Solubility of nitrogen in CaO-SiO2-CaF2 slag system

Equilibrium experiments between gas and slag were carried out to understand the thermodynamic behaviour of nitrogen in the CaO-SiO₂-CaF₂ slag system at 1600°C. The solubility of nitrogen in this slag system increased as the oxygen potential decreased and as the reaction temperature increased. The values of the nitride capacity have a minimum at about 2.0 slag basicity, having higher values in both more acidic and basic regions. This may be explained by two mechanisms for nitrogen dissolution; incorporated nitride ion and free nitride ion state. In slag with 2.0 basicity or less, MgO content increased the nitride capacity slightly. At higher slag basicity, however, nitride capacity decreased with MgO content. The effects of BaO to substitute CaO on nitride capacity showed similar behaviour as MgO. This complex relationship between basicity of slag and nitride capacity is explained by using optical basicity. It was found that nitride capacity and optical basicity had a close relationship even in the different basic oxide systems.     

Oxidation state and activities of chromium oxides in CaO-SiO2-CrOx slag system

The activities of chromium oxides in a CaO-SiO₂-CrO _x slag system were determined with the electromotive force (EMF) method by equilibrating with metallic chromium at 1873 K. The effect of slag basicity on the activity coefficients of CrO and CrO_1.5 was analyzed. The results showed that increasing the slag basicity increased the activity coefficient of CrO; however, the effect on that of CrO_1.5 was not significant. The oxidation state of chromium in CaO-SiO₂-CrO _x slags was systematically investigated at both 1873 and 1863 K. It was found that divalent and trivalent chromium coexists in the slags. Divalent chromium oxide is favored, instead of trivalent chromium oxide, because of low slag basicity and low oxygen potential. It was concluded that the oxidation state of chromium in the slag system varied greatly from almost pure “CrO” to a composition corresponding to Cr₃O₄. In addition, the thermodynamic data in the slag system were assessed based on the regular solution model to mathematically describe the activities of chromium oxides in the slags. A group of model parameters were obtained. The calculated activities of chromium oxides were comparable to the measured data.     

Thermodynamic behaviour of carbonate in CaO based slag

Carbonate solubility was measured for CaO bearing slag systems at 1600 °C under different thermodynamic conditions by using equilibration techniques. Carbonate solubility increased with activity of (CaO). The reaction mechanism of the carbonate dissolution in slag can be expressed as a reaction between CO₂ gaseous phase and oxygen ion to form carbonate (CO₃^2-). Carbonate capacities of various slags depended not only on oxygen ion but also activity coefficient of carbonate ion. The activity coefficient of carbonate ion in CaO-SiO₂ slag changed with CaO content, but that of CaO-Al₂O₃ slag did not change remarkably. Substitution of MgO by CaO for solubility of carbonate had a similar effect as in the case of carbide in CaO-SiO₂-MgO slag. The critical oxygen potential for carbide and carbonate stability was found to be 10-¹⁰ bar.     

CaO-SiO2-Al2O3-Fe2O3渣系脱磷行为

利用Factsage软件计算了Al2O3含量对CaO-SiO2-Al2O3-Fe2O3四元渣系熔点和黏度的影响,并通过实验研究了在1 400℃时,CaO-SiO2-Al2O3-Fe2O3四元渣系对高磷铁水脱磷行为的影响.结果表明:渣中Al2O3的质量分数在3％～6％之间时,随着A12O3含量的增加,渣系的熔化温度迅速降低,进一步增加渣中的A12O3含量,渣系的熔化温度逐渐增加;Al2O3对CaO-SiO2-Al2O3-Fe2O3渣系的黏度影响不大;渣中Al2O3的质量分数在3％～6％之间变化时,渣系脱磷能力变化不是很大,脱磷率维持在91％左右,进一步增加渣系中A12O3的量,脱磷率逐渐下降;Al2O3对脱磷率产生影响可能是其改变了炉渣中液相所占比例,进而影响磷从铁水中向液相渣的传质过程.     

Thermodynamics of chromium oxides in CaO-SiO2-CaF2 slag

The distribution ratio of chromium between a CaO-SiO₂-CaF₂ slag and liquid silver under the oxygen partial pressure used in practical hot-metal dephosphorization treatment was measured at 1623 K. The distribution ratio was minimal when the basicity index of a slag, wt pct CaO/wt pct SiO₂, was about 2. The redox equilibrium between CrO (Cr²⁺) and CrO_1.5 (Cr³⁺) in the slag was also measured as a function of slag composition. The calculated activity coefficient of CrO had a maximum value at wt pct CaO/wt pct SiO₂=2, whereas that of CrO_1.5 decreased monotonously with the increase in slag basicity.     

CaO-SiO2-FeOx及CaO-SiO2-P2O5-FeOx渣系热力学性质的研究

CaO-SiO2-FeOx三元渣系和CaO-SiO2-P2O5-FeOx四元渣系是转炉脱磷用渣的主要子渣系,研究这两种渣系的热力学性质可为脱磷渣的高效利用提供理论依据。利于相图软件FactSage分别绘制了这两种渣系的相图,并分析了温度和氧分压对体系相平衡关系和液相线的影响规律。分析结果表明:升高温度会使这两种渣系的液相区扩大,初晶相稳定区域显著减小;降低氧分压会导致尖晶石固溶体相的初晶区消失,磷石英(SiO2)、伪硅灰石(CaSiO3)、α’-Ca2SiO4固溶体相减小。     

碱度对CaO-SiO2-Al2O3系熔渣微观结构的影响

为了明确精炼渣冶金功能的微观本质,本文模拟精炼渣的化学组成,采用拉曼光谱测定并解析了CaO-SiO2-Al2 O3系实验渣的熔体结构.结果表明,熔渣中Si4+以[SiO4]-四面体结构形式存在,随着碱度的升高,Q1Si和Q2Si含量减少,Q0Si含量增加;Al3+以[AlO4]-四面体和[AlO6]-八面体结构形式存在...     

CaO-SiO2-B2O3熔渣的热力学计算模型

根据CaO-SiO2、CaO-B2O3和SiO2-B2O3二元相图确定了熔渣的结构单元,利用熔渣的分子离子共存理论建立了CaO-SiO2-B2O3三元熔渣活度模型。通过对模型求解,可以计算出熔渣中CaO、SiO2、B2O3、CS、C2S、C3B、C2B、CB和CB2的组分活度。分析了熔渣碱度、B2O3含量及温度对熔渣组分活度的影响,其中熔渣碱度的影响最大,B2O3含量的影响次之,温度的影响最小。     

温度对CaO-SiO2-Al2O3-MgO高炉渣系Al2O3活度的影响

 Al₂O₃作为熔渣中的主要组元之一,其对熔渣的冶金性能的影响尤为突出。对于高炉炼铁而言,高炉渣中Al₂O₃增加会对炼铁及脱硫造成不利影响。然而,随着中国钢铁工业的不断发展,相对低廉的高Al₂O₃进口铁矿石使用量不断攀升,使得高炉渣中Al₂O₃含量明显增加,高炉渣中Al₂O₃质量分数往往大于15%,更高的甚至大于20%。目前关于高Al₂O₃高炉渣系中Al₂O₃组元的热力学性质(例如采用参考渣法测定Al₂O₃的活度)及其对炉渣冶金性能的影响等研究鲜有报道,而温度是影响冶金熔渣冶金性能的重要热力学因素之一,因此探讨温度对冶金熔渣中Al₂O₃组元活度影响的规律不仅具有重要的研究意义,同时也为现场实践提供坚实的理论依据。采用参考渣法对1 773～1 873 K温度条件下CaO-SiO₂-Al₂O₃-MgO高炉渣系Al₂O₃活度进行测定,并采用Raman光谱对熔渣的结构进行检测。考察了温度对CaO-SiO₂-Al₂O₃-MgO高炉渣系Al₂O₃活度的影响。结果表明,随着温度的增加,熔渣中Al₂O₃的化学势降低,熔渣与铜金属熔液之间的反应向右移动来达到新的平衡,因而Al₂O₃的活度随着温度的增加逐渐降低。温度的增加使熔渣中Al₂O₃与碱性金属氧化物发生反应,使钙铝酸盐(CaO·Al₂O₃和CaO·2Al₂O₃)和镁铝酸盐(MgO·Al₂O₃)等复合物生成量增加,此时熔渣的结构由于O2-的增加而逐渐发生解聚,熔渣中的自由Al₂O₃减少,从而导致Al₂O₃活度逐渐降低。     

MgO和MnO对CaO-SiO2-Fe2O3-P2O5渣的物相影响

转炉渣中的磷主要存在于n2CaO·SiO2-3CaO·P2O5（以下简记为nC2S-C3P）固溶体的富磷相中。为了深入理解转炉渣的物相,便于有效富集钢渣中的磷,研究MgO和MnO含量的变化对CaO-SiO2-Fe2O3-P2O5渣中nC2S-C3P固溶体的磷含量及渣结晶物相的影响,并对其进行热力学分析。结果表明：在CaO-SiO2-Fe2O3-P2O5四元渣系中加入少量MgO或MnO,可以在一定程度上提高nC2S-C3P固溶体中的磷含量;继续提高MgO或MnO含量,固溶体中的磷含量不再发生变化。随着MgO或MnO的加入,富铁相增多,有利于钢渣的磁选分离。     

基于转炉CaO-SiO2-FeO-10%MgO渣系脱磷行为

 基于CaO-SiO2-FeO-10%MgO渣系,从热力学角度对渣钢界面的脱磷行为进行分析,归纳出磷分配比与钢液温度、碳质量分数以及炉渣成分间的表达式,并在此基础上绘制出了CaO-SiO2-FeO-10%MgO渣系的等磷分配比线,同时分析了转炉终渣氧化性、碱度以及温度对磷分配比的影响情况。研究结果表明,转炉吹炼过程磷分配比是钢液温度、碳质量分数和炉渣成分的函数,通过与实际生产数据进行验证,发现其与实际结果吻合良好。基于该预测公式,在其他条件不变情况下,随着炉渣FeO质量分数增加,磷分配比[LP]先增加后减小,当终渣FeO质量分数为18%左右时达到最大值;随着终渣碱度的增加,渣钢间磷分配比增加,当终渣超过4.0时,磷分配比增加不再明显。     

Thermodynamic study on the effect of CaF2 on the nitrogen and carbon solubility in the CaO-Al2O3-CaF2 slag system

The nitrogen and carbon solubilities in the CaO-Al₂O₃-CaF₂ slag system at 1723K were measured to understand the effect of CaF₂ on the nitrogen and carbon dissolution behaviour using thermochemical equilibration technique. The nitride capacity in the CaO_satd.-Al₂O₃-CaF₂ system was constant until X_Al2O₃ / X_CaF2 = 0.23, followed by decrease with an increase in X_Al2O₃ / X_CaF2 ratio, and then showed a constant value. The carbide capacity in the CaO_satd.-Al₂O₃-CaF₂ system also showed the similar behaviour to the nitride capacity, however, the effect of CaF₂ on the activity coefficient of nitride and carbide ions showed some differences in case of X_CaF2 = 0.2. The effect of CaF₂ on the activity coefficient of carbide and nitride ions would not be significant in case of CaO-rich region of X_CaO / X_CaF2 = 0.31. However, CaF₂ could be expected to affect the activity coefficient of each ion in case of the Al₂O₃-rich region, causing compensating effect of the incorporated nitride (carbide) mechanism. The relationship between nitride and carbide capacity was also discussed.     

CaO-SiO2-MgO-Al2O3-BaO渣系脱硫能力研究

为了探究温度、碱度（R）、MgO质量分数和BaO质量分数对高炉渣脱硫能力影响,以酒钢现场高炉渣实际成分为基准,选取分析纯化学试剂配制实验渣样,采用双层石墨坩埚法研究了含钡渣系的脱硫能力,并考察BaO对脱硫动力学条件的影响。研究结果表明,增大高炉渣碱度,提高渣中MgO质量分数均能使硫分配比增加,炉渣脱硫能力增强。渣中BaO质量分数由0增加到4%,硫分配比先逐渐升高后略有降低,BaO质量分数为35%左右时硫分配比达到最大值。BaO质量分数增加使得熔渣中硫的传质系数增大,脱硫速率明显提升。     

An assessment of the CaO-SiO2 system

An evaluation of the CaO-SiO₂ system has been made using a newly developed model, a two-sublattice model for ionic solutions. Two alternatives were tested. In the first one, three anions were assumed, O⁻², SiO₄ ⁻⁴, and SiO₃ ⁻². In the second one, SiO₃ ⁻² was omitted. A set of parameter values describing the Gibbs energy of the liquid phase and solid phases was fixed for each alternative by a computer-operated optimization procedure called PARROT. Satisfactory assessments were achieved over the whole phase diagram range with both alternatives. The main difference between them occurs at the monotectic point. A comparison between calculated properties and experimental data is given. Formerly Research Associate, Royal Institute of Technoloy     

CaO-SiO_2-FeO-P_2O_5-Al_2O_3脱磷渣系中组元活度的计算

2CaO·SiO_2-3CaO·P_2O_5含磷固溶体的生成可提高转炉液相渣的脱磷能力,减少渣量.但目前CaO-SiO_2-FeO-P_2O_5-Al_2O_3渣系中各组元活度的变化规律尚不明确,无法为分析含磷固溶体的形成机理提供理论依据.为此,本文依据分子离子共存理论建立了熔渣组元的活度模型,分析了不同条件下组元活度的变化规律.结果表明:随渣中Al_2O_3含量的增加,2CaO·SiO_2、3CaO·P_2O_5、3FeO·P_2O_5的活度逐渐降低;随着碱度的增大,3CaO·P_2O_5的活度升高,2CaO·SiO_2、3FeO·P_2O_5的活度则呈先升高后降低的趋势;随着渣中FeO含量的增加,2CaO·SiO_2、3FeO·P_2O_5及CaO·Al_2O_3的活度逐渐增大,并在w(FeO)为15%时达到最大值,之后逐渐降低;升高温度会导致CaO、3CaO·SiO_2的活度增大,2CaO·SiO_2的活度降低.     

Some observations on the draining of CaO-SiO2-Al2O3 slag bubble films

Fundamentals of slag foaming were investigated by withdrawing slag bubble films from pools of CaO-SiO₂-Al₂O₃ slags using platinum wire frames in order to measure their draining rate and lifetime before rupture. Studies were carried out using a series of developed gravimetric and optical techniques. The results showed that increasing the temperature increased the rate of draining of the slag films; however, the influence of SiO₂ concentration for a given slag temperature appears rather complicated. Measurements of the thickness of bubble film plateau borders as a function of time showed slag temperature to be very important in influencing their draining behavior, i.e., the activation energy for the plateau-border thinning was found to be ∼ 150 kJ/mol, very close to that required for viscous flow in the system studied (∼60 kJ/mol). A lowering of the slag surface tension by addition of surface-active oxides (such as P₂O₅ and Na₂O) profoundly decreased the rate of draining of the films, irrespective of the slag temperature. This article is based on a presentation made in the “Geoffrey Belton Memorial Symposium,” held in January 2000, in Sydney, Australia, under the joint sponsorship of ISS and TMS.     

Fe-Cr-C金属与CaO-SiO2-MgO-(Al2O3)-CrOx渣反应平衡时渣中Cr含量预测

摘要：冶炼不锈钢或高温还原法处理不锈钢工业典型固废时,渣金反应终点渣中残Cr含量 (w(Cr)slag)的高低是评价还原操作经济性以及残渣是否无害的关键参数。借助热化学软件FactSage,计算了Fe-Cr-C熔体中［Cr］的活度、反应体系的氧势及CaO-SiO2-MgO-(Al2O3)-CrOx-O2熔渣的等活度图,并构建了残Cr预测模型,综合讨论了平衡态时金属成分(［Cr］、［C］含量)、熔渣成分(二元碱度、MgO、Al2O3)以及温度对渣中残Cr含量的影响,得到了不同条件下渣中残Cr含量的极限值。实验室试验结果与模型预测结果基本一致,验证了模型的可靠性。     

CaO-SiO2-FeO-Cr2O3-MgO-MnO渣系物相组成的热力学计算

摘要：在含铬铁水转炉冶炼过程中,Cr很容易被氧化成Cr2O3进入渣中,并与渣中其他成分反应生成高熔点含铬尖晶石。采用FactSage热力学软件计算了CaO-SiO2-FeO-Cr2O3-MgO-MnO转炉渣系在冶炼温度1300～1700℃下的物相组成,研究了Cr2O3、FeO和碱度对炉渣中尖晶石相含量的影响规律。研究结果表明,温度和渣系成分都会影响炉渣的物相组成。渣系中含有Cr2O3时,物相中均含有MgCr2O4、FeCr2O4和MgFe2O4尖晶石相,尖晶石相的总含量随着Cr2O3和碱度的增加而增加,随着炉温的升高而减少。温度为1300～1500℃时,炉渣中尖晶石含量随着FeO的增加而增加;温度为1500～1700℃时,尖晶石含量随着FeO的增加而略有减少。在温度小于1500℃的转炉冶炼前中期,炉渣物相组成中尖晶石相所占比例较大,易造成化渣不良或者炉渣粘稠,影响转炉冶炼工艺的顺行。     

Phase relations in the system CaO-SiO2-ZrO2 at 1573 K

Zirconia-based solid electrolytes with zircon (ZrSiC₄) as the auxiliary electrode have been suggested of sensing silicon concentrations in iron and steel melts. A knowledge of phase relations in the ternary system MO-SiO₂-ZrO₂ (M = Ca, Mg) is useful for selecting an appropriate auxiliary electrode. In this investigation, an isothermal section for the phase diagram of the system CaO-SiO₂ZrO₂ at 1573 K has been established by equilibrating mixtures of component oxides in air, followed by quenching and phase identification by optical miroscopy, energy disperse analysis of X-rays (EDAX) and X-ray diffraction analysis (XRD). The equilibrium phase relations have also been confirmed by computation using the available thermodynamic data on condensed phases in the system. The results indicate that zircon is not in thermodynamic equilibrium with calcia-stabilized zirconia or calcium zirconate. The silica containing phase in equilibrium with stabilized zirconia is Ca₃ZrSi₂O₉. Calcium zirconate can coexist with Ca₃ZrSi₂Og and Ca₂SiO₄.