Kinetics of chromite ore reduction from MgO-CaO-SiO2-FeO-Cr2O3-Al2O3 slag system by carbon dissolved in high carbon ferrochromium alloy bath

Abstract

Kinetic experiments were performed in an induction furnace to investigate the reduction of chromite ore by carbon dissolved in a high carbon ferrochromium alloy melt under conditions of varying Cr₂O₃ concentration, slag basicity, and temperature. The results obtained show that chromite reduction by dissolved carbon in slag systems of the type MgO-CaO-SiO₂-FeO-Cr₂O₃- Al₂O₃ occurs principally by a stagewise process encompassing an intermediate reaction in which the divalent chromium oxide species is involved. During the fast period, Cr₂O₃ reduction is controlled by the diffusion of oxygen species in the slag for which a mass transfer coefficient of 0·003 cm s^-1 was calculated. An activation energy value of 117 kJ mol ^-1 obtained for the reduction of Cr₂O₃ implies the rate controlling step is mass transfer of Cr₂O₃ from the slag to the slag/metal interface, since activation energies for metal phase control are typically <70 kJ mol ^-1. The second period represents a pseudo-equilibrium condition with respect to Cr₂O₃ reduction that is probably under thermodynamic control by a step or mechanism involving the reduction of divalent chromium oxide to chromium.     

Thermodynamic assessment of CaO‐SiO2‐Al2O3‐MgO‐Cr2O3‐MnO‐FetO slags for refining chromium‐containing steels

The slag system of CaO‐SiO₂‐Al₂O₃‐MgO‐Cr₂O₃‐MnO‐Fe_tO relevant to refining chromium‐containing steels such as bearing steel is thermodynamically assessed at 1873 K. The activity coefficient of Fe_tO shows an initially rapid increment followed by a gradual reduction according to Cr₂O₃ content at a constant basicity, and decreases with increasing slag basicity. γ_MnO is decreased abruptly by increasing Cr₂O₃ content and thereafter, maintains a nearly constant level. From the standpoint of inclusion control, the Cr₂O₃ presence in ladle refining slags is thermodynamically harmful in that it minimizes the inclusion level by inducing the increment of γ_FetO even though Cr₂O₃ exists in extremely small amounts. However, it is beneficial in that it diminishes AI reoxidation by decreasing γ_MnO. The presence of carbon in slag decreases γ_FetO and γ_MnO, which turns out to be favourable for the reduction of Al reoxidation. The thermodynamic equilibria of chromium and manganese are quantified in terms of Fe_tO and Cr₂O₃ content as well as slag basicity by using multiple regression analysis. L_Cr and L_Mn are increased by the presence of Cr₂O₃, indicating a low recovery efficiency of Cr and Mn in the treatment of ferroalloy addition. In determining L_S values, Cr₂O₃ is not so important as the basicity of slags.     

Dissolution Behavior of Chromite Ore in CaO-SiO2 System

Numerous investigations proposed that the dissolution of chromite ore is the rate-controlling step for the smelting reduction of chromite ore. The mechanism of chromite ore dissolution in the binary CaO-SiO₂ system is presented. The effect of basicity, temperature, and reducing conditions on chromite ore dissolution is elaborated. The solubility of chromite ore increases considerably when the basicity increases from 0.56 to 0.65. However, the solubility of chromite ore decreases when the basicity further increases from 0.65 to 0.74. The positive effect of reducing conditions on the solubility of chromite ore is evident. The maximum dissolved Cr₂O₃ in slag under reducing conditions by using a graphite crucible reaches 2.6 wt% after 15 min of dissolution. The element diffusion behavior at the chromite/slag interface is elaborated through SEM-EDS technology. The analysis suggests that the rate-controlling step in the early stage is the interface dissolution reaction. After a certain time, the rate-controlling step becomes the mass transfer of Cr₂O₃ from the chromite ore to the chromite/slag interface. The activation energy of the dissolution reaction is $E_{\mathrm{r}}$ = 285.29 kJ mol⁻¹.     

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.     

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.     

Reduction of synthetic stainless steel slags by aluminium

One of the most efficient ways to eliminate the harm of chromium oxide in stainless steel slag is to reduce chromium oxide in stainless steel slag using aluminium. In the present work, the Al reduction of synthetic CaO–SiO₂–Al₂O₃–MgO–Fe₂O₃–Cr₂O₃ stainless steelmaking slags at different conditions, including temperature, slag basicity and Al amount was investigated to get optimal conditions for the reduction and the metal–slag separation. It was found that the agglomeration of metal droplets and metal–slag separations were improved by increasing temperature. The reduction degrees of SiO₂, Fe₂O₃ and Cr₂O₃ were enhanced with increasing basicity of slag. The addition of CaF₂ in slag leads to better agglomerations of metal droplets and metal–slag separations. The highest reduction degree of chromium could reach 99% in slag with basicity of 2 at 1873 K.     

Chromium Oxide Reduction from Slag by Silicon and Magnesium

Experimental and theoretical studies were performed in order to estimate the effect of the basicity of the slag as well as the amount of reducing agents on the reduction of chromium oxide from a slag in contact with molten steel at 1600 °C. The aim of this work was to compare the efficiency of magnesium and silicon as reducing agents of Cr₂O₃. The slag system contained CaO, MgO, SiO₂, CaF₂ and Cr₂O₃ together with Fe‐alloys (Fe‐Si or Fe‐Si‐Mg). The maximum Cr yield was about 81% with Fe‐44%Si‐9%Mg and 88% with Fe‐75%Si. That means that the reducing effect of Mg was much better than that of Si. Some experiments were conducted to study the effect of initial Cr in steel on the chromium oxide reduction reaction. Three initial Cr contents were tested (0.15, 2 and 4 mass%). It was found that chrome was partially bound into stable spinel phase MgO·Cr₂O₃ in the final slag. Thermodynamic estimations were made to determine the effect of process temperature, slag basicity and the amount of reducing agents in the slag on the Cr recovery. The efficiency of Cr reducing agents increased in the order: Si, Al, Ca and Mg. The Cr yield increased with slag basicity and amount of reducing agents.     

Activity of Chromium Oxide in CaO‐SiO2 based Slags at 1873 K

Thermodynamic properties of chromium oxides in molten slags are very important for optimization of stainless steel refining processes as well as reduction processes of chromium ores. The solubility of chromite into molten slags has been found to vary drastically with oxygen partial pressure and slag composition in the former studies by the authors. In the present study, activity data and redox equilibria of chromium oxides measured under moderately reducing conditions, P_O2= 6.95×10^?11 atm, at 1873 K are summarized. For the CaO‐SiO₂‐CrO_x system, the activity coefficient of chromium oxide increased with increasing basicity and the optimized slag composition for stainless steel refining is assessed as that saturated with CaCr₂O₄ and Cr₂O₃ using the phase relations determined. On the other hand, the presence of MgO and Al₂O₃ brings about different behaviour of chromium oxide activity and redox equilibria and the 44 mass per cent CaO ‐ 39 mass per cent SiO₂ ‐11 mass per cent Al₂O₃ ‐ 6 mass per cent MgO slag is recommended to reduce the chromium oxidation loss in the practical stainless steel refining process at 1873 K.     

Rate of reduction of Cr2O3 by carbon and carbon dissolved in liquid iron alloys

The rate of reaction of Cr₂O₃ with carbon or carbon dissolved in liquid iron alloys, and the decarburization of Fe-Cr-C alloys in Ar-O₂ gas mixtures has been investigated. The rate of reduction of dense Cr₂O₃ on the surface of Fe-Cr-C alloys was controlled by the diffusion of carbon to the surface of the melt. The chemical diffusion coefficient derived from the results (8.5 × 10^-5 cm²/s) is in agreement with previous work. The decarburization of Fe-Cr-C alloys in Ar-O₂ gas mixtures was apparently carried out by the Cr₂O₃ which formed on the surface of the melt by the reaction of the dissolved Cr with the oxygen gas and the rate of decarburization was controlled by the diffusion of carbon to the surface. The rate of reduction of Cr₂O₃ by various types of carbon was also investigated at temperatures from 1300 to 1600°C; the initial rate appears to be controlled by gas phase mass transfer of the CO away from the surface of the reactants.     

Minimization of Hexavalent chromium in magnesite-chrome refractory

The fundamentals on the formation of Cr⁶⁺ have been studied from two points of view: thermodynamic and kinetic. Thermodynamically, the CaO-Cr₂O₃ phase diagram can be used as a guide to understand the formation of Cr⁶⁺ as a function of temperature and composition. The Cr⁶⁺ content, in the CaO-Cr₂O₃ phase diagram, increases with exposure to temperatures below 1022 °C and with an increase in CaO (from 0 to 42 pct CaO). In kinetics, the chromite phase size also plays a major role in the formation of Cr⁶⁺. A decrease in chromite phase size increases the Cr⁶⁺ content in the refractory. The use of fused grains also decreases the formation of Cr⁶⁺. In the case of magnesite-chrome refractories, temperature, basicity (CaO/SiO₂), and chromite phase size play important roles in Cr⁶⁺ formation. The formation of Cr⁶⁺ can be minimized by carefully controlling the amount of calcium oxide in the refractory and by avoiding the use of a fine chromite phase during brickmaking.     

Kinetics of chromium oxide reduction from a basic steelmaking slag by silicon dissolved in liquid iron

The reduction of chromium oxide from a basic steelmaking slag (45 wt pct CaO, 35 wt pct SiO₂, 10 wt pct MgO, 10 wt pct A1₂O₃) by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-limiting steps. The reduction is described by the reactions: (Cr₂O₃) + Si = (SiO₂) + (CrO) + Cr [1] and 2 (CrO) +Si = (SiO₂) + 2 Cr [2] The experiments were carried out under an argon atmosphere in a vertical resistance-heated tube furnace. The slag and metal phases were held in zirconia crucibles. The course of the reactions was followed by periodically sampling the slag phase and analyzing for total chromium, divalent chromium, and iron. Results obtained by varying stirring rate, temperature, and composition defined the rate-limiting mechanism for each reaction. The rate of reduction of trivalent chromium (reaction [1] above) increases with moderate increases in stirring of the slag, and increases markedly with increases in temperature. The effects of changes in composition identified the rate-limiting step for Cr⁺³ reduction as diffusion of Cr⁺³ from the bulk slag to the slag-metal interface. The rate of reduction of divalent chromium does not vary with changes in stirring of the slag, but increases in temperature markedly increase the reaction rate. Thus, this reaction is limited by the rate of an interfacial chemical reaction. The reduction of divalent chromium is linearly dependent on concentration of divalent chromium, but is independent of silicon content of the metal phase.     

Reduction of MnO from molten slags with liquid steel of high carbon content

This work estimated the reduction of MnO in slags of the CaO‐SiO₂‐FeO‐CaF₂‐MnO system and liquid steel with the initial composition (mass contents) 0.75 %Mn, 0.16 % Si and 0.5 to 2.0 % C, as an alternative to introducing Mn to the steel melt. The slag basicities (CaO/SiO₂) In the experiments were 2 and 3. MnO was obtained from manganese ore. The experiments were carried out in an open 10 kg induction furnace using Al₂O₃‐based refractory at 1873 K. The oxygen potential was measured throughout the experiments with a galvanic cell (ZrO₂‐solid electrolyte with a Cr/Cr₂O₃ reference electrode). The MnO reaction mechanism was analysed in terms of the slag basicity, the silicon and the initial carbon contents in the melt. The rate and the degree of MnO reduction were found to increase with the increasing of initial carbon content; however, the effect of slag basicity was less important. A kinetic analysis of the process was performed using a coupled reaction model.     

The Effects of CaF2, Basicity, and Atmospheric Conditions on the Solubility of Carbon and Nitrogen in the CaO-SiO2-Al2O3-Based Slag System

The solubility of carbon and nitrogen in the CaF₂-CaO-SiO₂-Al₂O₃ slag system was studied. The effects of the CaF₂, extended basicity (CaO/(SiO₂ + Al₂O₃)), and atmospheric conditions on the dissolution behavior of the carbon and nitrogen, as well as the correlations of the behaviors with the slag structure observed at 1773 K (1500 °C), are presented. Increases in the extended basicity and the CaF₂ increased the solubility of carbon in the slag. In the case of nitrogen dissolution, a characteristic parabolic curve with an identifiable minimum was observed for the slag. This curve shape correlated with a change in the dominant mechanism of dissolution from an incorporated to a free nitride. The solubility of carbon in the mixture of CO with N₂ was significantly higher than that of carbon in the mixture of CO with Ar and is likely due to the formation of cyanide. Thus, when carbon is present in significant quantities in the slag, the solubility of nitrogen in the slag increases. The degree of depolymerization of the slag with increased content of CaO/(SiO₂ + Al₂O₃) and CaF₂ was verified using Fourier transform infrared and Raman spectroscopy.     

Viscosity of CaO-SiO2-Al2O3-MgO-B2O3 slags

The viscosity of CaO-SiO₂-Al₂O₃ slags with 8% MgO and 4% B₂O₃ is investigated over a broad range of composition, by means of a simplex-lattice experiment design. For slag of basicity 6–8 in the upper left region of the local simplex, with 15–25% Al₂O₃, 8% MgO, and 4% B₂O₃, the viscosity is high: 9.4–26.4 P over the range 1500–1530°C. Displacement of the slags of basicity 5–8 to the lower region of the local simplex ensures high fluidity in the given range of Al₂O₃ concentration: the viscosity is 1.5–6.1 P over the range 1500–1530°C.     

Formation of hexavalent chromium by reaction between slag and magnesite-chrome refractory

The goal of this work was to understand how Cr⁶⁺ formation is affected by the interaction between chromite phases present in magnesite-chrome refractory and different slag compositions. In addition, the formation of Cr⁶⁺ as a function of chromite particle size and cooling rate due to the chromite phase/slag interaction was investigated. The following slag compositions were studied: calcium aluminate, calcium aluminum silicate, and calcium silicate. It was found that the presence of uncombined CaO in the calcium aluminate slags is responsible for a higher yield of Cr⁶⁺. However, the replacement of Al₂O₃ by SiO₂ in calcium aluminate slags decreases the formation of Cr⁶⁺. SiO₂ reacts with CaO to form stable 2CaO·Al₂O₃·SiO₂ and CaO·SiO₂ phases, consequently decreasing the amount of uncombined CaO available to react with the chromite phase to form Cr⁶⁺. Moreover, the content of Cr⁶⁺ is decreased by increasing chromite particle size and increasing the cooling rate of magnesite-chrome refractory.     

Dissolution Mechanism of Indium in CaO-Al2O3-SiO2 Slag at Low Silica Region

The solubility of indium was measured in the low-silica region (<20?mass pct SiO₂) of the CaO-Al₂O₃-SiO₂ system by a thermochemical equilibration technique. The dissolution mechanism of indium into the CaO-Al₂O₃-SiO₂ slag at 1773?K (1500?°C) under a reducing atmosphere was elucidated. The indium solubility increases in the calcium silicate-based flux and decreases in the calcium aluminate-based flux with increasing oxygen partial pressure. Also, the solubility was found to decrease initially with increasing slag basicity until the basicity reached a critical level after which the solubility increases. This behavior is believed to indicate that the indium dissolution mechanism changes according to the basicity of the slag.     

Simulation of primary-slag melting behavior in the cohesive zone of a blast furnace, considering the effect of Al2O3, Fe t O, and basicity in the sinter ore

The alumina content in the iron ore imported to Japan is increasing year by year, and some problems in blast furnace operation, due to the use of the high-alumina-containing sinter, have already been reported. In order to clarify the mechanism of the harmful effect of alumina on the blast furnace operation, the behavior of the primary melt, which is formed in the sinter at the cohesive zone of the blast furnace, has been simulated by dripping slag through an iron or oxide funnel. The effects of basicity, Al₂O₃, and Fe _t O contents in the five slag systems on the dripping temperature and weight of slag remaining on the funnel have been discussed. It was found that the eutectic melt formed in the sinter would play an important role in the dripping behavior of the slag in the blast furnace through the fine poreosity of the reduced iron and ore particles. Al₂O₃ increased the weight of the slag remaining on the funnel, and its effect became very significant in the acidic and low-Fe _t O-containing slag. It was estimated that the increase of the weight of the slag remaining on the funnel by Al₂O₃ in the ore could result in a harmful effect on the permeability resistance and an indirect reduction rate of the sinter in the blast furnace.     

Model for diffusion coefficient estimation of calcium ions in CaO–Al2O3–SiO2 slags

Abstract

As a common component in metallurgical slag, CaO plays an important role in desulphurisation, dephosphorisation and absorption of non-metallic inclusions. In order to better understand the mechanism of the slag/metal reactions, the diffusion dynamics of calcium ions in CaO–Al₂O₃–SiO₂ slags were studied. It was found that there was almost a linear relation between the logarithms of pre-exponential factor and diffusion activation energy. By combining the relation between the diffusion activation energy and the optical basicity corrected in the CaO–Al₂O₃–SiO₂ slags, a simple model used to estimate the diffusion coefficient of calcium ion is proposed. The estimated values of the CaO–SiO₂ and CaO–Al₂O₃–SiO₂ systems agree well with the experiment data, with a mean deviation of 35·3 and 22·5% respectively.     

Immobilization of Chromium in Slags using MgO and Al2O3

Chromium containing slags from stainless steelmaking may be leached by acidic environments, therefore they should be treated before being stockpiled or land filled. In this work, synthetic slags were prepared and the effect of CaO/SiO₂, Cr₂O₃, MgO and Al₂O₃ contents on the stability of the mineralogical species formed was analysed. The morphology and composition of the slags were determined by XRD and SEM‐EDS, whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that CaCr₂O₄ and CaCrO₄ are present in slags prepared with neither MgO nor Al₂O₃. The Al₂O₃‐based slags mainly produced Ca₂Al₂SiO₇ and the Cr(VI)‐containing oxide complex Ca₄Al₆CrO₁₆, whilst MgO‐based slags produced Mg Cr₂O₄ as main mineralogical species. Additionally, Eh‐pH diagrams for the Ca‐Cr‐H₂O and Mg‐Cr‐H₂O systems at 25°C were constructed. The results showed that the lowest chromium concentration levels in the leaching liquors corresponded to MgO‐based slags owing to the stable binding of chromium in spinel with MgO. It was also observed in the Al₂O₃‐based slags that when increasing the slag basicity from 1 to 2, the leachability of the slags was notably increased.     

Constitutional Segregation of Al2O3 in Mold Slag and Its Impact on Steel Cleanliness During Continuous Casting

The alumina pickup in a range of mold fluxes used for continuous casting of aluminum (Al)-killed ultralow carbon, low carbon, and peritectic steel have been measured. The Al₂O₃ pickup in slag varies approximately from 7 to 12 pct and depends on the slag basicity. Significantly higher Al₂O₃ pickup reported in basic slags and polynomial relationship exists between them. The effect of chemical composition on microstructure evolution and Al₂O₃ partitioning during crystallization was identified in all three types of mold slags. The microsegregation of Al₂O₃ inclusions in the constituent phase of CaO-SiO₂-Al₂O₃ based slag film is presented. Constitutional segregation of Al₂O₃ inclusion in slag was found to affect the Al₂O₃ pickup phenomena during continuous casting. Segregation of alkalis like Na and K was also observed in an Si-rich interdendritic matrix, whereas F was retained in the dendrites of all the slags studied. The Al₂O₃ inclusion partitioning and interdendritic segregation in the mold slag is studied with metallographic evidence.