【作者】 白晨光；

【导师】 徐楚韶；

【作者基本信息】 重庆大学 ， 钢铁冶金， 2003， 博士

【摘要】 攀枝花－西昌地区蕴藏的丰富钒钛磁铁矿资源是我国著名的三大复合共生矿之一，也是世界闻名的钒钛磁铁矿资源。攀西地区的钒钛磁铁矿资源工业规模开发和综合利用是过去三十年间中国冶金科技界的一项重要任务，经过多年的努力，攀钢已经建设成了我国大型的钢铁联合企业，铁、钒、钛资源的开发和利用均取得了一定成效。但是，攀枝花钒钛磁铁矿无论是在高炉冶炼过程，还是由此形成的高钛型高炉渣，都具有许多不同于普通铁矿石冶炼的物理化学问题，这些问题的深入研究有助于在理论上丰富复合矿分离科学的若干基本思想，为我国其它复合共生矿的综合利用提供有益的借鉴作用；在实践上可以进一步推进钒钛磁铁矿高炉冶炼工艺技术水平提高和含钛高炉渣的综合利用新工艺、新技术开发。本文在对国内外关于含钛高炉渣物理化学性质研究状况进行了较为深入细致分析的基础上，在实验室分别就含钛高炉渣的粘度、熔化性温度、表面张力、表面粘度、TiO2在炉渣中的活度等进行了测定；并在理论上利用共存理论模型对CaO-SiO2-TiO2-Al2O3-MgO五元渣系TiO2的活度进行了研究；利用非牛顿流体的理论对含钛高炉渣的泡沫化机理及其与各种物理化学性质之间的关系进行了分析；最后对微波与高钛高炉渣之间的作用效果进行了研究，并初步探讨了作用机理。本论文具体的研究工作和结论如下：对于含钛高炉渣的粘度问题，在实验室采用旋转粘度计测定了不同炉渣二元碱度、TiO2含量、还原程度以及TiC、TiN等高熔点物相对炉渣的粘度和熔化性温度的影响；应用流体力学的基本理论建立了采用旋转法测定熔渣粘度时，测头转速对熔体的作用范围以及应用在非牛顿熔体测试中的基本原则；对不同TiC、TiN浓度时粘度测定的结果进行了深入分析，根据胶体化学中的Einstein公式讨论了含钛高炉渣中，固相颗粒对粘度的作用，发现本研究中，固相粒子与熔渣粘度之间的关系，并不完全遵从Einstein公式，提出了此类熔渣是“类胶体”的概念。并由此探讨了TiC、TiN的分散形态对炉渣变稠的影响。通过实验研究和理论计算及分析表明：① 含钛高炉渣如果在中性或氧化性气氛下，炉渣的粘度并不会发生变稠的现象。炉渣变稠的问题主要与TiO2的还原程度有关，深度的还原产生的TiC、TiN固相颗粒较多，炉渣的表观粘度就会增大，TiC、TiN的重量百分含量超过6%时，炉渣粘度急剧增大；TiC、TiN在炉渣中的分散形态对粘度也有很大影响，相同的含量下，分散程度越高，炉渣粘度越大，反之亦然。反应动力学条件和扩散条件对TiC、TiN的分散形态有重要的影响。 <WP=6>② 含钛炉渣的熔化性温度普遍较高，大约比普通高炉渣高80～100℃。其原因主要是渣中存在着TiC、TiN等高熔点物相。容易在炉渣结晶过程中提供非均质形核的异相质点，降低形核所需的过热度。研究了炉渣的表面性质问题。在深入分析了低温溶液表面粘度测定方法的基础上，提出了采用激光束测定高温熔体表面粘度的思路，并据此设计了激光表面粘度测定仪，实际测定了各种不同炉渣组分时炉渣的表面粘度，分析了炉渣组分对表面粘度的影响以及表面粘度和炉渣涨泡性能之间的关系，研究结果充分表明：① 含钛高炉渣泡沫化现象的内在原因是，由于含钛氧化物以及在还原条件下产生的TiC、TiN等高熔点质点，改变了炉渣的表面性质，使之有利于气泡在渣中稳定存在；即炉渣中的固相质点不仅改变了体相性质，也改变了炉渣的表面性质。② 在炉渣的表面性质中，表面张力和表面粘度对泡沫化都具有重要的作用，但表面张力在起泡阶段起着重要作用，表面粘度在稳定泡沫阶段起着重要作用。炉渣中表面活性物质降低其表面张力，有利于泡沫的形成，但不一定会提高炉渣的表面粘度，对炉渣泡沫化的影响取决于两者之间的强弱。③ 采用激光法测定熔渣的表面粘度是可行的。特别是对高温熔体的表面性质的测定具有参考价值。但是还需要进一步改进，提高测定的精确性。今后研究的重点是物质的表面结构与表面粘度之间的关系。④ CaF2、MnO等表面活性物质不利于炉渣的泡沫化。对TiO2在炉渣中的活度进行了尝试性测定，并在理论上利用共存理论模型对CaO-SiO2-TiO2-Al2O3-MgO五元渣系中TiO2的作用浓度进行了计算。实验研究和理论分析说明：① 可以采用电动势法测定含钛炉渣中TiO2的活度，但是有很大的难度。 分子离子共存模型可以用于计算含钛炉渣中组元的活度。与实验结果相比较，误差是可以接受的。③ 含钛炉渣中TiO2的活度或作用浓度是随着其含量的增加而增加的。因此要抑制含钛炉渣的性能恶化，关键是降低其活度。含钛炉渣非牛顿流体性质的研究。按照非牛顿流体的测定方法，对含钛炉渣进行测定，并将测定结果与以前视为牛顿流体测定的结果进行对比，进行系统分析，并深入研究其内在的联系，以揭示含钛炉渣特殊性能的核心问题。通过研究表明：① 含钛炉渣具有非牛顿流体的特性。② 含钛炉渣的非牛顿流体特性与炉渣的其它物理化学性质之间有一定的关<WP=7>系，但准确的数学关系，需要进一步深入的研究，才能获得明确的结果。含钛高炉渣的微波处理研究。这是一个有意义的探索，通过微波处理含钛高炉渣，有?更多还原

【Abstract】 The Vanadic Titanomagnetite resource of Panzhihua and Xichang area is one of the most three famous composite paragentic mineral deposits in China, and is also a world-famous mineral resource. The exploitation and comprehensive utilization of the Vanadic Titanomagnetite in Panzhihua and XiChang areas was a main task of metallurgist of China in the past three decades, after year’s of hard work, PanZhihua iron and steel corporation has been one of the large-scaled united companies, and both its exploitation and utilization of iron, vanadium and titanium have attained great achievements. But, no matter the iron-smelt processing or the the special properties of its high-titanium slag, there are still some physicochemical problems which is different from the normal BF slags. The further research is helpful to enrich the basic theories of separation science of paragentic mineral, to provide a useful reference for other kind of paragentic mineral, and also, to improve practical technology of iron-smelting and the development levels of comprehensive utilization for BF slag bearing Titania. On the base of proper investigating of the present research development about the physicochemical property of high-titanium slag in domasitic and aboard, the following research works are finished in laboratory scale by the author: the measuring of some properties of BF slag bearing titania, including the viscosity, the free running temperature, the surface tension, the surface viscosity and the activity of titanium dioxide; and a research about the thermodynamic property and physicochemical property of CaO-SiO2-TiO2-Al2O3-MgO based on the structure model of different slag also has been done. With non-Newtonian fluid theory the relationship between foaming mechanics of high-titanium BF slag and its physicochemical property have been analyzed. A preliminary research of the effect between microwave and high-titanium BF slag finally was done whereas the mechanics has been discussed. The specific research and conclusions are shown as follows:(1)As for the viscosity of high-titanium BF slag, the dual basicity of different slag、the content of TiO2、the reducing level、the viscosity of high-smelting point titanium carbide and titanium nitride compared to slag and the free running temperature have been gotten by rotational viscometer in laboratory scale. In this situation, the range of action that speed of gauge head’s rotational contributes to slag and basic principle in the measurement process with application of non-Newtonian flux were got. After analyzing <WP=10>the viscosity results from different titanium carbide and titanium nitride contents, the contribution of solid phase particles to the viscosity was discussed based on the equation of Einstein, then the phenomenon that the relationship between solid phase particles and slag viscosity was not abided by the equation of Einstein was found, a concept of “sub-colloid” was conducted and the relationships between slag’s bodying and the scattered state of titanium carbide and titanium nitride was found subsequently. Via the experiment research and conduction in theory the results obtained include:①The viscosity of BF high-titanium slag will not curdle in the oxidation atmosphere or neutral atmosphere. The reduction extent of titanium dioxide plays a important role in the process of the slag’s bodying, and the apparent viscosity will increase because of the increase of titanium carbide and titanium nitride generated by the deep reductions, especially when the concentration of titanium carbide and titanium nitride exceeds six percent, the slag viscosity will increase sharply; It was also found that the scattered state of titanium carbide and titanium nitride played a important part in the increase of viscosity, in the case of same content, the greater the extent of scatter is , the higher the viscosity becomes, vice versa, the situations of reaction kinetics and scatter have a great effect to the scattered state ②It was found that the free running temperature is gen更多还原