含硼高炉钛渣粘性特征与结构的研究
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摘要
高炉渣对高炉冶炼的顺利进行具有决定性的作用，尤其是对于钒钛磁铁矿高炉冶炼过程。含钛高炉渣由于含有一定量的TiO_2，导致炉渣的性能与普通炉渣相比，有明显的变化，如炉渣粘度变大、稳定性变差、脱硫性能变坏等等。为了有效改善含钛高炉渣的性能，有效手段之一是调整炉渣的成分。攀钢曾经在冶炼高钛渣时加入一定量的CaF_2，大大改善了流动性能，但是氟化物的加入，会腐蚀高炉炉衬和设备，氟的挥发和酸化又会污染环境、危害人的身体健康，因此，在大力提倡绿色清洁冶金的时代，寻找具有良好粘性特征的中、高钛渣成分成为钒钛磁铁矿成功冶炼的关键之一。研究表明，B_2O_3在渣中具有显著的助熔功效，可以作为氟的替代品，因此如何充分利用硼对中、高钛炉渣的各种功能和作用，使其能够有效改善炉渣的流动性能、满足高炉生产的需要，成为冶金工作者关注的重要问题。
本论文以西南地区钢铁厂实际高炉渣为基础，结合企业炉料结构现状，重点考察了含硼不同成分炉渣的粘度、熔化性温度等特性和矿相结构，在实验研究含硼高炉钛渣粘性特征与矿物组成和利用热力学计算模型理论分析炉渣结构的基础上，探讨了硼、钛等组分对高炉钛渣性能和微结构的影响，得到了不同成分下钛渣的流动特性与矿相组成的关系，建立了炉渣粘度的预测模型。研究结果对于加大高炉冶炼过程中钒钛矿配入比例，提高攀西地区钒钛矿资源的有效利用、改善中、高钛高炉渣的性能以及丰富钒钛磁铁矿理论具有一定的理论和现实意义。
论文首先对无硼含钛高炉渣的粘性特征进行了实验研究和理论分析。研究结果发现：①当渣中TiO_2在18.65%～26.45%之间变动时，其粘度—温度曲线均表现出“短渣”特性。高温下TiO_2含量和温度对渣的粘度影响不明显。随着温度的降低，炉渣的粘度呈现快速增大趋势，尤其是低于转折点温度后，粘度急剧增加，很快增到4.0Pa.s以上。且渣中TiO_2含量越高，该渣样转折点对应的温度越高，粘度增加的越快。各渣样的粘度与温度之间的关系符合Arrhenius方程。②当渣中CaO/SiO_2比值在1.06～1.20之间变化时，粘度—温度曲线也表现出“短渣”特性。随着渣中CaO/SiO_2比的增加，粘度变化很小，说明高温下钛渣的粘度与炉渣碱度的关系不大。但是，当温度低于1360℃时，温度和CaO/SiO_2比对炉渣粘度的影响非常明显。且渣中CaO/SiO_2比值越高，该渣样转折点对应的温度越高。③当渣中MgO在8.65%～11.62%范围内变动时，钛渣的粘度和熔化性温度随MgO的含量增加而增大。但是含量超过9.64%后，增加的幅度迅速变缓。
通过对含硼钛渣的粘性特征进行实验研究，并与无硼钛渣的性能进行比较，发现：①含硼高钛渣同样具有短渣特性，渣中TiO_2在23.48%～27.28%范围内，B_2O_3在1%～4%范围内变化时，高温下(高于转折点温度)，无硼高炉钛渣和含硼高炉钛渣的粘度差别很小，但是在其他成分相同的情况下，含硼钛渣的转折点温度大大低于无硼高炉钛渣。这说明渣中增加B_2O_3含量可以有效降低炉渣的转折点温度，添加量越多，作用越明显，对于渣铁的顺利分离、化学反应动力学条件的改善，高炉冶炼周期的缩短起到至关重要的作用，为实现高炉稳定、顺行、高产、优质、低耗奠定良好基础。②当B_2O_3含量较低时，TiO_2含量增加会增大炉渣的粘度，且越来越明显，说明越来越多的TiO_2对炉渣性能的影响与B_2O_3的影响相比较，逐渐占据主导地位；而当TiO_2含量较高时，随B_2O_3含量的增加，粘度迅速降低，说明B_2O_3的助熔作用明显。此外，随TiO_2含量的增加，炉渣的转折点温度升高，且TiO_2含量越高，提升的幅度越大。TiO_2含量相同时，渣中添加的B_2O_3越多，熔化性温度降低得越快。③碱度的增加会使炉渣的粘度逐渐增大，且粘度曲线越来越密，说明高碱度增大粘度的作用显著，B_2O_3的加入，使炉渣粘度越来越低，有效地改善了炉渣的流动性，尤其是对于低碱度的炉渣。④高炉钒钛矿冶炼过程中添加适量B_2O_3替代CaF_2，改善钛渣的流动性能完全可行，有利于延长高炉的寿命、改善外界环境。
利用NBO/T和Q参数分析了硼对炉渣结构的影响，并根据实验结果对NBO/T参数的计算公式进行了修正。结合对无硼钛渣和含硼钛渣的流动性和熔化性的测试分析，通过XRD、SEM等方法对这两类钛渣的矿物组成进行了研究。①随着B_2O_3含量的增加，熔渣结构单元的类别和数量发生变化，网络化程度降低，从而粘度减小。②无硼高炉钛渣析出的主要是CaO·SiO_2·TiO_2或CaO·TiO_2等矿相，低钛渣以黄长石类矿物为主，中、高钛渣以钙钛矿类矿物居多。而含硼高炉钛渣析出的矿相中会含有一定量的CaO·B_2O_3，MgO·B_2O_3等硼酸盐矿相，使钙钛矿的析出数量减少，且B_2O_3添加量越多，效果越明显。本研究中因为加入的B_2O_3数量较少，所以生成的含硼矿相不多。③生成的钙钛矿等高熔点矿物的数量越多，炉渣的粘度和熔化性温度越高。渣中B_2O_3含量的增多，析晶率降低，钙钛矿等矿物数量减少，因而炉渣的粘度和熔化性温度降低。添加的数量的越多，作用越显著。在分子-离子共存理论的基础上建立了CaO-SiO_2-TiO_2-Al_2O_3-MgO-B_2O_3六元渣系的热力学计算模型，对含硼炉渣结构进行了理论分析。认为：在此六元渣系中，CaO和SiO_2主要可能形式存在是Ca_2SiO_4，MgO的主要可能存在形式为CaMgSiO_4，CaO和TiO_2主要可能形式存在是CaTiO_3、Ca_3Ti_2O_7，而CaO和B_2O_3主要可能形式存在为Ca_2B_2O_5和Ca_3B_2O_6。这与对炉渣进行矿相分析得出的结论相符。此外，进一步计算了熔渣混合自由焓和自由能随渣系组成的变化规律，随着渣中B_2O_3组分含量的增大，熔渣的混合自由焓和自由能同样呈降低趋势，但渣中TiO_2含量同时增加时二者的降低速度小于渣中碱度同时增大时引起的混合自由焓和自由能的变化速度，这说明渣中CaO、B_2O_3组分增多后，更容易发生反应，生成更多的硼酸钙等盐类。
在本研究的实验数据和阿累尼乌斯公式的基础上，对粘度预测模型中参数A和B进行了修正。通过比较本研究中粘度的实测值与计算值，效果尚可，但仍需进一步优化完善。
本论文的主要创新性研究成果：
①进行了含硼高炉钛渣流动性能和熔化性能研究，研究结果对于高炉进行高配比钒钛磁铁矿冶炼具有较好的指导意义；
②对NBO/T参数的计算公式进行了修正，充分考虑了各种酸性、碱性氧化物(如CaO、MgO和Al_2O_3等)对熔渣聚合程度的不同影响，从而能很好地反应熔渣粘度值的变化趋势；
③采用SEM、XRD等手段分析了无硼和含硼炉渣的矿相组成，明确了炉渣性能与矿相组成的关系，并通过在分子离子理论基础上建立的熔渣热力学计算模型对炉渣结构进行探讨分析，对调控高炉特殊矿冶炼过程具有较好的理论指导作用。
It is of great importance to the effect of blast furnace slag on blast furnaceironmaking process, particularly process of smelting titanomagnetite bearing vanadiumores. In comparison with blast furnace slag with titanium free, the properties of titaniumslag are quite different for containing certain TiO_2. For example, viscosity of slagincreases, stabilization lowers, desulfurization performance is poor and so on. One ofthe most effective instruments for improving performance of Ti bearing blast furnaceslag is to adjust the composition of the slag. The fluid property of high titania slag fromPangang is much improved by adding certain CaF_2to the slag. However, fluoride cancorrode furnace wall and equipment, and volatiles and acidizing of the fluorine canmake evironment pollutant, endanger a person's health. Therefore, the key of smeltingtitanomagnetite bearing vanadium ores successfully is to find a right slag compositionpossessing good viscosity characteristic. According to research, B_2O_3is helpful tomelting of slag and it can be used as a substitute for CaF_2. Hence, major concerns for allthe metallurgical workers are to effectively improve the fluid property to meet the needof production by making full use of the function of boron on titanium Slag.
Based on Ti-bearing blast furnace slag from the southwestern steel plant of China,integrate with the current status of charge structure, the properties such as viscosity,break temperature and mineralogical constitution of different BF slag were mainlyinvestigated. The effects of boron, titanium and other compositions on performance andmicrostructure of titanium Slag were discussed. And the relationships of the fluidproperty and mineralogical constitution of different titanium Slag were achieved.Moreover, the predicting model among viscosity, temperature and composition oftitanium slag with boron was built based on Arrhenius equation. The results providedimportant references for increasing the ratio of vanadium–titanium ores, improving theproperties of titanium slag, rising the effectiveness in the use of titanomagnetite bearingvanadium ores and enriching the theory of titanomagnetite bearing vanadium ores.
In this study, the fluid properties of normal titanium slag were investigated firstly.The results are:①The short-slag behaviors of viscosity–temperature curves of slags areobserved during the cooling process when TiO_2content in slag varies between18.65%and26.45%. TiO_2content in slag and temperature have no obvious influence on the slagviscosity under high temperature. The viscosity rapidly increases with decreasingtemperature. Especially below the break temperature, viscosities rises rapidly up to 4.0Pa.s. The higher TiO_2content in slag, the higher the break temperature is, the quickerthe slag viscosities increase. The relationship of viscosity and temperature accords withArrhenius equation.②The short-slag behaviors of viscosity–temperature curves ofslags are observed too during the cooling process when CaO/SiO_2varies between1.06and1.20. The slag viscosities alter little with temperature at high temperature. However,the influences of temperature and CaO/SiO_2ratio on the viscosity are very markedbelow1360℃. Moreover, the higher CaO/SiO_2ratio is, the higher break temperature ofthe slag is.③the viscosity and break temperature of titanium slag increase with MgOconten when MgO content varies between8.65%and11.62%. But the increase slowsquickly after MgO content in slag acceeds9.64%.
According to the experimental study of the viscosity chatacteristic of titanium slagwith boron, and comparison between titanium slag with boron or free, the results are:①adding B_2O_3into slag can effectively decrease the break temperature when TiO_2contentis in the range of23.48%～27.38%and B_2O_3content is in the range of1%～4%. MoreB_2O_3in slag, less viscosity is, Which is vitally important to separate slag–iron, improvereaction kinetics conditions and short the smelting time of production.②the normaleffect of higher and higher TiO_2content on slag viscosity gradually triumph over theside effect of lower B_2O_3content when TiO_2content and B_2O_3content in slagsimultaneously varied. In contrast, viscosity decreases rapidlly with B_2O_3content whenTiO_2content is higher. TiO_2can lead to the increase of break temperature and more TiO_2content results in more increase. Adding more B_2O_3into slag causes more decrease ofbreak temperature at a fixation of TiO_2content.③As previously mentioned, slagviscosity can increase with basicity and more basicity leads to more obvious changes.However, the viscosity drops even lower with more and more B_2O_3content, which isadvantage to the slag fluidity.④We substitute B_2O_3for CaF_2to improve the slagproperty is feasible, which is good to prolong the life of BF wall and imoroveenvironment.
The influence of boron on slag structure was analized by NBO/T and Q parameterand calculation formula of NBO/T parameter was corrected based on the experimentalresults. Then mineralogical constitution of normal titanium slag and titanium slag withboron were analyzed by XRD and SEM etc.①the kind and amount of mocrostructuralunit of slag changed, which reduced the extent of networking, thus viscosity decreased.②Minerals deposited from normal titanium slag are mainly CaO·SiO_2·TiO_2, CaO·TiO_2and so on. Minerals in low Ti bearing slag are mainly melilites and those in middle,high Ti bearing slag are mainly perovskite, However, Minerals in titanium slag with boron include some borates such as CaO·B_2O_3，MgO·B_2O_3etc and amount of perovskitein the slag reduced. More B_2O_3, better effect. In this study borates in slag is not more forless B_2O_3addition.③more perovskite and other high melting point minerals, higherslag viscosity and break temperature. More B_2O_3in slag, less perovskite and otherminerals with high melting temperature. So viscosity and break temperature decreased.
Thermodynamic calculation model of CaO-SiO_2-TiO_2-Al_2O_3-MgO-B_2O_3system isbuilt up with experimental data based on coexistence theory. The slag structure isdiscussed in theory. Results appear below: CaO and SiO_2probably exist as Ca_2SiO_4,and MgO May exist in the form of CaMgSiO_4, and CaO and TiO_2expect as CaTiO_3、Ca_3Ti_2O_7，and CaO和B_2O_3May exist in the form of Ca_2B_2O_5和Ca_3B_2O_6, which areconsistent with results from Mineral phase analysis. In addition, the changes of Freeenthalpy and Free energy with components are calculated. They reduce with B_2O_3concentration. However, Free enthalpy and Free energy with TiO_2and B_2O_3concentration Changes faster than those with basicity and B_2O_3concentration, which iseasy to react into more Calcium borate when more CaO and B_2O_3are added into slag.
According to experimental data from the study and Arrhenius formula, parametersA and B in the predicting model were given revision. The results were good throughcomparision between calculated and measured viscosities of boron-free and boronbearing blast furnace titanium slag using the present model. However, the model shouldbe further perfected in the future.
The innovative research works are as follows:
①The effects of boron and titanium on the fluidity of titanium slag were obtainedby experiment.
②The caculation formular of NBO/T was corrected to reflect the changing trendof slag viscosity based on considering the influence of various acid and alkalineoxide(CaO, MgO and Al_2O_3etc) on polymerization of slag.
③The relationship between slag performance and slag structure is clarifiedaccording to mineralogical constitution and theoretical analyses by thermodynamiccaculation model to redirect smelting special ores in blast furnace by SEM and XRD.
本论文以西南地区钢铁厂实际高炉渣为基础，结合企业炉料结构现状，重点考察了含硼不同成分炉渣的粘度、熔化性温度等特性和矿相结构，在实验研究含硼高炉钛渣粘性特征与矿物组成和利用热力学计算模型理论分析炉渣结构的基础上，探讨了硼、钛等组分对高炉钛渣性能和微结构的影响，得到了不同成分下钛渣的流动特性与矿相组成的关系，建立了炉渣粘度的预测模型。研究结果对于加大高炉冶炼过程中钒钛矿配入比例，提高攀西地区钒钛矿资源的有效利用、改善中、高钛高炉渣的性能以及丰富钒钛磁铁矿理论具有一定的理论和现实意义。
论文首先对无硼含钛高炉渣的粘性特征进行了实验研究和理论分析。研究结果发现：①当渣中TiO_2在18.65%～26.45%之间变动时，其粘度—温度曲线均表现出“短渣”特性。高温下TiO_2含量和温度对渣的粘度影响不明显。随着温度的降低，炉渣的粘度呈现快速增大趋势，尤其是低于转折点温度后，粘度急剧增加，很快增到4.0Pa.s以上。且渣中TiO_2含量越高，该渣样转折点对应的温度越高，粘度增加的越快。各渣样的粘度与温度之间的关系符合Arrhenius方程。②当渣中CaO/SiO_2比值在1.06～1.20之间变化时，粘度—温度曲线也表现出“短渣”特性。随着渣中CaO/SiO_2比的增加，粘度变化很小，说明高温下钛渣的粘度与炉渣碱度的关系不大。但是，当温度低于1360℃时，温度和CaO/SiO_2比对炉渣粘度的影响非常明显。且渣中CaO/SiO_2比值越高，该渣样转折点对应的温度越高。③当渣中MgO在8.65%～11.62%范围内变动时，钛渣的粘度和熔化性温度随MgO的含量增加而增大。但是含量超过9.64%后，增加的幅度迅速变缓。
通过对含硼钛渣的粘性特征进行实验研究，并与无硼钛渣的性能进行比较，发现：①含硼高钛渣同样具有短渣特性，渣中TiO_2在23.48%～27.28%范围内，B_2O_3在1%～4%范围内变化时，高温下(高于转折点温度)，无硼高炉钛渣和含硼高炉钛渣的粘度差别很小，但是在其他成分相同的情况下，含硼钛渣的转折点温度大大低于无硼高炉钛渣。这说明渣中增加B_2O_3含量可以有效降低炉渣的转折点温度，添加量越多，作用越明显，对于渣铁的顺利分离、化学反应动力学条件的改善，高炉冶炼周期的缩短起到至关重要的作用，为实现高炉稳定、顺行、高产、优质、低耗奠定良好基础。②当B_2O_3含量较低时，TiO_2含量增加会增大炉渣的粘度，且越来越明显，说明越来越多的TiO_2对炉渣性能的影响与B_2O_3的影响相比较，逐渐占据主导地位；而当TiO_2含量较高时，随B_2O_3含量的增加，粘度迅速降低，说明B_2O_3的助熔作用明显。此外，随TiO_2含量的增加，炉渣的转折点温度升高，且TiO_2含量越高，提升的幅度越大。TiO_2含量相同时，渣中添加的B_2O_3越多，熔化性温度降低得越快。③碱度的增加会使炉渣的粘度逐渐增大，且粘度曲线越来越密，说明高碱度增大粘度的作用显著，B_2O_3的加入，使炉渣粘度越来越低，有效地改善了炉渣的流动性，尤其是对于低碱度的炉渣。④高炉钒钛矿冶炼过程中添加适量B_2O_3替代CaF_2，改善钛渣的流动性能完全可行，有利于延长高炉的寿命、改善外界环境。
利用NBO/T和Q参数分析了硼对炉渣结构的影响，并根据实验结果对NBO/T参数的计算公式进行了修正。结合对无硼钛渣和含硼钛渣的流动性和熔化性的测试分析，通过XRD、SEM等方法对这两类钛渣的矿物组成进行了研究。①随着B_2O_3含量的增加，熔渣结构单元的类别和数量发生变化，网络化程度降低，从而粘度减小。②无硼高炉钛渣析出的主要是CaO·SiO_2·TiO_2或CaO·TiO_2等矿相，低钛渣以黄长石类矿物为主，中、高钛渣以钙钛矿类矿物居多。而含硼高炉钛渣析出的矿相中会含有一定量的CaO·B_2O_3，MgO·B_2O_3等硼酸盐矿相，使钙钛矿的析出数量减少，且B_2O_3添加量越多，效果越明显。本研究中因为加入的B_2O_3数量较少，所以生成的含硼矿相不多。③生成的钙钛矿等高熔点矿物的数量越多，炉渣的粘度和熔化性温度越高。渣中B_2O_3含量的增多，析晶率降低，钙钛矿等矿物数量减少，因而炉渣的粘度和熔化性温度降低。添加的数量的越多，作用越显著。在分子-离子共存理论的基础上建立了CaO-SiO_2-TiO_2-Al_2O_3-MgO-B_2O_3六元渣系的热力学计算模型，对含硼炉渣结构进行了理论分析。认为：在此六元渣系中，CaO和SiO_2主要可能形式存在是Ca_2SiO_4，MgO的主要可能存在形式为CaMgSiO_4，CaO和TiO_2主要可能形式存在是CaTiO_3、Ca_3Ti_2O_7，而CaO和B_2O_3主要可能形式存在为Ca_2B_2O_5和Ca_3B_2O_6。这与对炉渣进行矿相分析得出的结论相符。此外，进一步计算了熔渣混合自由焓和自由能随渣系组成的变化规律，随着渣中B_2O_3组分含量的增大，熔渣的混合自由焓和自由能同样呈降低趋势，但渣中TiO_2含量同时增加时二者的降低速度小于渣中碱度同时增大时引起的混合自由焓和自由能的变化速度，这说明渣中CaO、B_2O_3组分增多后，更容易发生反应，生成更多的硼酸钙等盐类。
在本研究的实验数据和阿累尼乌斯公式的基础上，对粘度预测模型中参数A和B进行了修正。通过比较本研究中粘度的实测值与计算值，效果尚可，但仍需进一步优化完善。
本论文的主要创新性研究成果：
①进行了含硼高炉钛渣流动性能和熔化性能研究，研究结果对于高炉进行高配比钒钛磁铁矿冶炼具有较好的指导意义；
②对NBO/T参数的计算公式进行了修正，充分考虑了各种酸性、碱性氧化物(如CaO、MgO和Al_2O_3等)对熔渣聚合程度的不同影响，从而能很好地反应熔渣粘度值的变化趋势；
③采用SEM、XRD等手段分析了无硼和含硼炉渣的矿相组成，明确了炉渣性能与矿相组成的关系，并通过在分子离子理论基础上建立的熔渣热力学计算模型对炉渣结构进行探讨分析，对调控高炉特殊矿冶炼过程具有较好的理论指导作用。
It is of great importance to the effect of blast furnace slag on blast furnaceironmaking process, particularly process of smelting titanomagnetite bearing vanadiumores. In comparison with blast furnace slag with titanium free, the properties of titaniumslag are quite different for containing certain TiO_2. For example, viscosity of slagincreases, stabilization lowers, desulfurization performance is poor and so on. One ofthe most effective instruments for improving performance of Ti bearing blast furnaceslag is to adjust the composition of the slag. The fluid property of high titania slag fromPangang is much improved by adding certain CaF_2to the slag. However, fluoride cancorrode furnace wall and equipment, and volatiles and acidizing of the fluorine canmake evironment pollutant, endanger a person's health. Therefore, the key of smeltingtitanomagnetite bearing vanadium ores successfully is to find a right slag compositionpossessing good viscosity characteristic. According to research, B_2O_3is helpful tomelting of slag and it can be used as a substitute for CaF_2. Hence, major concerns for allthe metallurgical workers are to effectively improve the fluid property to meet the needof production by making full use of the function of boron on titanium Slag.
Based on Ti-bearing blast furnace slag from the southwestern steel plant of China,integrate with the current status of charge structure, the properties such as viscosity,break temperature and mineralogical constitution of different BF slag were mainlyinvestigated. The effects of boron, titanium and other compositions on performance andmicrostructure of titanium Slag were discussed. And the relationships of the fluidproperty and mineralogical constitution of different titanium Slag were achieved.Moreover, the predicting model among viscosity, temperature and composition oftitanium slag with boron was built based on Arrhenius equation. The results providedimportant references for increasing the ratio of vanadium–titanium ores, improving theproperties of titanium slag, rising the effectiveness in the use of titanomagnetite bearingvanadium ores and enriching the theory of titanomagnetite bearing vanadium ores.
In this study, the fluid properties of normal titanium slag were investigated firstly.The results are:①The short-slag behaviors of viscosity–temperature curves of slags areobserved during the cooling process when TiO_2content in slag varies between18.65%and26.45%. TiO_2content in slag and temperature have no obvious influence on the slagviscosity under high temperature. The viscosity rapidly increases with decreasingtemperature. Especially below the break temperature, viscosities rises rapidly up to 4.0Pa.s. The higher TiO_2content in slag, the higher the break temperature is, the quickerthe slag viscosities increase. The relationship of viscosity and temperature accords withArrhenius equation.②The short-slag behaviors of viscosity–temperature curves ofslags are observed too during the cooling process when CaO/SiO_2varies between1.06and1.20. The slag viscosities alter little with temperature at high temperature. However,the influences of temperature and CaO/SiO_2ratio on the viscosity are very markedbelow1360℃. Moreover, the higher CaO/SiO_2ratio is, the higher break temperature ofthe slag is.③the viscosity and break temperature of titanium slag increase with MgOconten when MgO content varies between8.65%and11.62%. But the increase slowsquickly after MgO content in slag acceeds9.64%.
According to the experimental study of the viscosity chatacteristic of titanium slagwith boron, and comparison between titanium slag with boron or free, the results are:①adding B_2O_3into slag can effectively decrease the break temperature when TiO_2contentis in the range of23.48%～27.38%and B_2O_3content is in the range of1%～4%. MoreB_2O_3in slag, less viscosity is, Which is vitally important to separate slag–iron, improvereaction kinetics conditions and short the smelting time of production.②the normaleffect of higher and higher TiO_2content on slag viscosity gradually triumph over theside effect of lower B_2O_3content when TiO_2content and B_2O_3content in slagsimultaneously varied. In contrast, viscosity decreases rapidlly with B_2O_3content whenTiO_2content is higher. TiO_2can lead to the increase of break temperature and more TiO_2content results in more increase. Adding more B_2O_3into slag causes more decrease ofbreak temperature at a fixation of TiO_2content.③As previously mentioned, slagviscosity can increase with basicity and more basicity leads to more obvious changes.However, the viscosity drops even lower with more and more B_2O_3content, which isadvantage to the slag fluidity.④We substitute B_2O_3for CaF_2to improve the slagproperty is feasible, which is good to prolong the life of BF wall and imoroveenvironment.
The influence of boron on slag structure was analized by NBO/T and Q parameterand calculation formula of NBO/T parameter was corrected based on the experimentalresults. Then mineralogical constitution of normal titanium slag and titanium slag withboron were analyzed by XRD and SEM etc.①the kind and amount of mocrostructuralunit of slag changed, which reduced the extent of networking, thus viscosity decreased.②Minerals deposited from normal titanium slag are mainly CaO·SiO_2·TiO_2, CaO·TiO_2and so on. Minerals in low Ti bearing slag are mainly melilites and those in middle,high Ti bearing slag are mainly perovskite, However, Minerals in titanium slag with boron include some borates such as CaO·B_2O_3，MgO·B_2O_3etc and amount of perovskitein the slag reduced. More B_2O_3, better effect. In this study borates in slag is not more forless B_2O_3addition.③more perovskite and other high melting point minerals, higherslag viscosity and break temperature. More B_2O_3in slag, less perovskite and otherminerals with high melting temperature. So viscosity and break temperature decreased.
Thermodynamic calculation model of CaO-SiO_2-TiO_2-Al_2O_3-MgO-B_2O_3system isbuilt up with experimental data based on coexistence theory. The slag structure isdiscussed in theory. Results appear below: CaO and SiO_2probably exist as Ca_2SiO_4,and MgO May exist in the form of CaMgSiO_4, and CaO and TiO_2expect as CaTiO_3、Ca_3Ti_2O_7，and CaO和B_2O_3May exist in the form of Ca_2B_2O_5和Ca_3B_2O_6, which areconsistent with results from Mineral phase analysis. In addition, the changes of Freeenthalpy and Free energy with components are calculated. They reduce with B_2O_3concentration. However, Free enthalpy and Free energy with TiO_2and B_2O_3concentration Changes faster than those with basicity and B_2O_3concentration, which iseasy to react into more Calcium borate when more CaO and B_2O_3are added into slag.
According to experimental data from the study and Arrhenius formula, parametersA and B in the predicting model were given revision. The results were good throughcomparision between calculated and measured viscosities of boron-free and boronbearing blast furnace titanium slag using the present model. However, the model shouldbe further perfected in the future.
The innovative research works are as follows:
①The effects of boron and titanium on the fluidity of titanium slag were obtainedby experiment.
②The caculation formular of NBO/T was corrected to reflect the changing trendof slag viscosity based on considering the influence of various acid and alkalineoxide(CaO, MgO and Al_2O_3etc) on polymerization of slag.
③The relationship between slag performance and slag structure is clarifiedaccording to mineralogical constitution and theoretical analyses by thermodynamiccaculation model to redirect smelting special ores in blast furnace by SEM and XRD.
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