钒渣体系物化性能及相平衡的研究
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摘要
金属钒被称为“现代工业的味精”，广泛应用于钢铁、化工、航空航天等领域。我国的攀西地区拥有丰富的钒钛磁铁矿资源。我国目前主要是利用高炉工艺从钒铁磁铁矿中冶炼得到含钒铁水，然后将含钒铁水入转炉氧化获得钒渣和半钢。半钢作为炼钢的原料，钒渣则主要通过湿法冶金工艺提取产品V_2O_5。
在转炉提钒工艺中，钒渣的高温物理化学性能直接影响到含钒铁水中钒的收得率和提钒工艺能否顺利进行。含钒铁水中各元素氧化过程的物理化学性质如何，影响到钒渣的质量和钒渣的物理化学特性；钒渣的粘度特性主要反映渣的流动性能，其优劣影响到钒渣冶炼过程渣-铁界面各种反应进行的难易程度及渣铁分离是否彻底；钒渣中尖晶石的生成及长大研究关系到后续湿法提钒过程的效率高低；钒渣中存在各相的具体组成及平衡关系，是衡量钒渣质量高低的重要指标；对钒渣基础渣系的相平衡关系的研究，则是提钒工艺理论指导的基本要求。
本文基于攀钢转炉提钒工艺过程，研究了含钒铁水中各元素氧化的物理化学特性，钒渣的粘度特性，钒渣中尖晶石的生成及长大影响因素和铁钒体系的相平衡，初步构建了钒渣基础渣系的相图，拟为提钒工艺的进一步优化、钒渣质量的更加提高提供理论支撑。
本文通过对钒渣体系物理化学性能及相平衡的研究，得到的结论如下：
①对含钒铁水中各元素氧化过程物理化学特性的研究结果表明，弱氧化剂CO_2作为含钒铁水的氧化气体，能够氧化铁水中各元素，但氧化速度有明显差异，用强氧化剂O_2吹炼含钒铁水，V的氧化明显增强，但整个过程中，始终滞后于Ti的氧化速度和氧化程度，即只要铁水中有钛元素，钒渣中将优先形成TiO_2。
②钒在钒渣中以正式钒铁尖晶石FeV_2O_4和反式钒铁尖晶石Fe_2VO_4的形式存在。钒渣中钒铁尖晶石结晶的生成和长大需要一定的过冷度，其最适宜的生长温度为1250℃。钒渣中尖晶石的数量和粒径与V_2O_3含量和w(FeO)/w(SiO_2)比值都有关系。
③钒渣粘度与温度的关系符合阿累尼乌斯方程，即温度升高，钒渣的粘度降低。渣中组分SiO_2对钒渣粘度的影响较为明显，低SiO_2含量时，提高其浓度可以降低钒渣的粘度，但是当SiO_2含量较高时，提高其浓度反而会使钒渣粘度升高。钒渣的粘度随V_2O_3含量的增加而升高，随w(FeO)/w(SiO_2)比值的升高而下降。
④在铁钒体系中，由于FeO的存在，FeO将与VO_2发生耦合生成V_2O_3，但不能与V_2O_3发生耦合生成VO。温度和FeO含量影响提钒体系中产物的组成。FeVO4的生成条件是V_2O_5含量较高尚余部分未分解时。Fe_2VO_4的生成条件是V_2O_5含量较少全部分解，FeO含量较高而只有少量被氧化时。
⑤修正的准化学溶液模型理论可以用来计算钒渣体系的相图。在确定了相图计算及实验可靠性的基础上，对FeO-SiO_2-V_2O_3三元系进行了不同等温截面的计算，得到了钒渣冶炼温度下该体系的等温截面。
Metal vanadium is called "modern industrial monosodium glutamate" and widelyused in iron and steel industry, chemical industry and aerospace industry. Panzhihuaand Xichang region in China has abundant resources of vanadium titanium magnetite.At present in China, the hot metal containing vanadium is formed mainly by the blastfurnace process from vanadium titanium magnetite, and then hot metal containingvanadium is oxidized in converter to form vanadium slag and semi steel. Semi steel isthe raw material of steelmaking and vanadium slag is the raw material of extractingV_2O_5products through the wet metallurgy process mainly.
In converter V-recovering process, the physical and chemical properties ofvanadium slag at high temperature directly affect the vanadium yield in hot metalcontaining vanadium and vanadium extraction process. The physical and chemicalproperties of the elements in vanadium slag oxidation process would affect thevanadium slag quality and physical and chemical properties of vanadium slag. Theviscosity properties of vanadium slag mainly reflect the flow properties of slag. Thegood and bad flow properties affect how easy the reaction will be to go in the slag-ironinterface and slag iron separation degree in the vanadium slag smelting process. Theresearch on the generation and growth of spinel in vanadium slag is related to the highand low efficiency in subsequent wet vanadium extraction process. The compositionand balance relationship of the phase in vanadium slag is the important index tomeasure vanadium slag quality. The research on phase equilibrium relationship of thebasic slag system of vanadium slag is the basic requirement to theoretical guidance invanadium extraction process.
Based on Pan-steel converter V-recovering process the physical and chemicalcharacteristics of the elements oxidation in hot metal containing vanadium, the viscosityproperties of vanadium slag, the influence factors of spinel generation, growth invanadium slag and the phase equilibrium of steel slag containing vanadium are studiedin this paper. As results, the phase diagram of basic slag system of vanadium slag isconstructed, to provide theoretical support for further optimization of vanadiumentraction process and the more improvement of vanadium slag quality.
This paper studies the physical and chemical properties and the phase equilibriumof vanadium slag system and the conclusions are as follows:
①The research results of the physical and chemical properties of the elementsoxidation process in hot metal containing vanadium show that the weak oxidant CO_2, asthe low vanadium molten iron oxide gas, can oxide the elements in iron oxide. But theoxidation rates of the elements are distinctly different. The oxidation degree of elementvanadium would enhance obviously when the hot metal containing vanadium are blowninto strong oxidant O_2. But in the whole process, the oxidation rate and degree ofelement vanadium always be behind that of elelment titanium. That is to say, as long asthe hot metal contains element titanium, TiO_2would be formed in the vanadium slagfirstly.
②Existing forms of vanadium in vanadium slag are formal vanadium iron spinelFeV_2O_4and trans vanadium iron spinel Fe_2VO_4. The formation and growth of vanadiumiron spinel crystal in Vanadium slag need a certain degree of supercooling and the mostappropriate growth temperature is1250℃. The spinel’s quantity and size in vanadiumslag is related to V_2O_3content and w(FeO)/w(SiO_2) ratio.
③The relationship of vanadium slag viscosity and temperature obeys Arrhenius'equation. That is to say, when the temperature is raised vanadium slag viscosity wouldbe reduced. SiO_2, one of the slag compositions, obviously influence the vanadium slagviscosity. When the content of SiO_2is lower, to improve its concentration could reducethe vanadium slag viscosity. If the content of SiO_2is higher, to improve itsconcentration, on the contrary, would make the vanadium slag viscosity rise. Vanadiumslag viscosity would increase with the content of V_2O_3rising and would decrease withw(FeO)/w(SiO_2) ratio rising.
④In iron and vanadium system, due to the existence of FeO, FeO will coupleV_2O_5to generate V_2O_3, but can not couple V_2O_3to generate VO. Temperature and thecontent of FeO influence the composition of the products in iron and vanadium system.The generation condition of FeVO4is that the content of V_2O_5is high enough and partof them has not decomposed. The generation condition of Fe_2VO_4is that the content ofV_2O_5is less and all of them has decomposed, but the content of FeO is higher and onlya small amount of them is oxidized.
⑤Modified quasi chemical solution model theory can be used to deal withthephase diagram of vanadium slag system. On the basis of determining the phasediagram calculation and experimental reliability, the isothermal sections ofFeO-SiO_2-V_2O_3ternary system at smelting temperature have been obtained bythermodynamic computation.
在转炉提钒工艺中，钒渣的高温物理化学性能直接影响到含钒铁水中钒的收得率和提钒工艺能否顺利进行。含钒铁水中各元素氧化过程的物理化学性质如何，影响到钒渣的质量和钒渣的物理化学特性；钒渣的粘度特性主要反映渣的流动性能，其优劣影响到钒渣冶炼过程渣-铁界面各种反应进行的难易程度及渣铁分离是否彻底；钒渣中尖晶石的生成及长大研究关系到后续湿法提钒过程的效率高低；钒渣中存在各相的具体组成及平衡关系，是衡量钒渣质量高低的重要指标；对钒渣基础渣系的相平衡关系的研究，则是提钒工艺理论指导的基本要求。
本文基于攀钢转炉提钒工艺过程，研究了含钒铁水中各元素氧化的物理化学特性，钒渣的粘度特性，钒渣中尖晶石的生成及长大影响因素和铁钒体系的相平衡，初步构建了钒渣基础渣系的相图，拟为提钒工艺的进一步优化、钒渣质量的更加提高提供理论支撑。
本文通过对钒渣体系物理化学性能及相平衡的研究，得到的结论如下：
①对含钒铁水中各元素氧化过程物理化学特性的研究结果表明，弱氧化剂CO_2作为含钒铁水的氧化气体，能够氧化铁水中各元素，但氧化速度有明显差异，用强氧化剂O_2吹炼含钒铁水，V的氧化明显增强，但整个过程中，始终滞后于Ti的氧化速度和氧化程度，即只要铁水中有钛元素，钒渣中将优先形成TiO_2。
②钒在钒渣中以正式钒铁尖晶石FeV_2O_4和反式钒铁尖晶石Fe_2VO_4的形式存在。钒渣中钒铁尖晶石结晶的生成和长大需要一定的过冷度，其最适宜的生长温度为1250℃。钒渣中尖晶石的数量和粒径与V_2O_3含量和w(FeO)/w(SiO_2)比值都有关系。
③钒渣粘度与温度的关系符合阿累尼乌斯方程，即温度升高，钒渣的粘度降低。渣中组分SiO_2对钒渣粘度的影响较为明显，低SiO_2含量时，提高其浓度可以降低钒渣的粘度，但是当SiO_2含量较高时，提高其浓度反而会使钒渣粘度升高。钒渣的粘度随V_2O_3含量的增加而升高，随w(FeO)/w(SiO_2)比值的升高而下降。
④在铁钒体系中，由于FeO的存在，FeO将与VO_2发生耦合生成V_2O_3，但不能与V_2O_3发生耦合生成VO。温度和FeO含量影响提钒体系中产物的组成。FeVO4的生成条件是V_2O_5含量较高尚余部分未分解时。Fe_2VO_4的生成条件是V_2O_5含量较少全部分解，FeO含量较高而只有少量被氧化时。
⑤修正的准化学溶液模型理论可以用来计算钒渣体系的相图。在确定了相图计算及实验可靠性的基础上，对FeO-SiO_2-V_2O_3三元系进行了不同等温截面的计算，得到了钒渣冶炼温度下该体系的等温截面。
Metal vanadium is called "modern industrial monosodium glutamate" and widelyused in iron and steel industry, chemical industry and aerospace industry. Panzhihuaand Xichang region in China has abundant resources of vanadium titanium magnetite.At present in China, the hot metal containing vanadium is formed mainly by the blastfurnace process from vanadium titanium magnetite, and then hot metal containingvanadium is oxidized in converter to form vanadium slag and semi steel. Semi steel isthe raw material of steelmaking and vanadium slag is the raw material of extractingV_2O_5products through the wet metallurgy process mainly.
In converter V-recovering process, the physical and chemical properties ofvanadium slag at high temperature directly affect the vanadium yield in hot metalcontaining vanadium and vanadium extraction process. The physical and chemicalproperties of the elements in vanadium slag oxidation process would affect thevanadium slag quality and physical and chemical properties of vanadium slag. Theviscosity properties of vanadium slag mainly reflect the flow properties of slag. Thegood and bad flow properties affect how easy the reaction will be to go in the slag-ironinterface and slag iron separation degree in the vanadium slag smelting process. Theresearch on the generation and growth of spinel in vanadium slag is related to the highand low efficiency in subsequent wet vanadium extraction process. The compositionand balance relationship of the phase in vanadium slag is the important index tomeasure vanadium slag quality. The research on phase equilibrium relationship of thebasic slag system of vanadium slag is the basic requirement to theoretical guidance invanadium extraction process.
Based on Pan-steel converter V-recovering process the physical and chemicalcharacteristics of the elements oxidation in hot metal containing vanadium, the viscosityproperties of vanadium slag, the influence factors of spinel generation, growth invanadium slag and the phase equilibrium of steel slag containing vanadium are studiedin this paper. As results, the phase diagram of basic slag system of vanadium slag isconstructed, to provide theoretical support for further optimization of vanadiumentraction process and the more improvement of vanadium slag quality.
This paper studies the physical and chemical properties and the phase equilibriumof vanadium slag system and the conclusions are as follows:
①The research results of the physical and chemical properties of the elementsoxidation process in hot metal containing vanadium show that the weak oxidant CO_2, asthe low vanadium molten iron oxide gas, can oxide the elements in iron oxide. But theoxidation rates of the elements are distinctly different. The oxidation degree of elementvanadium would enhance obviously when the hot metal containing vanadium are blowninto strong oxidant O_2. But in the whole process, the oxidation rate and degree ofelement vanadium always be behind that of elelment titanium. That is to say, as long asthe hot metal contains element titanium, TiO_2would be formed in the vanadium slagfirstly.
②Existing forms of vanadium in vanadium slag are formal vanadium iron spinelFeV_2O_4and trans vanadium iron spinel Fe_2VO_4. The formation and growth of vanadiumiron spinel crystal in Vanadium slag need a certain degree of supercooling and the mostappropriate growth temperature is1250℃. The spinel’s quantity and size in vanadiumslag is related to V_2O_3content and w(FeO)/w(SiO_2) ratio.
③The relationship of vanadium slag viscosity and temperature obeys Arrhenius'equation. That is to say, when the temperature is raised vanadium slag viscosity wouldbe reduced. SiO_2, one of the slag compositions, obviously influence the vanadium slagviscosity. When the content of SiO_2is lower, to improve its concentration could reducethe vanadium slag viscosity. If the content of SiO_2is higher, to improve itsconcentration, on the contrary, would make the vanadium slag viscosity rise. Vanadiumslag viscosity would increase with the content of V_2O_3rising and would decrease withw(FeO)/w(SiO_2) ratio rising.
④In iron and vanadium system, due to the existence of FeO, FeO will coupleV_2O_5to generate V_2O_3, but can not couple V_2O_3to generate VO. Temperature and thecontent of FeO influence the composition of the products in iron and vanadium system.The generation condition of FeVO4is that the content of V_2O_5is high enough and partof them has not decomposed. The generation condition of Fe_2VO_4is that the content ofV_2O_5is less and all of them has decomposed, but the content of FeO is higher and onlya small amount of them is oxidized.
⑤Modified quasi chemical solution model theory can be used to deal withthephase diagram of vanadium slag system. On the basis of determining the phasediagram calculation and experimental reliability, the isothermal sections ofFeO-SiO_2-V_2O_3ternary system at smelting temperature have been obtained bythermodynamic computation.
引文
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