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真空碳热还原制备碳氧钛的动力学研究 被引量:3

Kinetic Study on Preparation of Titanium Oxycarbide by Vacuum Thermal Reduction
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摘要 采用非等温固相模型对碳热还原TiO2历程和动力学条件进行研究.结果表明,真空碳热还原TiO2可分为四个阶段,第一阶段(1 373~1 523 K)主要物相为C和TinO2n-1(n≥5),第二阶段(1 523~1 673 K)主要物相为C、TiC0.5O0..5和TinO2n-1(2≤n≤4),第三阶段(1 673~1 833 K)主要物相为C、Ti2O3和TiC0.5O0.5,第四阶段(1 833~1 973 K)主要物相为TiC0.5O1.5;第一阶段动力学方程为α2=kt,受一维扩散控制,表观活化能为113.55 kJ/mol,第二阶段动力学方程为(1-α)1-1=kt,受二级化学反应控制,温度对还原率影响较大,表观活化能为303.36 kJ/mol,第三阶段动力学方程为2[(1-α)1/2-1]=kt,受1.5级化学反应控制,还原剂不足对反应影响较大,表观活化能为53.93kJ/mol,第四阶段动力学方程为1-2α/3-(1-α)2/3=kt,受三维扩散控制,物料疏松成为晶核长大的限制环节,表观活化能为99.22 kJ/mol. The process and dynamic condition of TiO2 carbothermic reduction were studied by non-isothermal solid model.The results show that carbothermic reduction process is divided into four stages.C and Tin O2n-1(n≥5)are the main phases of the first stage (1 373~1 523 K),which gradually change into C,TiC0.5O0.5 and TinO2n-1(2≤n≤4)at the second stage (1 523~1 673 K).C,Ti2O3 and TiC0.5O0.5 are the main phases of the third stage(1 673~1 833 K),which finally change into TiC0.5O0.5 at the fourth stage (1 833~ 1 973 K).The kinetic equation of the first stage presents as α2 =kt,which is controlled by one-dimension diffusion with apparent activation energies of 113.55 kJ/mol.The kinetic equation of the second stage presents as (1-α)-1-1 =kt,which is controlled by the second-order reaction with apparent activation energies of 303.36 kJ/mol.Temperature exerts significant influence in this stage.The kinetic equation of the third stage presents as 2[(1-α)-1/2-1] =kt,which is controlled by 1.5-order reaction with apparent activation energies of 53.93 kJ/mol,and this stage is limited by inadequate reducing agent.The kinetic equation of the last presents as 1-2α/3-(1-α)2/3 =kt,which is controlled by three-dimension diffusion with apparent activation energies of 99.22 kJ/mol,and this stage is mainly restricted by the loosing structure of product.
出处 《有色金属(冶炼部分)》 CAS 北大核心 2014年第3期46-50,共5页 Nonferrous Metals(Extractive Metallurgy)
基金 国家重点基础研究发展计划(973计划)项目(2013CB632606)
关键词 碳氧钛 动力学 还原历程 表观活化能 titanium oxycarbide dynamics reduction process apparent activation energy
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