved that presence of low valent titanium oxides is possible since chlorination of low valent titanium oxides is easier than that of TiO2 when temperature is lower than 1100℃. The research results give reasonable scientific basis for improving suitable conditions of the carbochlorination reduction.