Isothermal reduction behaviour of MnO2 doped Fe2O3 compacts with H2 at 1073–1373 K

Abstract

Pure Fe₂O₃ and Fe₂O₃ doped with 2, 4, and 6 mass% of MnO₂ (>99%) compacts annealed at 1473 K for 6 h were isothermally reduced with H₂ at 1073–1373 K. The O₂ weight loss resulted from the reduction of compacts was continuously recorded as a function of time using thermogravimetric analysis (TGA). High pressure mercury porosimeter, optical and scanning electron microscopes, X-ray phase analysis and vibrating sample magnetometer were used to characterise both the annealed and reduced samples. In MnO₂ containing samples, manganese ferrite (MnFe₂O₄) was identified. The rate of reduction of pure and doped compacts increased with temperature and decreased with the increase in MnO₂ content. Unlike in pure compacts, the reduction of MnO₂ containing samples was not completed and stopped at different extents depending on MnO₂ (mass%). At initial reduction stages, the decrease in the rate was due to the presence of poorly reducible manganese ferrite (MnFe₂O₄) phase which was partially reduced to iron manganese oxide (FeO_0.899, MnO_0.101) at the final stages. The reduction mechanism was predicted from the correlation between the reduction kinetics and the structure of partially reduced samples at different temperatures. The reduction of pure and doped samples was controlled by a combined effect of interfacial chemical reaction and gaseous diffusion mechanism at their initial stages. At final stages, the interfacial chemical reaction was the rate controlling mechanism.     

Volume Changes of Iron Oxide Compacts under Isothermal Reduction Conditions

Compacts made from chemically grade Fe₂O₃ were fired at 1473K for 6 hrs. The fired compacts were isothermally reduced either by hydrogen or carbon monoxide at 1073–1373K. The O₂ weight‐loss resulting from the reduction process was continuously recorded as a function of time using TGA technique, whereas the volume change at different reduction conditions was measured by displacement method. Porosity measurements, microscopic examination and X‐ray diffraction analysis were used to characterize the fired and reduced products. The rate of reduction at both the initial and final stages was increased with temperature. The reduction mechanism deduced from the correlations between apparent activation energy values, structure of partially reduced compacts and application of gas‐solid reaction models revealed the reduction rate (dr/dt) at both the initial and final stages. At early stages, the reduction was controlled by a combined effect of gaseous diffusion and interfacial chemical reaction mechanism, while at the final stages the interfacial chemical reaction was the rate determining step. In H₂ reduction, maximum swelling (80%) was obtained at 1373K, which was attributed to the formation of metallic iron plates. In CO reduction, catastrophic swelling (255%) was obtained at 1198K due to the formation of metallic iron plates and whiskers.     

Effects of Mn ore on the Dephosphorization and Desulphurization in Hot Metal Pretreatment

In order to examine the possibility of utilizing Mn ore in the pretreatment process of liquid iron, experiments were carried out in a system with liquid iron and CaO‐SiO₂‐MgO‐Al₂O₃‐FeO slag with additives (Mn ore and Fe₂O₃+MnO₂) in a magnesia crucible at 1673K. When Mn ore was added to the pretreatment slag, decarburization, desiliconization, dephosphorization and desulphurization proceeded simultaneously with the reduction of Mn ore. The reduction rate of MnO and the Mn concentration in the melt increased with increasing initial Si content. The maximum dephosphorization was obtained when the additive consisted of 66.6 mass% Fe₂O₃ and 33.4 mass% MnO₂. The desulphurization ratio increased with increasing the relative amount of MnO₂ in the additives. The amount of additives comprising Fe₂O₃ and MnO₂ required for a targeted manganese content could be predicted using the mass balance. Effects of the additives on dephosphorization were also estimated.     

Electrochemical Measurements of Oxygen Potentials in the Slag System CaO‐P2O5‐SiO2‐FexO

The liquidus compositions of the four‐phase assemblages in the quaternary system of CaO‐P₂O₅‐SiO₂‐Fe_xO were determined at 1473 and 1573 K by employing electron probe microanalysis. Measurements were also made on the Fe_xO activities at temperatures between 1373K and 1699K by employing an electrochemical technique involving stabilized zirconia electrolyte.     

Viscosities of the Quaternary Al2O3‐CaO‐MgO‐SiO2 Slags

Viscosities of some quaternary slags in the Al₂O₃‐CaO‐MgO‐SiO₂ system were measured using the rotating cylinder method. Eight different slag compositions were selected. These slag compositions ranging in the high basicity region were directly related to the secondary steel making operations. The measurements were carried out in the temperature range of 1720 to 1910 K. Viscosities in this system and its sub‐systems were expressed as a function of temperature and composition based on the viscosity model developed earlier at KTH. The iso‐viscosity contours in the Al₂O₃‐CaO‐MgO‐SiO₂ system relevant to ladle slags were calculated at 1823 K and 1873 K for 5 mass% MgO and 10 mass% MgO sections. The predicted results showed good agreement with experimental values and the literature data.     

Effect of Na2O on the Reduction of Fe2O3 Compacts with CO/CO2

Compacts of Fe₂O₃ and Fe₂O₃ doped with varying amounts of Na₂O were isothermally reduced at several temperatures, using CO/CO₂ mixed gas in a vertical resistance furnace. To determine the effect of Na₂O on the reduction of Fe₂O₃ compacts, the mass loss due to oxygen removal was continuously recorded, from which the reduction rate and rate constant were obtained. Na₂O was found to retard the reduction of Fe₂O₃ compacts. The apparent activation energy (E _a) of reaction and the mathematical relationship for pore gas diffusion suggested that the reduction behavior at the initial stages was controlled by a combination of pore gas diffusion and interfacial chemical reaction. At the intermediate and late stages of reduction, pore gas diffusion was the sole contributing factor. Morphological examination of the reduced compacts showed the formation of a liquid phase during the reduction process, which appeared to lower the rate of reaction.     

Effects of Reducing Gas on Swelling and Iron Whisker Formation during the Reduction of Iron Oxide Compact

The effects of different types of reducing gas on swelling and iron whisker formation during the reduction of iron oxide compacts were investigated. The compacts sintered in air at 1273 K were reduced at 1173 K in different reducing atmospheres. The results indicated that catastrophic swelling can happen in CO but not when H₂ is present in the reducing gas mixture. Scanning electron microscope (SEM) micrographs showed that catastrophic swelling was caused by a large amount of long iron whiskers formed during the reduction. The presence of N₂ and CO₂ in CO changed the amount of long iron whiskers and its distribution, which determined the extent of swelling.     

Oxidation of Fe–18%Mn–0.6%C Steels in Air and a N2–CO2–O2 Mixed Gas Atmosphere at 1273–1473 K

Austenitic Fe–18 wt% Mn–0.6 wt% C steels were oxidized at 1273, 1373, and 1473 K for up to 2 h in either atmospheric air or an 85%N₂–10%CO₂–5%O₂ gas mixture. The alloys oxidized faster in air than in the mixed gas, but the morphology and composition of the oxide scale formed were similar in both atmospheres. The scales that consisted primarily of FeO, Fe₂O₃, and MnFe₂O₄ were highly susceptible to cracking and spallation due to the severe oxidation condition. Since Mn was consumed to form MnFe₂O₄, the original γ‐matrix changed to an α‐matrix in the subscale area, in which Mn‐rich internal oxide precipitates formed locally.     

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.     

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.     

Synthesis and Characterization of Fe2MoO4 as a Precursor Material for Mo Alloying in Steel

Iron molybdate (Fe₂MoO₄) has been studied as a new potential precursor for Mo additions in high alloy steel processing. Fe₂MoO₄ was synthesized by high temperature reactions between MoO₃, FeO_x and carbon by holding the mixture first for 23 hours at 873 K and then for 16 hours at 1373 K. The Fe₂MoO₄ syntheses were carried out with pure reagents as well as commercial grade materials supplied by steel industry. A thermodynamic analysis of the stabilities of the various phases in the Fe‐Mo‐O‐C quaternary was carried out. The synthesis processes, leading to the Fe₂MoO₄ formation from the precursors and further reduction by carbon were studied with the aid of thermogravimetric analysis (TGA), high‐temperature X‐ray diffraction (HT‐XRD) and evolved gas analysis by gas chromatography (GC). The maximum temperature in the case of all the experiments was 1373 K. It was found that the reactions between the precursor components start already above 873 K. The precursor mixture from commercial grade materials offers an economically advantageous process route with high Mo yield in steel.     

Composition Control of CaO‐MgO‐Al2O3‐SiO2 Inclusions in Tire Cord Steel ‐ a Thermodynamic Analysis

The effect of oxide component content on the low melting point zone (LMP) in the CaO‐MgO‐Al₂O₃‐SiO₂ system has been analysed using FactSage software. The contents of dissolved elements [Si], [Mg], [O] and [Al] in liquid steel in equilibrium with the LMP inclusions in the CaO‐MgO‐Al₂O₃‐SiO₂ system have been calculated. The results show that the CaO‐MgO‐Al₂O₃‐SiO₂ system has the largest LMP zone (below 1400°C) when the Al₂O₃ content is 20% or the MgO content is 10%. The LMP zone becomes wide with the increase in CaO content (within the range of 0~30 mass%) and the decrease in SiO₂ (from 25 to 5 mass%). To obtain the LMP (below 1400°C) inclusions, the [Mg], [Al] and [O] contents must be controlled within the range of 0.2~2 ppm, 1.0~2.0 ppm and 60~100 ppm, respectively.     

Effect of TiO2 on the Viscosity and Slag Structure in Blast Furnace Type Slags

TiO₂ additions up to 10 mass% behaved as a basic oxide and lowered the viscosity in the CaO–SiO₂–17 mass% Al₂O₃–10 mass% MgO‐based slags by depolymerizing the silicate network structure. Raman spectroscopy revealed the sum of NBO/Si 1 and 3 decreased while the sum of NBO/Si 2 and 4 increased with TiO₂ content. Unlike the silicate structures, the aluminate structures seems to be relatively unaffected by TiO₂ additions according to the FTIR results. 5 mass% TiO₂ significantly decreased the viscosity compared to the TiO₂ free slags, but beyond 5 mass% TiO₂ meaningful changes in the viscosity was not observed. From the comparison of the viscosity at constant TiO₂ of 5 and 10 mass% and varying CaO/SiO₂ ratio, increasing the CaO/SiO₂ ratio was more effective in decreasing the viscosity than TiO₂ additions.     

Effect of dispersed oxides of rare earths and other reactive elements on the high temperature oxidation resistance of Fe-20Cr alloy

The isothermal oxidation resistance in air at 1273, 1323, and 1373 K of Fe-20Cr alloys with 1 wt pct dispersoid of Y₂0₃, La₂O₃, A1₂O₃, TiO₂, SiO₂, Cr₂O₃ and without dispersoid prepared by a conventional sintering and rolling procedures was examined. It was found that SiO₂ dispersoid reduced, while A1₂O₃ dispersoid slightly increased the oxidation resistance. The dispersoids of TiO₂ and Cr₂O₃ showed no beneficial effect on the oxidation resistance except for the oxidation after 10 h at 1373 K. The oxidation behavior after 10 h at 1373 K was rather complex including accelerated oxidation. The beneficial effect of La₂O₃ and Y₂O₃ dispersoids was excellent at all temperatures. The oxidation rates during the early stage of oxidation for the alloys with dispersoid were apparently dependent on the type of the dispersoid. There was no evidence that dispersoid accumulated at the scale-alloy interface. Comparison of results obtained for the oxidation of the alloys prepared by a powder metallurgical procedure with results for the alloys by arc-melting procedure indicated that the grain size of the alloy is an important factor for reduction of oxidation rate but does not seem to be critical, because the grain size of the alloys with dispersoid was not dependent on the type of the dispersoid. Ion Microanalyses of the Cr₂O₃ scale formed after 1 h oxidation at 1373 K showed an interesting feature in that all the dispersed elements were incorporated in the scale and the iron content of the scale was lower on the alloys which exhibited better oxidation resistance.     

Reduction Behaviour of Wüstite Doped with MgO

Compacts made from pure wüstite and compacts doped with 2% MgO were annealed at 1000°C for 3 hrs in 50%CO‐CO₂ gas mixtures. The annealed samples were isothermally reduced at 800‐1100°C in H₂ gas. Selected samples were isothermally reduced at 1000°C with pure CO and 50%H₂‐CO gas mixture to investigate the effect of gas composition on the reduction processes. The oxygen weight loss resulting from the reduction of the samples was recorded as a function of time. X‐ray diffraction (XRD), scanning electron microscopy (SEM), optical microscopy and porosity measurements were used to characterize the annealed and reduced samples. Magnesio‐wüstite (MgO·FeO) phase was formed during the annealing of MgO doped wüstite. The MgO·FeO in turn decreased the porosity of the annealed doped samples compared to pure wüstite compacts. The influence of temperature, gas composition and MgO content on the reduction behaviour and the morphology of the annealed samples was investigated. The values of the apparent activation energy were calculated from Arrhenius plots and correlated with the reduction mechanism. The reduction rate increased with reaction temperature. In doped compacts, the MgO·FeO phase was not completely reduced both at lower reduction temperature (800°C) and during reduction with pure CO. From the activation energy values, the initial reaction stage was controlled by the combined effect of chemical reaction and gas diffusion while solid state diffusion controlled the final stage of reduction. Morphologically, metallic iron was formed in different shape structures under the effect of MgO addition and reduction conditions.     

Thermoanalysis of the combined Fe3O4-reduction and CH4-reforming processes

The chemical equilibrium composition of the system Fe₃O₄ + 4CH₄, at 1300 K and 1 atm consists of solid Fe and a 2:1 gas mixture of H₂ and CO. Thermogravimetric (TG) analysis combined with gas Chromatographic measurements was conducted on the reduction of Fe₃O₄ (powder, 2-μm mean particle size) with 2.3, 5, 10, and 20 pct CH₄ in Ar, at 1273, 1373, 1473, and 1573 K. The reduction proceeded in two stages, from Fe₃O_{4 to FeO, and finally to Fe. CR}, conversion and H₂ yield increased with temperature, while the overall reaction rate increased with temperature and CH4 concentration. C (gr) deposition, due to the cracking of CR,, was observed. By applying a topochemical model for spherical particles of unchanging size, the reaction mechanism was found to be mostly controlled by gas boundary layer diffusion. The apparent activation energy reached a maximum at 30 pct reduction extent and decreased monotonically until completion. When compared with the results using instead either H₂ or CO as reducing gas, the reduction achieved completion faster using CH₄, at temperatures above 1373 K.     

Metallic iron whisker formation and growth during iron oxide reduction: basicity effect

Abstract

The effect of basicity on the metallic iron whisker growth during wüstite reduction was studied in the present investigation. Compacts of pure and CaO/SiO₂ doped wüstite were synthesised. The annealed compacts were isothermally reduced in thermogravimetric apparatus with CO gas at 800–1100°C. The course of reduction was followed by measuring the weight loss as a function of time. X-ray diffraction (XRD), scanning electron microscope (SEM), optical microscope and porosity measurements were used to characterise the annealed and reduced samples. The influence of temperature and basicity (CaO/SiO₂) on the reduction behaviour and the morphology of the annealed samples were investigated. The reduction rate increased with temperature but decreased by increasing basicity value. Metallic iron whisker shape structure was detected in the pure wüstite samples after reduction at high temperatures while in basic wüstite samples, whiskers were formed at the surface of the compacts. From the activation energy values, the reduction of pure wüstite is most likely controlled by a combined effect of gaseous diffusion and interfacial chemical reaction mechanisms. The reduction of basic wüstite compacts with 0·2 and 0·5 basicity ratios are most likely controlled by chemical reaction mechanism while for 0·8 basicity ratio, the reduction rate is most likely controlled by solid state reaction mechanism.     

Selective separation of iron and scandium from Bayer Sc-bearing red mud

In this study, we investigated the separation of iron and scandium from Sc-bearing red mud. The red mud object of our study contained 31.11 wt% total iron (TFe), 0.0045 wt% Sc, hematite (Fe₂O₃) and ferrosilite (FeO·SiO₂) as the main Fe-bearing minerals. The Sc-bearing red mud was treated by a novel deep reduction roasting and magnetic separation process that includes the addition of coke and CaO to extract Fe and enriching Sc from the Sc-bearing red mud. The addition of coke and CaO enhances the transformation of hematite (Fe₂O₃) to metallic iron (Fe⁰) and magnetite (Fe₃O₄) as well as the transformation of ferrosilite into metallic iron (Fe⁰). The test results show that utilizing the new process a Fe concentrate with a TFe content of 81.22 wt% and Fe recovery of 92.96% was obtained. Furthermore, magnetic separation tailings with Sc content of 0.0062 wt% and Sc recovery of 98.65% were also obtained. The test results were achieved under the following process conditions: roasting temperature of 1373 K, roasting time of 45 min, calcium oxide dosage of 20 wt%, coke dosage of 25 wt%, grinding fineness of 90% < 0.04 mm, and magnetic field intensity of 0.24 T. The major minerals in the Fe concentrate are metallic iron (Fe⁰) and magnetite (Fe₃O₄). The main minerals in the magnetic separation tailings with a low TFe content of 2.62% are CaO·SiO₂, Na₂O·SiO₂, FeO·SiO₂, Ca₃Fe₂Si₃O₁₂, CaAl₂SiO₆ and CaFe(SiO₃)₂.     

Effect of Al2O3 and TiO2 on Viscosity,Surface Tension,and Density of Blast Furnace Slag with CaO/SiO2 = 1.13

The influence of Al₂O₃ in the range of 10–20 mass% and TiO₂ in the range of 0.55–5 mass% on the flow behavior, viscosity, density, and surface tension of molten industrial blast furnace slag with CaO/SiO₂ = 1.13 is investigated using a high-temperature microscope, a rotating viscometer, and the maximum bubble pressure method. The measurement results show that Al₂O₃ acts as a network former in the studied CaO–SiO₂–MgO–Al₂O₃–TiO₂ slags. With an increase in the Al₂O₃ content from 10 to 20 mass%, the viscosity and surface tension of the slags increase and the density decreases. In contrast to Al₂O₃, the TiO₂ acts as a surfactant and network breaker in the range of up to 15 mass%. The addition of TiO₂ up to 15 mass% results in a decrease in the viscosity in the liquid-dominated region and a decrease in the surface tension of the studied slags. Therefore, the density increases with the addition of TiO₂ due to increasing molar volume. The behavior of the breakpoint temperature on all the viscosity curves is in complete agreement with the behavior of the flow point temperature and crystallization temperatures of melilite and perovskite.     

Possibility of Selective Oxidation of Vanadium from Iron and Phosphorus in Fe‐V‐P Melt

Experiments on a vanadium recovery method from vanadium containing BOF‐slag using both a Tamman furnace (3 kg scale) and an induction furnace (150 kg scale) were conducted. The vanadium was extracted into the slag phase by bubbling oxidation gas into a metal bath consisting mainly of V (1–10 mass%), Si (less than 1 mass%) and P (about 1 mass%). The first experiments revealed that the slag formed during oxidation reaction had considerably high phosphate capacity. High phosphorus content would rule out the possibility of using the slag as a raw material for the production of ferrovanadium of high quality. In order to reduce the P‐content in the slag, addition of slag former to reduce phosphate capacity was necessary. A suitable slag system (having the initial composition 40 mass% Al₂O₃ ‐ 25 mass% CaO ‐ 35 mass% SiO₂) and a suitable atmosphere, by using CO₂, that enhanced the oxidation of vanadium, but limit the oxidation of iron and phosphorus was found. However, more efforts should be put forward, e.g. study of the phase diagram, the viscosity of the slag and even oxide activities to gain more insight into the slag formed by selective oxidation.