A Thermodynamic Model for Prediction of Iron Oxide Activity in Some FeO‐Containing Slag Systems

A thermodynamic model for calculating the mass action concentrations of structural units in CaO–SiO₂–MgO–FeO–MnO–Al₂O₃–CaF₂ slags, i.e., the IMCT‐N_i model, has been developed based on the ion and molecule coexistence theory (IMCT). The calculated comprehensive mass action concentration of iron oxides $N_{{\rm Fe}_{t} {\rm O}} $ has been compared with the reported activity of iron oxide $a_{{\rm Fe}_{t} {\rm O}} $ in 14 FeO‐containing slag systems from literatures. The good agreement between the calculated $N_{{\rm Fe}_{t} {\rm O}} $ and reported $a_{{\rm Fe}_{t} {\rm O}} $ indicates that the developed IMCT‐N_i model can be successfully applied to predict the activity of iron oxide $a_{{\rm Fe}_{t} {\rm O}} $ as well as the slag oxidation ability of CaO–FeO (s1), SiO₂–FeO (s2), CaO–SiO₂–FeO (s3), CaO–FeO–Al₂O₃ (s4), SiO₂–MgO–FeO (s5), SiO₂–FeO–Al₂O₃ (s6), CaO–SiO₂–FeO–Al₂O₃ (s7), CaO–SiO₂–MgO–FeO–Al₂O₃ (s8), SiO₂–FeO–MnO (s9), SiO₂–FeO–MnO–Al₂O₃ (s10), FeO–MnO (s11), FeO–MnO–Al₂O₃ (s12), CaO–FeO–CaF₂ (s13), and CaO–SiO₂–FeO–CaF₂ slags (s14) in a temperature range of 1473–1973 K.     

Effects of Influencing Factors on Distribution Behaviors of Vanadium between Hot Metal and FeO‐SiO2‐MnO (‐TiO2) Slag System

The distribution behavior of vanadium between a hot metal and a FeO‐SiO₂‐MnO (‐TiO₂) slag system was studied under laboratory conditions, together with the effects of influencing factors such as temperature, slag composition, the ratio of slag to hot metal, and the initial Si and/or Ti content in hot metal. The results suggested that in a ternary FeO‐SiO₂‐MnO slag system, with an increase in temperature and an increase in the SiO₂ content of slag, the extraction ratio ($\eta _{V} $ ), distribution ratio of V ($L_{V} $ ) and the vanadium capacity of the slag ($C_{VO_{3} {}^{3{-} } } $ ) decreased, while the effect of MnO content in slag showed a different tendency under different situations. For both high and low ratios of slag to hot metal, the extraction ratio of V reached its maximum value under slag compositions of 13%–25% MnO and 10%–24% SiO₂, which correspond to the regions with lower melting point and lower viscosity of the slag. In a quaternary FeO‐SiO₂‐MnO‐TiO₂ slag system,$\eta _{V} $ ,$L_{V} $ , and $C_{VO_{3} {}^{3{-} } } $ decreased, while the activity coefficient of V₂O₃ increased, as the TiO₂ content increased. Further, the data suggested that under laboratory conditions the effects of influencing factors on the extraction ratio of V from hot metal decreased in the following order: final slag composition > temperature > initial Si and/or Ti content in hot metal.     

Distribution of P2O5 between Phosphorus‐Enrichment Phase and Matrix Phase in Phosphorus‐Containing Slag

In order to make better recovery utilization of the phosphorus in the steel slag, and as P₂O₅ mainly exists in phosphorus‐enrichment phase and matrix phase of steel slag, it is a must to study the distribution of P₂O₅ between those two phases in the phosphorus‐containing slag and its related influencing factors. Heat experiments were conducted in this research, and the final slag was analyzed with the method of scanning electron microscope (SEM) + energy disperse spectroscopy (EDS). Then L_p, r_p, and C_p in both phosphorus‐enrichment phase and matrix phase were calculated, respectively. From this study, is has been found that CaO% in matrix phase, the basicity of slag and mass fraction of P₂O₅ in both phosphorus‐enrichment phase and matrix phase influence the distribution ratio of P₂O₅ in the slag. Adding CaF₂ also has effect on P₂O₅ partition while adding MgO and MnO has no obvious effect. Besides, for the low content of T.Fe in matrix phase, there is no linear relationship between L_p or $\gamma _{{\rm P}_{2} {\rm O}_{5} } $ and T.Fe in matrix phase.     

The Effect of Carbon in Slag on Steel Reoxidation by CaO‐SiO2‐Al2O3‐MgO‐MnO‐FetO Slags

An equilibrium study was carried out at 1873K to ascertain the effect of carbon in CaO‐SiO₂‐Al₂O₃‐MgO‐MnO‐Fe_tO slag systems on their Fe_tO and MnO activity coefficients, representing the slags’ thermodynamic potential for steel reoxidation. Both γf e_to and γm no showed not only a sharp increment but also a simultaneous slow decrement by increasing carbon content in slag, suggesting opposite roles of the carbon according to its stable forms. XPS (X‐ray photoelectron spectroscopy) was introduced to clarify the stable forms of carbon in slag. XPS results prove that carbon dissolves in slag as carbonate, and carbide ions under oxidizing and reducing atmospheres, respectively. It was concluded that carbonate ions increase γf e_to and γm no , but that carbide decreases them. This paper suggests an application method of the present results to actual ladle refining processes, in order to enhance steel cleanliness with maintaining (Fe_tO + MnO) in slag to some allowable amount.     

In‐Situ Measurement of CO‐ and CO2‐Concentrations in BOF Off‐Gas

Improvement of the efficiency and productivity of steelmaking requires accurate and real‐time process information to precisely adjust the tapping conditions. The response time of BOF process control systems is commonly depending on the time needed for off‐gas sampling and analysis. A FTIR based measurement system was adapted and installed at an industrial steel converter of ArcelorMittal España S.A. in Aviles. An advanced data interpretation routine based on the quantum mechanical fundamentals of remote infrared (IR) spectroscopy was developed to enable precise determination of the {CO}‐ and {CO₂}‐concentrations, resp. their ratio, in the off‐gas. The results of the industrial measurement showed the ability of the FTIR based system for real‐time measurement of temperature, {CO}‐ and {CO₂}‐concentrations in the hot and dusty off‐gas. The influence of dust at the chosen defined optical path lengths in the IR wavelengths region can be neglected, but the collector lens clean has to be kept clean.     

Influence of SiO2 Addition on the Properties of Al2O3‐CaO‐CaF2 Slag

The Al₂O₃‐CaO‐CaF₂ slag system is used in making special quality steels by the electro‐slag re‐melting process (ESR). The purpose of our investigation was to analyse ESR slag that contained SiO₂. The slag samples with different SiO₂ fractions (0 ‐ 20 mass %) were examined by chemical analysis, differential thermal analysis, simultaneous thermal analysis, X‐ray diffraction, electron microscopy and wetting angle measurement. With addition of SiO₂ the polymerization of slags was increased due to the formation of new silicate complex compounds that influenced their melting points and wetting angles.     

Reaction between CaO‐SiO2‐Al2O3 Slags and H2 + HCl + H2O Gas Mixtures

To better understand the thermodynamic behaviour of chlorine in blast furnaces, CaO‐SiO₂‐Al₂O₃ slags were brought into equilibrium with Ar + H₂ + HCl + H₂O gas mixtures at temperatures between 1673 K and 1798 K. The dissolution of chlorine into molten slags could be well interpreted through a reaction: (1/2) {CaO}_slag + (HCl) = {Ca_1/2Cl}_slag + (1/2) (H₂O). Conforming to this formula, a linear relation was observed between log (%CI) and log with an anticipated slope of 1/2.     

Water Capacity Model of Al2O3‐CaO‐MgO‐SiO2 Quaternary Slag System

The focus of the present work was to develop a water capacity model for the quaternary slag system Al₂O₃‐CaO‐MgO‐SiO₂. In the model, a silicate melt was considered to consist of two ion groupings, viz. cation grouping and oxygen ion. The water capacity of a melt is supposed to depend on the interactions between the cations in the presence of oxygen ions. These interactions were determined on the basis of the experimentally measured water solubility data. Only binary interactions were employed in the model. For the system CaO‐SiO₂, disagreement in the literature data was found. Since the interaction between Ca²⁺ and Si⁴⁺ would play an important role, experiments were carried out to determine the water capacities of some CaO‐SiO₂ slags. For this purpose a thermogravimetric method was employed. Iso‐lines of water capacities at constant MgO contents were predicted by the model and compared with the experimental data from literature. The model calculations agreed well with the experimental results.     

Interfacial Tension between CaO‐Al2O3 Slag and Iron Containing Nonmetal or Tramp Elements

The interfacial tension between CaO‐Al₂O₃ slag and iron was studied for the iron containing nonmetal or tramp elements. The sessile drop technique was used to measure interfacial tensions under argon atmosphere at 1853K. Oxygen in liquid iron markedly reduced the interfacial tension. This effect was taken into consideration when analysing the interfacial tension between the slag and Fe‐S, Fe‐C, Fe‐Sn, Fe‐Sb and Fe‐Cu alloys. When adding S, Sn, Sb, or Cu to the iron, the interfacial tension was observed to decrease while carbon had no significant effect.     

Manganese Distribution between FeO‐MnO‐SiO2–CaO–MgO‐Al2O3 Slags and Molten Iron

Pretreatment of high manganese hot metal is suggested to produce hot metal suitable for further processing to steel in conventional LD converter and rich manganese slags satisfy the requirements for the production of silicomanganese alloys. Manganese distribution between slag and iron represents the efficiency of manganese oxidation from hot metal. The present study has been done to investigate the effect of temperature, slag basicity and composition of oxidizer mixture on the distribution coefficient of manganese between slag and iron. Ferrous oxide activity was determined in molten synthetic slag mixtures of FeO‐MnO‐SiO₂–CaO–MgO‐Al₂O₃. The investigated slags had chemical compositions similar to either oxidizer mixture or slags expected to result from the treatment of high manganese hot metal. The technique used to measure the ferrous oxide activity in the investigated slag systems was the well established one of gas‐slag‐metal equilibration in which molten slags contained in armco iron crucibles are exposed to a flowing gas mixture with a known oxygen potential until equilibrium has been attained. After equilibration, the final chemical analysis of the slags gave compositions having a particular ferrous oxide activity corresponding to the oxygen potential of the gas mixture. The determined values of ferrous oxide activity were used to calculate the equilibrium distribution of manganese between slag and iron. Higher manganese distribution between slag and iron was found to be obtained by using oxidizer containing high active iron oxide under acidic slag and relatively low temperature of about 1350°C.     

Effect of FeO and Al2O3 on the MgO Solubility in CaO–SiO2–FeO–Al2O3–MgO Slag System at 1823 K

The MgO solubility in CaO–SiO₂–FeO–Al₂O₃–MgO quinary slag system at 1823 K was measured to evaluate the effect of FeO and Al₂O₃ on the MgO solubility. It was found that the MgO solubility was decreased with higher optical basicity, FeO concentration, and increased with higher Al₂O₃ concentration. The MgO solubility was affected by activity coefficient of Mg²⁺ ($\gamma _{{\rm Mg}_{{\rm 2 + }} } $ ). Increase of the activity coefficient of Mg²⁺ ($\gamma _{{\rm Mg}_{{\rm 2 + }} } $ ) with higher FeO or lower Al₂O₃ decreased the MgO solubility. The increment in MgO solubility is remarkably reduced beyond a critical $X_{{\rm Al}_{2} {\rm O}_{{\rm 3}} } /(X_{{\rm Al}_{2} {\rm O}_{{\rm 3}} } + X_{{\rm FeO}} )$ ratio. The significant decrease of the increment of MgO solubility is caused by the change of the molten slag structure. The excess stability function of Al₂O₃ and the Fourier transform infrared (FT‐IR) analysis were applied to indirectly verify the existence of the spinel structure in the CaO–SiO₂–FeO–Al₂O₃–MgO slag system.     

The Activities of FexO in {CaO‐SiO2‐Al2O3‐MgO‐FexO} Slags at 1723 K

In Japanese steelworks, hot metal is now produced by scrap melting process. With this process removal of sulphur is very much handicapped because of very high sulphur levels (0.04 to 0.09 pct by weight) and relatively low tapping temperatures (1623 to 1723 K). In order to overcome such disadvantages, the authors explored on the phase diagrams of {CaO‐SiO₂‐Al₂O₃‐MgO} slags, and this research revealed that those slags at 35 wt%‐Al₂O₃ would be good candidates as reagents for the removal of sulphur from high sulphur hot metal at relatively low temperatures. For better understanding of the thermodynamic properties of the candidate slags, in this study, activities of Fe_xO were determined by using solid‐state electrochemical cells incorporating MgO‐stabilized zirconia and Mo + MoO₂ reference electrode.     

Phase Equilibrium of the System CaO‐P2O5‐SiO2 between 1473 K and 1673 K

Phase equilibrium was investigated in the ternary system of CaO‐P₂O₅‐SiO₂ at 1473K, 1573K and 1673K.