电磁场影响渣金界面反应动力学条件的实验研究
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摘要
渣金界面反应是冶金工业中最重要的多相反应之一,因此渣金界面反应动力学条件的改善对于提高冶金生产效率具有重要意义。作为电磁冶金的重要手段,交流移动磁场以及稳恒强磁场都可以对金属液行为进行有效控制,从而显著改变渣金界面反应的动力学条件。但目前交流移动磁场在钢铁冶金中的应用研究主要集中于连铸过程钢液内的流场、温度场和浓度场的均匀化,而强磁场影响渣金界面反应动力学条件的研究也非常有限。因此,本研究在国家自然科学基金项目支持下对交流移动磁场(电磁搅拌)条件下的渣金界面反应和金属液行为以及强磁场条件下的渣金界面反应进行了系统的实验研究,探讨了电磁场下渣金界面反应动力学条件及电磁场对该条件的影响机理。
本研究以钢铁冶金中典型的渣金反应-铁水预处理脱硫为例,对不同电磁搅拌方式及强度下的铁水脱硫反应进行了实验研究,获得了不同条件下硫的容量传质系数；研究结果表明电磁搅拌可以大幅加快铁水脱硫速率,并且脱硫速率随着电磁搅拌强度的增加而加快,不同电磁搅拌方式下的脱硫速率差异明显,电磁搅拌通过改变铁水与熔渣间的界面形态,硫传质的边界层厚度以及铁水卷渣行为影响铁水脱硫速率；载气方式加入脱硫剂并结合电磁搅拌作用可以显著增加脱硫剂和铁水的接触面积和接触时间,是一种比较优越的工艺；旋转电磁搅拌可以获得很高的硫传质系数,从而提高铁水脱硫效率以及脱硫剂的利用率,是一种有应用前景的环境友好工艺。
为深入研究渣金界面反应动力学条件的改善与电磁搅拌对金属液行为(内部流动,表面形状和表面波动等)的促进作用的关系,本研究首次利用超声波多普勒测速仪对与钢液物理性质非常相似的Pb-Sn-Bi合金液的内部流速进行了测量与分析,同时,本研究还使用激光液位仪对钢包精炼中常用电磁搅拌下金属液的自由表面形状和表面波动状况进行了考察,量化电磁搅拌对渣金界面积等动力学条件的影响。结果表明不同电磁搅拌方式对金属液行为影响的差异明显,在实际冶金生产中,可以针对不同的工艺要求进行调整。如果需要优先考虑改善动力学条件,促进渣金反应,可以优先采用单侧或对向电磁搅拌方式；如果对夹杂物控制要求较高,需要防止卷渣现象的发生,并保证相对稳定的金属液流动状态,则可以采用对称电磁搅拌方式。本研究结果对冶炼工艺中电磁搅拌方式的合理选择以及操作参数的优化具有指导意义；另外,本研究也为电磁场下冶金反应动力学条件的研究提供了新的思路。
渣金界面处金属液卷渣行为对渣金界面反应动力学条件的控制具有重要意义。本研究首次使用超声波多普勒测速仪对电磁搅拌条件下钢包炉模型内渣金界面处的卷渣临界流速进行了测量分析,研究结果表明,由于边界条件限制,金属液表面的最大水平流速随着搅拌强度的增加而呈抛物线式增加,因此应根据工艺要求,将搅拌强度调节在—定合理范围内。本研究对应的实际钢包卷渣临界流速为800mm/s,临界韦伯数We为20,靠近搅拌器一侧钢包壁面处的卷渣临界磁场强度为0.023T,对应的钢液中心位置处的磁场强度为0.0023T。实际钢包精炼生产中可以依据卷渣临界流速对电磁搅拌下冶炼工艺的进行优化。
另一方面,本研究首次考察了强磁场对渣金界面反应动力学条件的影响。在不同强磁场条件下,Al-Cu合金与质量配比为MgF2:CaF2:LiF:ZrF4=1.7:1:1.5:9.3的四元熔渣间发生的渣金反应的速率表明,施加无梯度强磁场时,渣金界面反应速率在微观磁流体效应影响下加快；而在梯度强磁场条件下,金属液流动同时受到梯度强磁场引发的磁化力以及微观磁流体效应的影响,因此渣金界面反应速率会相应发生改变。
Slag-metal interfacial reaction is one of the most important multiphase reactions in metallurgical industry, so improvement on slag-metal interfacial reaction kinetics is beneficial to promotion of metallurgical efficiency. Traveling magnetic field and high magnetic field can effectively influence the behaviors of liquid metal so as to change the slag-metal interfacial reaction kinetics greatly, while most of the researches on application of electromagnetic stirring in ferrous metallurgy mainly focused on continuous casting process, and researches on effect of high magnetic field on slag-metal interfacial reaction are quite limited so far. Therefore, slag-metal interfacial reactions with imposition of traveling magnetic field (electromagnetic stirring) and high magnetic field were investigated experimentally with support of national natural science foundation projects of china to study influence mechanism of electromagnetic field on slag-metal interfacial reaction kinetics.
Desulphurization in hot metal pretreatment is a typical slag-metal interfacial reaction in ferrous metallurgy. Desulphurization experiments with different electromagnetic stirring intensity and stirring types were investigated, and the volume mass transfer coefficients corresponding to different stirring conditions were determined finally. The experiment results show that desulphurization rate of hot metal differed with electromagnetic stirring types, and electromagnetic stirring could change the interfacial state and boundary layer thickness of sulphur mass transfer so as to promote the desulphurization process. The contacting area and contacting time of desulphurizer and hot metal would increase greatly when the desulphurizer was carried into hot metal with argon. The volumetric mass transfer coefficient of sulphur in desulphurization experiment with rotating electromagnetic stirring was very large, and the desulpurization efficiency in the desulphurization process was improved greatly. The environment-friendly technology has potential to be widely used in metallurgical industry.
The effect of electromagnetic stirring on slag-metal interfacial reaction kinetics is mainly caused by promotion of electromagnetic stirring on liquid metal behaviors (internal flow, free surface shape, level fluctuation, etc.)-Internal flow of Pb-Sn-Bi alloy was successfully measured with ultrasonic Doppler velocimetry for the first time in order to further study flow field of liquid metal exposed to various electromagnetic stirring types. Furthermore, free surface shape and level fluctuation of liquid metal exposed to various electromagnetic stirring types were measured and analyzed with laser liquid level apparatus in order to quantify the effect of electromagnetic stirring on slag-metal interfacial reaction kinetics in this study. The results showed that effect of electromagnetic stirring on internal flow and level fluctuation of liquid metal differed with electromagnetic stirring types, so different electromagnetic stirring types should be introduced to meet technological requirements. The study also provides evidence for stirring parameter adjustment. Due to the physical properties of Pb-Sn-Bi alloy are similar to molten steel, this study is of important guiding significance for research on metallurgical kinetics under the imposition of magnetic field.
The internal flow distribution of liquid metal on slag-metal interface was measured and analyzed with ultrasonic Doppler velocimetry for the first time to determine the important metallurgical parameters such as critical velocity of slag entrapment as well as the relevant parameters of actual ladle furnace. The results showed that the maximum horizontal velocity on the slag-metal interface increased parabolically with the increase of stirring intensity. The determined critical velocity of slag entrapment, weber number, magnetic field intensity in molten steel next to electromagnetic stirrer and magnetic field intensity in the center of ladle furnace were800mm/s,20,0.023T and0.0023T respectively. Different electromagnetic stirring intensity should be introduced to meet different refining requirements according to the critical velocity of slag entrapment.
On the other hand, rate of slag-metal interfacial reaction in high magnetic field under different conditions was investigated to make sure of how the high magnetic field influence every step in the reaction process on slag-metal interface and the global reaction rate. The reaction rate between Al-Cu alloy and quaternionic slag revealed that the reaction rate was quickened owing to the micro-MHD effect if the high magnetic field applied to the reaction interface is of zero gradient, while the reaction rate changed in gradient magnetic field because the reaction interface was under the action of both the magnetization force evoked by the magnetic field and micro-MHD effect. A conclusion is thus drawn that the reaction rate on slag-metal interface can be controlled efficiently via high magnetic field.
本研究以钢铁冶金中典型的渣金反应-铁水预处理脱硫为例,对不同电磁搅拌方式及强度下的铁水脱硫反应进行了实验研究,获得了不同条件下硫的容量传质系数；研究结果表明电磁搅拌可以大幅加快铁水脱硫速率,并且脱硫速率随着电磁搅拌强度的增加而加快,不同电磁搅拌方式下的脱硫速率差异明显,电磁搅拌通过改变铁水与熔渣间的界面形态,硫传质的边界层厚度以及铁水卷渣行为影响铁水脱硫速率；载气方式加入脱硫剂并结合电磁搅拌作用可以显著增加脱硫剂和铁水的接触面积和接触时间,是一种比较优越的工艺；旋转电磁搅拌可以获得很高的硫传质系数,从而提高铁水脱硫效率以及脱硫剂的利用率,是一种有应用前景的环境友好工艺。
为深入研究渣金界面反应动力学条件的改善与电磁搅拌对金属液行为(内部流动,表面形状和表面波动等)的促进作用的关系,本研究首次利用超声波多普勒测速仪对与钢液物理性质非常相似的Pb-Sn-Bi合金液的内部流速进行了测量与分析,同时,本研究还使用激光液位仪对钢包精炼中常用电磁搅拌下金属液的自由表面形状和表面波动状况进行了考察,量化电磁搅拌对渣金界面积等动力学条件的影响。结果表明不同电磁搅拌方式对金属液行为影响的差异明显,在实际冶金生产中,可以针对不同的工艺要求进行调整。如果需要优先考虑改善动力学条件,促进渣金反应,可以优先采用单侧或对向电磁搅拌方式；如果对夹杂物控制要求较高,需要防止卷渣现象的发生,并保证相对稳定的金属液流动状态,则可以采用对称电磁搅拌方式。本研究结果对冶炼工艺中电磁搅拌方式的合理选择以及操作参数的优化具有指导意义；另外,本研究也为电磁场下冶金反应动力学条件的研究提供了新的思路。
渣金界面处金属液卷渣行为对渣金界面反应动力学条件的控制具有重要意义。本研究首次使用超声波多普勒测速仪对电磁搅拌条件下钢包炉模型内渣金界面处的卷渣临界流速进行了测量分析,研究结果表明,由于边界条件限制,金属液表面的最大水平流速随着搅拌强度的增加而呈抛物线式增加,因此应根据工艺要求,将搅拌强度调节在—定合理范围内。本研究对应的实际钢包卷渣临界流速为800mm/s,临界韦伯数We为20,靠近搅拌器一侧钢包壁面处的卷渣临界磁场强度为0.023T,对应的钢液中心位置处的磁场强度为0.0023T。实际钢包精炼生产中可以依据卷渣临界流速对电磁搅拌下冶炼工艺的进行优化。
另一方面,本研究首次考察了强磁场对渣金界面反应动力学条件的影响。在不同强磁场条件下,Al-Cu合金与质量配比为MgF2:CaF2:LiF:ZrF4=1.7:1:1.5:9.3的四元熔渣间发生的渣金反应的速率表明,施加无梯度强磁场时,渣金界面反应速率在微观磁流体效应影响下加快；而在梯度强磁场条件下,金属液流动同时受到梯度强磁场引发的磁化力以及微观磁流体效应的影响,因此渣金界面反应速率会相应发生改变。
Slag-metal interfacial reaction is one of the most important multiphase reactions in metallurgical industry, so improvement on slag-metal interfacial reaction kinetics is beneficial to promotion of metallurgical efficiency. Traveling magnetic field and high magnetic field can effectively influence the behaviors of liquid metal so as to change the slag-metal interfacial reaction kinetics greatly, while most of the researches on application of electromagnetic stirring in ferrous metallurgy mainly focused on continuous casting process, and researches on effect of high magnetic field on slag-metal interfacial reaction are quite limited so far. Therefore, slag-metal interfacial reactions with imposition of traveling magnetic field (electromagnetic stirring) and high magnetic field were investigated experimentally with support of national natural science foundation projects of china to study influence mechanism of electromagnetic field on slag-metal interfacial reaction kinetics.
Desulphurization in hot metal pretreatment is a typical slag-metal interfacial reaction in ferrous metallurgy. Desulphurization experiments with different electromagnetic stirring intensity and stirring types were investigated, and the volume mass transfer coefficients corresponding to different stirring conditions were determined finally. The experiment results show that desulphurization rate of hot metal differed with electromagnetic stirring types, and electromagnetic stirring could change the interfacial state and boundary layer thickness of sulphur mass transfer so as to promote the desulphurization process. The contacting area and contacting time of desulphurizer and hot metal would increase greatly when the desulphurizer was carried into hot metal with argon. The volumetric mass transfer coefficient of sulphur in desulphurization experiment with rotating electromagnetic stirring was very large, and the desulpurization efficiency in the desulphurization process was improved greatly. The environment-friendly technology has potential to be widely used in metallurgical industry.
The effect of electromagnetic stirring on slag-metal interfacial reaction kinetics is mainly caused by promotion of electromagnetic stirring on liquid metal behaviors (internal flow, free surface shape, level fluctuation, etc.)-Internal flow of Pb-Sn-Bi alloy was successfully measured with ultrasonic Doppler velocimetry for the first time in order to further study flow field of liquid metal exposed to various electromagnetic stirring types. Furthermore, free surface shape and level fluctuation of liquid metal exposed to various electromagnetic stirring types were measured and analyzed with laser liquid level apparatus in order to quantify the effect of electromagnetic stirring on slag-metal interfacial reaction kinetics in this study. The results showed that effect of electromagnetic stirring on internal flow and level fluctuation of liquid metal differed with electromagnetic stirring types, so different electromagnetic stirring types should be introduced to meet technological requirements. The study also provides evidence for stirring parameter adjustment. Due to the physical properties of Pb-Sn-Bi alloy are similar to molten steel, this study is of important guiding significance for research on metallurgical kinetics under the imposition of magnetic field.
The internal flow distribution of liquid metal on slag-metal interface was measured and analyzed with ultrasonic Doppler velocimetry for the first time to determine the important metallurgical parameters such as critical velocity of slag entrapment as well as the relevant parameters of actual ladle furnace. The results showed that the maximum horizontal velocity on the slag-metal interface increased parabolically with the increase of stirring intensity. The determined critical velocity of slag entrapment, weber number, magnetic field intensity in molten steel next to electromagnetic stirrer and magnetic field intensity in the center of ladle furnace were800mm/s,20,0.023T and0.0023T respectively. Different electromagnetic stirring intensity should be introduced to meet different refining requirements according to the critical velocity of slag entrapment.
On the other hand, rate of slag-metal interfacial reaction in high magnetic field under different conditions was investigated to make sure of how the high magnetic field influence every step in the reaction process on slag-metal interface and the global reaction rate. The reaction rate between Al-Cu alloy and quaternionic slag revealed that the reaction rate was quickened owing to the micro-MHD effect if the high magnetic field applied to the reaction interface is of zero gradient, while the reaction rate changed in gradient magnetic field because the reaction interface was under the action of both the magnetization force evoked by the magnetic field and micro-MHD effect. A conclusion is thus drawn that the reaction rate on slag-metal interface can be controlled efficiently via high magnetic field.
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