Reduction of FeO in smelting slags by solid carbon: Experimental results

The reduction of CaO-SiO₂-Al₂O₃-FeO slags containing less than 10 wt pct FeO by solid carbonaceous materials such as graphite, coke, and coal char was investigated at reaction temperatures of 1400 °C to 1450 °C. The carbon monoxide evolution rate from the system was measured using stationary and rotating carbon rods, stationary horizontal carbon surfaces, and pinned stationary spheres as the reductants. The measured reaction rate ranged from 3.25 × 10^?7 mol cm^?2 s^?1 at 2.1 pct FeO under static conditions to 3.6 × 10^?6 mol cm^?2 s^?1 at 9.5 pct FeO for a rotating rod experiment. Visualization of the experiment using X-ray fluoroscopy showed that gas evolution from the reduction reaction caused the slag to foam during the experiment and that a gas film formed between the carbon surface and the slag at all times during experimentation. The reaction rate increased with increased slag FeO contents under all experimental conditions; however, this variation was not linear with FeO content. The reaction rate also increased with the rotation speed of the carbon rod at a given FeO content. A small increase in the reaction rate, at a given FeO content, was found when horizontal coke surfaces and coke spheres were used as the reductant as compared to graphite and coal char. The results of these experiments do not fit the traditional mass transfer correlations due to the evolution of gas during the experiment. The experimental results are consistent, however, with the hypothesis that liquid phase mass transfer of iron oxide is a major factor in the rate of reduction of iron oxide from slags by carbonaceous materials. In a second article, the individual rates of the possible limiting steps will be compared and a mixed control model will be used to explain the measured reaction rates.     

Kinetic model for reduction of iron oxide in molten slags by iron-carbon melt

Rate of reduction of iron oxide in iron and steelmaking slags by mass contents of dissolved carbon (>3%) in molten iron depends upon activity of FeO, temperature, mixing of bulk slag and other experimental conditions. A general kinetic model is developed by considering mass transfer of FeO in slag, chemical reaction at gas-metal interface and chemical reaction at gas-slag interface, respectively, as the three rate controlling steps. A critical analysis of the experimental data reported in literature has been done. It is shown that in the case of slags containing mass contents of less than 5% FeO, the reduction of FeO is controlled by mass transfer of FeO in slag plus chemical reaction at gas-metal interface; when slags contain more than 40% FeO, the reduction of FeO is controlled by chemical reaction at gas-metal interface plus chemical reaction at gas-slag interface; at intermediate FeO mass contents (between ～ 5 and 40% FeO), the reduction of FeO is controlled by all three steps, namely, mass transfer of FeO in slag, chemical reaction at gas-metal interface and chemical reaction at gas-slag interface. The temperature dependence of rate constant for the gas-slag reaction is obtained as: In k₂ = –32345.4(&6128)/ T + 19.0(&3.42); σ_lnk2,1/T = &0.3. where k₂ is expressed in mol m^-2 s^-1 bar^-1. The mass transfer coefficient of iron oxide in bulk slag is found to vary in the range 1.5 × 10^-5 to 5.0 × 10^-5 m/s, depending upon the slag composition as well as experimental conditions.     

Slag foaming in bath smelting

Slag foaming measurements in terms of the foaming index (∑) were conducted on bath smelting-type slags (CaO-SiO₂-FeO, CaO-SiO₂-MgO-Al₂O₃-FeO) at 1773 K. It was found that the slag foam stability decreases with increasing FeO (FeO > 2 pct) content and basicity. For the slag system (CaO-SiO₂-FeO), no stable foam was observed at very low FeO content (<2 pct). As pct FeO increases, the slag foaming index goes through a maximum and then decreases; a similar phenomenon was observed for CaO-SiO₂-NiO slags with respect to the NiO content. The foaming index determined from the normal small-scale experiments (3.8-cm ID diameter) were confirmed on a larger scale (9.2-cm ID diameter), indicating that the foaming index is independent of container size. Measurements were also made for the actual compositions for bath smelting slags. For these slags, the foaming index is higher than those of simple CaO-SiO₂-FeO slags, because MgO and Al₂O₃ may increase their viscosities. The foam index is believed to be a function of the physical properties of the slag. Consequently, a dimensional analysis was performed, and a correlation was developed relating the foaming index to the viscosity, surface tension, and density of the slag. An estimation of slag foaming in actual pilot plant trials was also made from the results of the present study. Good agreement was observed between the predicted and observed foam heights and indicated coke in the slag can reduce the foam height by more than 50 pct. R. Jiang, Formerly Graduate Student, Carnegie Mellon University, is deceased.     

Slag foaming in smelting reduction processes

In order to understand the effect of slag composition on foaming in the smelting reduction process, slag foaming was quantitatively studied for CaO–SiO₂–FeO slags in the temperature ranging 1250–1400 °C. It was found that slag foaming could be characterized by a foaming index Σ which is equal to the retention or travelling time of the gas in the slag and by the foam life. The effects of P₂O₅, S, MgO and CaF₂ on foaming were studied. As expected slag foaming increased with increasing viscosity and decreasing surface tension. The results were extrapolated to bath smelting process to predict the foam height. Slag foaming heights as high as 3–5 meters are predicted for a typical operation.     

Phase Equilibria in the System “FeO”-CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO at Different CaO/SiO<Subscript>2</Subscript> Ratios

The “FeO”-containing slags play an important role in the operation of an ironmaking blast furnace (BF), in particular the primary slags such as the system “FeO”-CaO-SiO₂-Al₂O₃-2 mass pct MgO with CaO/SiO₂ weight ratios of 1.3, 1.5, and 1.8 saturated with metallic iron. To investigate the characteristics of such a slag system and its behavior in BF, the phase equilibria and liquidus temperatures in the slag system have been experimentally determined using the high-temperature equilibration and quenching technique followed by an electron probe X-ray microanalysis (EPMA). Isotherms between 1553 K and 1603 K (1280 °C and 1330 °C) were determined in the primary phase fields of dicalcium silicate, melilite, spinel, and monoxide [(Mg,Fe²⁺)O]. Pseudo-ternary phase diagrams of (CaO + SiO₂)-Al₂O₃-“FeO” with a fixed MgO concentration at 2 mass pct and at CaO/SiO₂ ratios of 1.3, 1.5, and 1.8 have been discussed, respectively, simplifying the complexity of the slag system for easy understanding and applying in BF operation. It was found that the liquidus temperatures increase in melilite and spinel primary phase fields, but decrease in dicalcium silicate and monoxide primary phase fields with increasing Al₂O₃/(CaO + SiO₂) ratio. In addition, the liquidus temperatures decrease with increasing “FeO” concentration in dicalcium silicate and melilite primary phase fields, while showing an increasing trend in the spinel and monoxide primary phase fields. The data resulted from this study can be used to improve and optimize currently available database of thermodynamic models used in FactSage.     

Study on the foaming of CaO-SiO2-FeO slags: Part I. Foaming parameters and experimental results

In order to understand the effect of slag composition on foaming in iron and steelmaking processes, slag foaming was quantitatively studied for CaO-SiO₂-FeO slags in the temperature range of 1250 °C to 1400 °C. It was found that slag foaming could be characterized by a foaming index (Σ), which is equal to the retention or traveling time of the gas in the slag, and the average foam life ( τ). The effects of P₂O₅, S, MgO, and CaF₂ on foaming were studied. As expected, slag foaming increased with increasing viscosity and decreasing surface tension. It was found that suspended second-phase solid particles such as CaO, 2CaO SiO₂, and MgO stabilized the foam and had a larger effect on foaming than changes in viscosity and surface tension for the slags studied. Kimihisa Ito, Research Associate, formerly with the Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University     

Evaluation of the reduction of iron oxide from liquid slags using a graphite rotating disk

The rotating disk methodology has been used for examination of the reduction of FeO from CaO-FeO-SiO₂ liquid slags (20 and 60 pct FeO) with a CaO/SiO₂ ratio equal to 0.66 and 1.27, in the temperature range 1350 °C to 1420 °C. It has been found that the reduction proceeds under diffusion control. The calculated diffusion coefficients fall in the range 0.76·10⁻⁷ to 1.6·10⁻⁶ cm²/s. Comparison of these values with those given in the literature suggests that the calculated coefficients are related to the diffusion of oxygen ions in the slag. The calculated thickness of the limiting diffusion layer, δ, ranges from 0.65·10⁻³ to 5.25·10⁻³ cm, depending on the reduction conditions. The largest decrease in the limiting diffusion layer thickness takes place at low rotational speeds, i.e., 100 and 400 rev/min. The maximum value of the mass transfer coefficient is 1.71·10⁻³ cm/s for reduction from slag with a CaO/SiO₂ ratio of 1.27, 60 pct FeO, at 1420 °C and 2000 rev/min, and the minimum value is 0.27·10⁻⁴ cm/s for reduction from slag with a CaO/SiO₂ ratio of 0.66, 20 pct FeO, at 1350 °C and 100 rev/min. Good agreement has been found between experimental and calculated reduction rates at low disk rotations (100 and 400 rev/min).     

The effect of carbon content on the rate of reduction of FeO in slag relevant to iron smelting

In the iron smelting, or bath smelting, process the tapped metal contains high amounts of sulfur and the slag contains high amounts of FeO, relative to blast furnace slag. After tapping, the FeO can be further reduced by carbon in the metal, which will also lead to better desulfurization. Although there have been many studies of the reaction of carbon in iron with FeO in slag, discrepancies exist with regards to the effect of carbon in iron on the rate of FeO reduction in slag, which is the subject of this study. Experiments were conducted at 1723 K, using a slag with basicity close to one with an FeO mass content of 5 %. The rate of reduction was measured using a pressure increase technique. For moderate and high sulfur contents, as in the case of iron smelting, the rate is primarily controlled by the dissociation of CO₂ on the surface of the molten iron. Furthermore, if the effect of carbon on sulfur is taken into account, for the range of carbon mass contents of 2 to 4.5 %, there is no effect of the carbon level on the rate of FeO reduction. At low sulfur contents it was found that there is considerable slag foaming, which inhibits mass transfer of FeO in the slag, and significantly reduces the rate. Even when there is no slag foaming at low sulfur contents, mass transfer of FeO in the slag can influence the rate of FeO reduction.     

Influence of slag and foam characteristics on reduction of FeO-containing slags by solid carbon

The present study reports experimental results on the reduction of FeO in molten CaO-SiO₂-Al₂O₃-MgO-FeO slags by solid carbon in an extended-arc plasma reactor. The reduction reaction was found to be controlled by mass transport of FeO in liquid slag. The CO gas generated stirs the bath to establish a convective mass transport system. CO also causes foaming. An analysis using dimensionless numbers provides correlations between the rate constant, k, as well as the foaming index, Σ, with some properties of the slag such as viscosity, surface tension, and density. A correlation between k and Σ is also developed using these parameters for slag characteristics.     

An experimental study of the viscosities of Al2O3-CaO-“FeO” slags

Experimental determinations of the viscosities of some Al₂O₃-CaO-“FeO” ternary slags were carried out in the temperature range from 1550 to 1764 K using the rotation cylinder method. The measurements were conducted in the composition range from 36 to 48 mass pct Al₂O₃, 28 to 42 mass pct CaO, and 10 to 33 mass pct FeO. The viscosity was found to show a decreasing trend with the increase of FeO content. Based on the experimental data, the liquidus temperatures of the slags were evaluated using the second derivatives of the activation energies for viscous flow with respect to temperature. The evaluated liquids temperatures were compared with the results of differential thermal analysis (DTA) on the same slag samples.     

Effects of transition metals on the kinetics of slag-refractory reactions

The dissolution kinetics of dense alumina discs in calcium aluminosilicate based melts was determined with a rotating disc technique at 1560 °C to 1590 °C, under a controlled atmosphere of Ar-CO-CO₂. The effects of rotation speed and the concentration of iron and manganese oxides on the dissolution rate of alumina into slags were measured by monitoring the concentration of species in the slag. Analysis of the results obtained indicated that at low concentrations of these transition metal oxides in 53 pct CaO-5 pct MgO-12 pct SiO₂-30 pct Al₂O₃ slags, the dissolution rate is most likely controlled by mass transfer in the slag phase. The rate data obtained also showed that the addition of iron oxide or manganese oxide results in considerable increase in the mass transfer by increasing the apparent diffusivities of species in the slag. Comparison of these results with published data on the diffusivities of species in similar slags are made and practical implications of the findings are briefly discussed.     

The reaction behavior of Fe-C-S droplets in CaO-SiO2-MgO-FeO slags

The rate of reduction of FeO in the slag by carbon in iron droplets (2.9 wt pct C, 0.01 wt pct S) was studied for CaO-SiO₂-MgO slags containing between 3 and 35 wt pct FeO and temperatures ranging from 1643 to 1763 K. The effects of Fe₂O₃ additions to the slag and sulfur variations in the metal on the reaction rate were also studied. It was found that the behavior of the metal droplets in the slag, as observed by X-ray fluoroscopy, changed significantly with FeO content in the slag. Below 10 wt pct FeO, the droplet remained intact while reacting with the slag; however, above this FeO concentration, the droplet became emulsified within the slag. The large increase in surface area of the metal droplet due to emulsification caused the rate of reaction to be one to two orders of magnitude faster than for droplets that did not become emulsified. It was suggested that when the droplet is emulsified, the surface area and reaction kinetics are greatly increased, and the rate becomes controlled by mass transfer of FeO as Fe²⁺ and O²⁻ ions in the slag to the emulsified droplet. At low FeO contents for which the droplet does not emulsify, the rate is controlled by dissociation of CO₂ on the metal. It was also found that a critical temperature exists for a given FeO content at which point the rate of CO evolution increases dramatically. Additions of Fe₂O₃ to the slag and sulfur to the metal caused significant changes to the rate of reaction possibly by affecting the emulsification behavior of the droplet.     

Effect of FeO and CaO on the Sulfide Capacity of the Ferronickel Smelting Slag

The effect of FeO and CaO on the sulfide capacity in MgO-SiO₂-FeO based slags equilibrating with Fe-Ni alloys at 1773 K and 1873 K (1500 °C and 1600 °C) was investigated. The sulfide capacity in the MgO-SiO₂-FeO and MgO-SiO₂-CaO-FeO slags increased with higher FeO content and higher temperatures due to an increase in the activity of O^2? and a decrease in the activity coefficient of sulfide ion in slag. The sulfide capacity of the MgO-SiO₂-CaO-FeO slag also increased with an increase in the CaO content due largely to the increase in the activity of O^2?. Furthermore, CaO and FeO seem to be more effective than MgO in increasing the sulfide capacity in the MgO-SiO₂-CaO-FeO slag system. In addition, the comparison of the experimental results with the theoretical estimate using the modified empirical optical basicity showed relatively good linear agreement.     

The settling of metallic lead from lead blast furnace slag

As a consequence of inadequate working methods, excessive losses of lead can occur in the slags of lead blast furnaces. The settling of metallic lead from a slag containing 20.5 pct SiO₂, 33.4 pct FeO, 16.8 pct CaO, 12.4 pct ZnO, 0.9 pct S, and 6.1 pct Pb has been studied as a function of the temperature (1200 to 1300 °C), composition (addition of CaO, ZnO, and Fe), and time (up to 2 hours). Under these conditions sufficient, although not total, sedimentation of the metal retained is achieved. The best conditions were obtained at 1260 °C with no modification to the composition of the slag. The settled lead was visible macroscopically in a section of the lower part of the melts.     

Manganese Recovery by Silicothermic Reduction of MnO in BaO-MnO-MgO-CaF<Subscript>2</Subscript> (-SiO<Subscript>2</Subscript>) Slags

The effects of reducing agent, CaF₂ content, and reaction temperature upon the silicothermic reduction of MnO in the BaO-MnO-MgO-CaF₂ (-SiO₂) slags were investigated. Mn recovery was proportional to Si activity in the molten alloy. Moreover, 90 pct yield of Mn recovery was obtained under 5 mass pct CaF₂ content and 1873 K (1600 °C) reaction temperature. Increasing CaF₂ content above 5 pct yielded little or no further increase in Mn recovery, because it was accompanied by increased slag viscosity owing to the precipitation of high melting point compounds such as Ba₂SiO₄.     

Distribution of Bi Between Slags and Liquid Copper

The distribution of Bi between liquid copper and calcium ferrite slag containing 24 wt pct CaO, iron silicate slag with 25 wt pct SiO₂, and calcium iron silicate slags was measured at 1573 K (1300 °C) under controlled CO-CO₂ atmosphere. The experimental results showed that bismuth distribution is affected by the oxygen partial pressure, and bismuth is likely to exist in slags in the 2+ oxidation state, i.e., as BiO. The distribution ratio between calcium ferrite slag and metal was found to be close to that of iron silicate slag. The Bi distribution ratio was found to decrease with increasing SiO₂ and Al₂O₃ content in slag. Increasing temperature was found to decrease the Bi distribution ratio between slag and metal. Using the measured equilibrium data on Bi content of the metal and slag and composition dependence of the activity of Bi in liquid copper, the activity and hence activity coefficient of BiO in the slag was calculated. The close value of activity coefficient of BiO in both slags at the same oxygen partial pressure indicates that the CaO-BiO and SiO₂-BiO interactions are likely to be at the same level, or the FeO _x -BiO interaction is the predominant interaction for BiO in the slag. Therefore at a constant FeO _x content in the slag, the CaO-BiO and SiO₂-BiO interactions doesn’t affect \( \gamma_{\text{BiO}} \) significantly.     

Rate of slag reduction in a laboratory electric furnace—alternating vs direct current

The objective of this laboratory investigation was to measure the reduction kinetics of nickel smelting and converting slags using alternating current (AC) and direct current (DC). The two slags tested contained 34 and 51 pct total iron in the form of FeO and Fe₃O₄. Laboratory experiments were carried out between 1200 °C and 1450 °C, and the rate of reduction was measured based on the CO and CO₂ contents in the off-gas from the furnace. Upon application of power to a pair of electrodes immersed in the molten slag, the reduction rate increased rapidly. This increase is explained by an increase in the electrode tip temperature enhancing the rate of the Boudouard reaction. The rate of reduction of the converter slag containing 29 pct Fe₃O₄ was 2 to 3 times faster than the smelting slag. With DC, the reduction rates at the anode and cathode were basically identical to each other, while for the smelting slag with only 8 pct Fe₃O₄, the anode and cathode reduction rates were quite different. With increasing current or power density, the temperatures of the electrodes increase above that of the bulk slag.     

Measurement of FeO activity and solubility of MgO in smelting slags

In bath smelting, the FeO activity of the slag must be known to predict the equilibrium of slag-metal reactions and for effective control of the rate of reduction in the system. Also, knowledge of the solubility of MgO in these slags is useful for reducing refractory consumption. A series of measurements of the FeO activity in simulated bath smelting slags (CaO-SiO₂-Al₂O₃-MgO_sat-FeO) were conducted by the electromotive force (EMF) technique. The influence of the slag composition on the relationship between the FeO activity coefficient and FeO content was studied. It has been found that the measured FeO activity coefficient decreases with increasing FeO content in the slag and increases slightly with increasing slag basicity, which is defined as (CaO + MgO)/(SiO₂ + Al₂O₃) on a mole fraction basis. The measured values of the FeO activity coefficient are in reasonable agreement with previously published data. The solubility of MgO was also measured and found to rang from 16 to 30 pct and decrease with increasing basicity.     

Interfacial Reaction Between CaO-SiO2-MgO-Al2O3 Flux and Fe-xMn-yAl (x = 10 and 20 mass pct, y = 1, 3, and 6 mass pct) Steel at 1873 K (1600 °C)

This study investigated the interfacial reaction kinetics and related phenomena between CaO-SiO₂-MgO-Al₂O₃ flux and Fe-xMn-yAl (x = 10 and 20 mass pct, y = 1, 3, and 6 mass pct) steel, which simulates transformation-induced plasticity (TRIP) and twinning-induced plasticity (TWIP) steels at 1873 K (1600 °C). It also examines the effect of changes in the composition of the steel and slag phases on the interfacial reaction rate and the reaction mechanisms. The content of Al and Si in the 1 mass pct Al-containing steel was found to change rapidly within the first 15 minutes of the reaction, but then it remained relatively constant. The content of Al and Si in the 3 to 6 mass pct Al-containing steels, in contrast, changed continuously throughout the entire reaction time. In addition, the content of Mn in the 1 mass pct Al-containing steels initially decreased with increasing time, but the content did not change in the 3 to 6 mass pct Al-containing steels. Furthermore, the mass transfer coefficient of Al, k _Al, in the 1 mass pct Al-containing systems was significantly higher than that in other systems; i.e., the k _Al can be arranged such that 1 mass pct Al systems >> 3 mass pct Al systems ≥ 6 mass pct Al systems. The compositions of the final slags were close to the saturation lines of the [Mg,Mn]Al₂O₄ and MgAl₂O₄ spinels when the slags reacted with 1 mass pct Al and 3 to 6 mass pct Al-containing steels, respectively. These results, which show the effect of Al content on the reaction phenomena, can be explained by the significant increase in the apparent viscosity of the slags that reacted with the 3 to 6 mass pct Al-containing steels. This reaction was likely caused by the precipitation of solid compounds such as MgAl₂O₄ spinel and CaAl₄O₇ grossite at locally alumina-enriched areas in the slag phase. This analysis is in good accordance with the combination of Higbie’s surface renewal model and the Eyring equation.