含钛炉渣中TiO_2作用浓度及炉渣粘度研究
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摘要
我国四川攀西地区钒钛磁铁矿TiO_2含量较高，TiO_2对高炉冶炼过程具有重要的影响，主要是还原条件下，会有一系列钛的低价氧化物和TiC（熔点3 140℃）、TiN（熔点2 930℃）以及Ti(C、N)等高熔点物质生成，对炉渣的物理化学性质有很大改变。含钛高炉渣的特殊性与TiO_2的热力学性质-活度密切相关，因此有必要研究含钛高炉渣中TiO_2的活度，建立其计算模型并将计算值与实测值进行对比讨论，为深入研究含钛炉渣的各种物理化学性质提供重要支持。
本文通过对以往研究活度的热力学模型的总结，归纳了目前较常用的一些热力学模型的特点及其适用范围。不同的热力学计算模型，活度有不同的计算方法，但对含TiO_2渣系的热力学计算模型方面的报道并不多，尤其是含TiO_2的多元渣系，针对此问题，依据共存理论有，作用浓度即服从质量作用定律的浓度和能较广泛地应用于多元渣系的特点，尝试建立含TiO_2渣系的作用浓度计算模型有较大的理论和实际意义。
本文以FeO-MnO-TiO_2三元系、CaO-SiO_2-TiO_2三元系、CaO-Al2_O_3-SiO_2-TiO_2四元系及CaO-MgO-SiO_2-Al2_O_3-TiO_2五元系为研究对象，根据共存理论，确定渣系的结构单元，分别建立了各个渣系中组元作用浓度的计算模型。借助Matlab5.3程序设计语言编制相应的计算程序，求解非线性方程组，并得到计算结果。本文所做的主要研究和结果如下：
（1）对于FeO-MnO-TiO_2三元系，根据共存理论，首先确定了可能的结构单元，并计算组元的作用浓度，再根据计算结果，利用Visual Basic6.0 语言编制了具有可视化界面的应用程序，同时绘制了温度为1 748.15K及1 773.15K时，TiO_2的等作用浓度曲线。
（2）对于CaO-SiO_2-TiO_2三元系，分别建立了作用浓度计算模型和粘度计算模型，并利用Visual Basic6.0 语言编制了具有可视化界面的应用程序，分别绘制了温度为1 773.15K及1 673.15K时，TiO_2的等作用浓度曲线及渣系粘度曲线。
（3）对于CaO-Al2_O_3-SiO_2-TiO_2四元系，建立了作用浓度计算模型和粘度计算模型，并绘制了温度为1 673.15K时，TiO_2的作用浓度随成分变化的曲线，随着渣中TiO_2含量的增加，其作用浓度增加。
（4）对于CaO-MgO-SiO_2-Al2_O_3-TiO_2五元渣系，建立了渣系的作用浓度计算模型。根据熔渣中TiO_2作用浓度随组成的变化曲线，其作用浓度的理论计算结果左右与李道昭等人预测的比较吻合。
总之，在对含TiO_2的三元至五元典型渣系的基本结构单元进行分析的基础上，
根据分子离子共存理论建立渣中组元作用浓度计算模型，并将计算结果与文献中的实测值进行了对比，表明共存理论应用于含钛炉渣的组元作用浓度是可行的。
The percentage of TiO_2 in the titanium-vanidium-magenite located in Sichuan-Panxi in China is considerable high. TiO_2 has a significant influence on blast furnace smelting process. At reducing condition, high melting-point matter, such as a serial of low oxide containing Ti and TiC(3 140℃)、TiN(2 930℃) as well as Ti(C、N), are produced. Physicochemical properties of slag could be modified by these matters. And special performance of slag containing Ti is related to thermodynamics property of TiO_2-activity. Therefore, it is necessary to study activity of TiO_2 and establish its thermodynamics model and compared calculated values with measured ones. Important support is provided for further study of various physicochemical properties slag containing Ti.
By summarizing published activity of thermodynamic model, the paper concludes properties and application range of some thermodynamic models at present. For different thermodynamic calculation models, activity has different calculation methods. But the reports were few concerning thermodynamic calculation model of TiO_2-containing system, especially multicomponent slag system. Aiming at this problem, and according to the characteristics of coexistence theory , in which mass action concentration(N) is the concen -tration obeying mass active law, and can be widely applied to multicomponent slag system. Thermodynamic models are established with theory and practice meaning.
FeO-MnO-TiO_2 system, CaO- SiO_2-TiO_2 system, CaO-Al2_O_3-SiO_2-TiO_2 system as well as CaO-MgO-SiO_2-Al2_O_3- TiO_2 system are regarded as research objects. According to coexistence theory, structural units are determined and mass action concentrations calculation model of every system are established. Corresponding calculation programs are written by means of programming language Matlab5.3, resolving non-linear equations. Calculated results are mass action concentrations. Main conclusions are as follows:
(1) For FeO-MnO-TiO_2 system, according to coexistence theory, the mass action concentrations of the slag contents have been calculated after slag units are determined. And with these results, application program is formulated by means of programming language Visual Basic6.0 with visual surface. Iso-mass action concentrations of TiO_2 are plotted at 1 748.15K and 1 773.15K.
(2) For CaO-SiO_2-TiO_2 system, mass action concentrations model and viscosity model are created. And application program is formulated by means of programming language Visual Basic6.0 with visual surface. Iso-mass action concentrations of TiO_2 are plotted at 1 773.15K and 1 673.15K.
(3) For CaO-Al2_O_3-SiO_2-TiO_2 system, mass action concentrations model and viscosity model are produced. Curve for mass action concentrations of TiO_2 with composition is plotted at 1 673.15K. With the increase of TiO_2 in slag, mass action concentrations increased.
(4) For CaO-MgO-SiO_2-Al2_O_3-TiO_2 slag system, mass action concentrations model are established. In terms of curve for mass action concentrations of TiO_2 in slag with composition calculated result is, which fits measured values, , predicted by Li Daozhao well.
In conclusion, on the basis of analysis structure for ternary system to quinary system containing TiO_2, mass action concentrations model are established, according to coexistence theory. Comparing calculated values with measured data, the results present that coexistence theory could be applied to slag containing Ti.
本文通过对以往研究活度的热力学模型的总结，归纳了目前较常用的一些热力学模型的特点及其适用范围。不同的热力学计算模型，活度有不同的计算方法，但对含TiO_2渣系的热力学计算模型方面的报道并不多，尤其是含TiO_2的多元渣系，针对此问题，依据共存理论有，作用浓度即服从质量作用定律的浓度和能较广泛地应用于多元渣系的特点，尝试建立含TiO_2渣系的作用浓度计算模型有较大的理论和实际意义。
本文以FeO-MnO-TiO_2三元系、CaO-SiO_2-TiO_2三元系、CaO-Al2_O_3-SiO_2-TiO_2四元系及CaO-MgO-SiO_2-Al2_O_3-TiO_2五元系为研究对象，根据共存理论，确定渣系的结构单元，分别建立了各个渣系中组元作用浓度的计算模型。借助Matlab5.3程序设计语言编制相应的计算程序，求解非线性方程组，并得到计算结果。本文所做的主要研究和结果如下：
（1）对于FeO-MnO-TiO_2三元系，根据共存理论，首先确定了可能的结构单元，并计算组元的作用浓度，再根据计算结果，利用Visual Basic6.0 语言编制了具有可视化界面的应用程序，同时绘制了温度为1 748.15K及1 773.15K时，TiO_2的等作用浓度曲线。
（2）对于CaO-SiO_2-TiO_2三元系，分别建立了作用浓度计算模型和粘度计算模型，并利用Visual Basic6.0 语言编制了具有可视化界面的应用程序，分别绘制了温度为1 773.15K及1 673.15K时，TiO_2的等作用浓度曲线及渣系粘度曲线。
（3）对于CaO-Al2_O_3-SiO_2-TiO_2四元系，建立了作用浓度计算模型和粘度计算模型，并绘制了温度为1 673.15K时，TiO_2的作用浓度随成分变化的曲线，随着渣中TiO_2含量的增加，其作用浓度增加。
（4）对于CaO-MgO-SiO_2-Al2_O_3-TiO_2五元渣系，建立了渣系的作用浓度计算模型。根据熔渣中TiO_2作用浓度随组成的变化曲线，其作用浓度的理论计算结果左右与李道昭等人预测的比较吻合。
总之，在对含TiO_2的三元至五元典型渣系的基本结构单元进行分析的基础上，
根据分子离子共存理论建立渣中组元作用浓度计算模型，并将计算结果与文献中的实测值进行了对比，表明共存理论应用于含钛炉渣的组元作用浓度是可行的。
The percentage of TiO_2 in the titanium-vanidium-magenite located in Sichuan-Panxi in China is considerable high. TiO_2 has a significant influence on blast furnace smelting process. At reducing condition, high melting-point matter, such as a serial of low oxide containing Ti and TiC(3 140℃)、TiN(2 930℃) as well as Ti(C、N), are produced. Physicochemical properties of slag could be modified by these matters. And special performance of slag containing Ti is related to thermodynamics property of TiO_2-activity. Therefore, it is necessary to study activity of TiO_2 and establish its thermodynamics model and compared calculated values with measured ones. Important support is provided for further study of various physicochemical properties slag containing Ti.
By summarizing published activity of thermodynamic model, the paper concludes properties and application range of some thermodynamic models at present. For different thermodynamic calculation models, activity has different calculation methods. But the reports were few concerning thermodynamic calculation model of TiO_2-containing system, especially multicomponent slag system. Aiming at this problem, and according to the characteristics of coexistence theory , in which mass action concentration(N) is the concen -tration obeying mass active law, and can be widely applied to multicomponent slag system. Thermodynamic models are established with theory and practice meaning.
FeO-MnO-TiO_2 system, CaO- SiO_2-TiO_2 system, CaO-Al2_O_3-SiO_2-TiO_2 system as well as CaO-MgO-SiO_2-Al2_O_3- TiO_2 system are regarded as research objects. According to coexistence theory, structural units are determined and mass action concentrations calculation model of every system are established. Corresponding calculation programs are written by means of programming language Matlab5.3, resolving non-linear equations. Calculated results are mass action concentrations. Main conclusions are as follows:
(1) For FeO-MnO-TiO_2 system, according to coexistence theory, the mass action concentrations of the slag contents have been calculated after slag units are determined. And with these results, application program is formulated by means of programming language Visual Basic6.0 with visual surface. Iso-mass action concentrations of TiO_2 are plotted at 1 748.15K and 1 773.15K.
(2) For CaO-SiO_2-TiO_2 system, mass action concentrations model and viscosity model are created. And application program is formulated by means of programming language Visual Basic6.0 with visual surface. Iso-mass action concentrations of TiO_2 are plotted at 1 773.15K and 1 673.15K.
(3) For CaO-Al2_O_3-SiO_2-TiO_2 system, mass action concentrations model and viscosity model are produced. Curve for mass action concentrations of TiO_2 with composition is plotted at 1 673.15K. With the increase of TiO_2 in slag, mass action concentrations increased.
(4) For CaO-MgO-SiO_2-Al2_O_3-TiO_2 slag system, mass action concentrations model are established. In terms of curve for mass action concentrations of TiO_2 in slag with composition calculated result is, which fits measured values, , predicted by Li Daozhao well.
In conclusion, on the basis of analysis structure for ternary system to quinary system containing TiO_2, mass action concentrations model are established, according to coexistence theory. Comparing calculated values with measured data, the results present that coexistence theory could be applied to slag containing Ti.
引文
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