Effects of oxygen atmosphere,FeOx and basicity on mineralogical phases of CaO–SiO2–MgO–Al2O3–FetO–P2O5 steelmaking slag

ABSTRACT

The mineralogical phase of slag after crystallisation is essential to utilisation of steelmaking slag. The mineralogical phases of cooled multicomponent CaO–SiO₂–MgO–Al₂O₃–Fe_tO–P₂O₅ slag with different iron oxide contents and basicities (defined as the ratio of mass percentage of CaO to mass percentage of SiO₂ (w(CaO)/w(SiO₂))) in different atmospheres were investigated in the present work by scanning electronic microscopy and energy dispersed spectroscopy analysis and X-ray diffraction. The mineralogical phases in steelmaking slag cooled in argon are mainly nCa₂SiO₄-Ca₃(PO₄)₂ (thereafter nC₂S-C₃P) solid solution, (Fe, Mn, Mg)O (RO) phase. Some CaMgSiO₄ phases could be found in slag with lower basicity. The mineralogical phases in steelmaking slag cooled in air are mainly nC₂S-C₃P solid solution, spinel phase. The overall crystallisation of slag cooled in both argon and air was enhanced with increasing basicity. However, the crystal sizes become smaller in sample with high basicity. The Fe-enriched phases were transformed from non-faceted RO phase in sample cooled in argon to faceted spinel phases in sample cooled in air. The crystallisation of slag cooled in both argon and air was promoted with increasing FeO_x content. The phosphorus content in solid solution was elevated with decreasing basicity and increasing FeO_x content. It was implied by the present work that appropriate basicity and air oxidation would be beneficial to magnetic separation and phosphorus utilisation.     

Effects of basicity,MgO and MnO on mineralogical phases of CaO–FeOx–SiO2–P2O5 slag

The selective separation phosphorous rich phase from steel slag could be an effective way to utilise the steel slag. The mineralogical phase after cooling of steel slag is essential to selective separation of steel slag. In the present work, the mineralogical phases of CaO–FeO_x–SiO₂–P₂O₅ slag after controlled cooling were investigated by X-ray diffraction and scanning electronic microscopy and energy dispersed spectroscopy technique. It was found that the heat treatment at 1573?K would lead to the precipitation of Ca₂SiO₄–Ca₃P₂O₈ (C2S-C3P) solid solution for all samples. The heat treatment at 1273?K would lead to the precipitation of C2S-C3P, CaSiO₃ and Fe₂O₃. The increase of basicity would promote the crystallisation of CaO–FeO_x–SiO₂–P₂O₅ slag. The Effects of additions of MgO and MnO on phase formations of CaO–FeO_x–SiO₂–P₂O₅ slag were also studied. Fe₂O₃ gradually transformed into MgFe₂O₄ and MnFe₂O₄ in slag after crystallisation with addition of MgO and MnO, respectively. The sizes of MgFe₂O₄ and MnFe₂O₄ crystals increased with increases of MgO and MnO content. The increase of MgO and MnO content would promote the precipitation of MgFe₂O₄ phase and MnFe₂O_4, respectively. The precipitation of crystals from slag during cooling was interpreted by the kinetic and thermodynamic factors. It was proposed that addition of MgO and MnO in slag would be beneficial to magnetic separation of steel slag.     

Study on electrical conductivity of FexO–CaO–SiO2–Al2O3 slags

The composition dependences of electrical conductivity of Fe_xO–CaO–SiO₂–Al₂O₃ slags at different oxygen potentials and temperatures have been studied experimentally in the present work. From the experimental results, the total electrical conductivity and electronic conductivity for all the slags monotonously decrease as increasing CO/CO₂ ratio from about 0 to 1. With the increase of Fe_xO content, the total electrical conductivity and electronic conductivity increase at a fixed CO/CO₂ ratio. It is also found that the ionic conductivity of all the studied slags increases as increasing the CO/CO₂ ratio, which is resulted from the increase of Fe²⁺ ion concentration. In addition, the temperature dependences of ionic, electronic and total conductivity for different compositions obey the Arrhenius law. The electronic transference number exhibits a strong relationship with oxygen potential, but is independent of temperature.     

Experimental studies of viscosities of some CaO–CaF2–SiO2 slags

Abstract

In the present work, the viscosities of some CaO–CaF₂–SiO₂ slags were measured using the rotating cylinder method. The effects of various volatile fluorine compounds on the change in slag composition are discussed on the basis of thermodynamic calculations. The kinetic factors concerning the escape of the volatile fluorides under the experimental conditions were also examined. It was found that the formation of gaseous species SiF₄ was the main source for compositional changes during the viscosity measurements. In the case of CaO–CaF₂–SiO₂slags, the formation of SiF₄ would be somewhat limited owing to the existence of CaO. The composition change during the measurements was only about ±1 wt-% for all components in most cases. Viscosity measurements are reported for slags, based on the post-measurement compositions. It was found that the addition of CaF₂ causes a significant decrease in viscosity.     

Smelting reduction reactions by solid carbon using induction furnace: foaming behaviour and kinetics of FeO reduction in CaO–SiO2–FeO slag

Abstract

Smelting reduction process technology is progressing rapidly, and research to understand the reduction of FeO in molten slag and the associated foaming behaviour has gained importance. The present paper reports experimental data on the reduction of FeO in molten slag generated in a 30 kW capacity induction furnace. The influence of FeO content in the slag and temperature on the foaming and kinetics is discussed. The foaming index, a parameter describing the travel time of gas in the reactor, is shown to decrease with an increase in the superficial gas velocity. The quantitative dependence of the foaming index on slag properties viscosity, surface tension and density has been studied. The data have also been analysed to give an estimation of the activation energy for the reduction reaction. The reduction reaction, initiated by direct slag–graphite contact, produces CO gas, which spreads into the molten slag bath causing foaming of the slag; further reduction of FeO proceeds mostly via indirect reduction. The rate of reduction is found to depend directly on the initial FeO content. An increase in temperature increases the rate of reduction, which has an activation energy of 118 kJ mol^?1 of FeO. The results indicate that transport of FeO in the liquid phase is the rate controlling step. The major findings are in agreement with those reported by earlier investigators.     

Viscosity of low silica CaO–5MgO–Al2O3–SiO2 slags

Abstract

The viscosity of CaO–5MgO–Al₂O₃–SiO₂ slag with low silica was measured by rotating cylinder method up to 1823 K. Slag compositions were chosen based on five different levels of SiO₂ content between 0 and 11·80%. The MgO content was 5·0%. The mass ratio of CaO/Al₂O₃ was varied from 0·66 to 1·95. It was shown that viscosity decreased with increasing temperature and decreased with increasing the mass ratio of CaO/Al₂O₃, following by an increase with further increasing the mass ratio of CaO/Al₂O₃. The viscosity decreased with the NBO/T ratio increasing, and the trend that flow activation energy changes with the NBO/T ratio of slag was the same as the trend that viscosity changes with the NBO/T ratio. Based on the experimental data as the boundary of the homogenous phase region, the mass triangle model was used to calculate the viscosity of low silica region.     

Molecular dynamics simulations of microstructural properties of CaO–SiO2–TiO2 fluorine-free slag systems

The microstructural properties of F-free slag, the CaO–SiO₂–TiO₂ (CST) systems, are investigated by molecular dynamics (MD) simulations. The results show that in the CST system, the average bond length of Si–O remains in 1.61?Å. The addition of TiO₂ contributes to the increase in the concentrations of 4-coordinated Si and 4-coordinated Ti. Increasing the amount of CaO decreases the proportion of bridging oxygen (BO) atoms and the degree of network connectivity (Q³ and Q⁴), suggesting the simplification of melt polymerisation. Substituting CaO with SiO₂ and maintaining a constant TiO₂ level causes the microstructure of the slag to become more complex. Both SiO₂ and TiO₂ contribute to the more complex structures of the melts. Simultaneously, Si–O–Ti linkages are more favourable than Si–O–Si or Ti–O–Ti linkages. Thus, TiO₂ is regarded as network former in terms of its structure within CST system when the content of TiO₂ excessed 28 mass%.     

Dissolution behaviour of MgO based refractories in CaO–Al2O3–SiO2 slag

Abstract

Magnesium oxide (MgO) based refractories are widely used in secondary refining processes, and their dissolution into refining slag is the primary cause of their shortened lifespan. The dissolution rate was investigated for sintered MgO and commercial MgO–C and MgO–Cr₂O₃ refractories in a synthesised 50CaO–45Al₂O₃–5SiO₂ liquid (mass-%) slag. The change in slag composition was measured after a refractory sample was placed into the molten slag that was stirred by flowing argon gas at 1773?K. The dissolution rate of the sintered MgO was above those of the MgO–C and MgO–Cr₂O₃ refractories under the same gas flowrate, although the dissolution rate of all samples increased as the gas flowrate was increased from 25 to 75?mL·min^??1. The slag containing 5?mass-% FeO considerably promoted the dissolution of the MgO–C refractory because of the oxidation of carbon by FeO. The dissolution of all the refractories was greatly affected by penetration of the liquid slag, with the mass transfer of MgO in the penetrating slag at lower gas flowrates likely being the rate controlling step. At high gas flowrates, Ar bubbles covered the surface and blocked the contact between the liquid slag and the solid phase, reducing the dissolution rate.     

Effect of K2O on Phase Relation and Viscosity of the CaO–SiO2—ZnO—FeO–Al2O3 System Slags

Russian Journal of Non-Ferrous Metals - The effect of K2O on phase relation and viscosity of the CaO–SiO2–25 wt % “FeO”–12 wt % ZnO–3 wt % Al2O3 slags...     

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.     

A thermodynamic model for calculating manganese distribution ratio between CaO–SiO2–MgO–FeO–MnO–Al2O3–TiO2–CaF2 ironmaking slags and carbon saturated hot metal based on the IMCT

A thermodynamic model (IMCT-L_Mn) for calculating manganese distribution ratio between CaO–SiO₂–MgO–FeO–MnO–Al₂O₃–TiO₂–CaF₂ slags and carbon saturated liquid iron have been developed based on the ion and molecule coexistence theory. The predicted manganese distribution ratio shows a reliable agreement with the measured ones. With the aid of the IMCT-L_Mn model, the respective manganese distribution ratio of (Mn²⁺?+?O^2?), MnO·SiO₂, 2MnO·SiO₂, MnO·Al₂O₃, MnO·TiO₂, and 2MnO·TiO₂ are investigated. The results indicate that the structural units SiO₂?+?FeO play a key role in CaO–SiO₂–MgO–FeO–MnO–Al₂O₃–TiO₂–CaF₂ slags in demanganisation process in the course of hot metal treatment at 1673?K. The manganese distribution ratio at a given binary basicity range increases with CaF₂ content, while that decreases with TiO₂ content at different binary basicity scopes, which demonstrate that high Mn in the metal is favoured by TiO₂ content. In the present study, various critical experiments are carried out in an effort to clarify the effect of temperature on demanganisation ability, indicating that the lower temperature of molten metal is, the faster the rate of demanganisation reaction is and the shorter the thermodynamic equilibrium time is and the lower end-point Mn content is. It can be deduced from the obtained experimental results that the greater oxygen potential of slags or iron-based melts, lower content of basic oxides in slags, and lower temperature at reaction region is benefit for demanganisation reaction.     

Kinetics of Na2O evaporation from CaO–Al2O3–SiO2–MgO–TiO2–Na2O slags

The present work is carried out to study the evaporation of Na₂O from CaO–Al₂O₃–SiO₂–TiO₂–MgO–Na₂O slags with high basicity and high alumina in the temperature range of 1500–1560°C. The ratio of evaporation was determined by monitoring the Na₂O content change of the slag melt under isothermal reduction conditions. The results show that the evaporation ratio increases with increasing the temperature. Higher basicity and increasing concentrations of Na₂O, Al₂O₃ are also found to increase the evaporation ratio of Na₂O, while MgO addition only slightly enhances the evaporation ratio. With TiO₂ content increasing, the evaporation ratio first increases and then decreases. The evaporation rate of Na₂O appears to be controlled by chemical reaction at the slag/gas interface in the beginning, followed by a mixed reaction-mass transfer regime, and finally a liquid-phase mass transport step. The apparent activation energy is 134.74?kJ?mol^?1 for the chemical reaction regime and 268.53?kJ?mol^?1 for the liquid-phase mass diffusion step.     

Copper solubility in FeO−Fe2O3−SiO2−Al2O3 slag and distribution equilibria of Pb,Bi, Sb and As between slag and metallic copper

The solubility of copper in silica-unsaturated fayalite slags containing an average of about 8 pct Al₂O₃ was measured by equilibrating the slag with metallic copper at 1200 and 1300°C under CO?CO₂ atmospheres with oxygen potentials in the rangep _{O 2}=10^?6 to 10^?11 at. The copper solubility, which was found to be dependent upon the oxygen potential, was expressed in terms of the Fe/SiO₂ ratio, temperature and activity of CuO_0.5. The distribution of Pb, Bi, Sb and As between copper and slag was measured concurrently by doping the metallic copper. The distribution coefficient was defined by (mole fractionX in metal)/(mole fractionX in slag) assuming the FeO?FeO_1.5?SiO₂?AlO_1.5?CuO_0.5 system slag. The distribution coefficient for lead was found to be a function of the oxygen potential, and a PbO activity in the slag of 0.07±0.01 was measured over the range of 1200 to 1300°C. Dissolution of Bi, Sb and As in the slag was found to be independent of the oxygen potential suggesting atomic rather than oxidic dissolution. The observed distribution coefficient for Bi and Sb was 30. The observed distribution coefficient for As was 300, but this is subject to error up to one order of magnitude due to analytical uncertainty of slag. The data are useful in analyzing minor element behavior in copper smelting processes.     

Relationship between structure and viscosity of CaO–SiO2–MgO–30.00 wt-%Al2O3 slag by molecular dynamics simulation with FT-IR and Raman spectroscopy

Structure of CaO–SiO₂–MgO–30.00?wt-%Al₂O₃ slag was investigated using molecular dynamics simulation at 1873?K, and viscosities with different basicities were measured for quantitatively studying the relationship between structure and viscosity. With the increase of basicity, the three-dimensional networks formed by Si and Al are depolymerised, which is consistent with the analysis using FT-IR and Raman spectroscopy. Additionally, FT-IR analysis shows a dampening of [Al–O–Si] trough, indicating a decrease in the linkage between [SiO₄] and [AlO₄]. Increasing the basicity results in that the BO decreases rapidly, while NBO increases from 32.75% up to 50.23%, which leads to the decrease of viscosity. Variations of CN_Al–O and Al–O–Al indicate that Al₂O₃ prefers to form complicated unit, and Al₂O₃ within this slag should act as a network former. Calculated activation energies of samples A11–A14 are 212, 186, 168 and 161?kJ?mol^?1, respectively. Variation of viscosity linearly depends on Q⁴, and a strong linear relationship could also be found between viscosity and NBO/T. However, the variation of activation energy mainly depends on Q⁴(Si) comparing with Q⁴(Al), Q⁴(Si?+?Al) or NBO/T.