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.     

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.     

Reduction of Sn-Bearing Iron Concentrate with Mixed H<Subscript>2</Subscript>/CO Gas for Preparation of Sn-Enriched Direct Reduced Iron

The development of manufacturing technology of Sn-bearing stainless steel inspires a novel concept for using Sn-bearing complex iron ore via reduction with mixed H₂/CO gas to prepare Sn-enriched direct reduced iron (DRI). The thermodynamic analysis of the reduction process confirms the easy reduction of stannic oxide to metallic tin and the rigorous conditions for volatilizing SnO. Although the removal of tin is feasible by reduction of the pellet at 1223 K (950 °C) with mixed gas of 5 vol pct H₂, 28.5 vol pct CO, and 66.5 vol pct CO₂ (CO/(CO + CO₂) = 30 pct), it is necessary that the pellet be further reduced for preparing DRI. In contrast, maintaining Sn in the metallic pellet is demonstrated to be a promising way to effectively use the ore. It is indicated that only 5.5 pct of Sn is volatilized when the pellet is reduced at 1223 K (950 °C) for 30 minutes with the mixed gas of 50 vol pct H₂, 50 vol pct CO (CO/(CO + CO₂) = 100 pct). A metallic pellet (Sn-bearing DRI) with Sn content of 0.293 pct, Fe metallization of 93.5 pct, and total iron content of 88.2 pct is prepared as a raw material for producing Sn-bearing stainless steel. The reduced tin in the Sn-bearing DRI either combines with metallic iron to form Sn-Fe alloy or it remains intact.     

Influence of Manganese Oxide and Silica on the Morphological Structure of Hematite Compacts

Dry compacts of pure Fe₂O₃ and Fe₂O₃ doped with either (2–6 mass%) MnO₂, (2.5–7.5 mass%) SiO₂ or with both (2–6% MnO₂ + 7.5% SiO₂) were indurated at 1373 K for 6 hours and physically and chemically characterized. The fired compacts were isothermally reduced with pure CO gas at 1073–1373 K. The O₂‐weight loss was continuously recorded as a function of time using TGA technique. The external volume of pure and doped compacts was measured at different reduction conditions and the volume change was calculated. The structural changes accompanying the reduction process were visually and microscopically examined and the different phases were identified by X‐ray diffraction analysis. After firing, manganese ferrite (MnFe₂O₄) phase was identified in MnO₂‐doped compacts. In pure Fe₂O₃ compacts, the external volume of compacts was increased with reduction temperature, showing a maximum swelling value at 1198 K. Catastrophic swelling was observed in MnO₂‐doped Fe₂O₃ compacts, the volume change increased with MnO₂ content showing catastrophic swelling in compacts containing 6%MnO₂ at 1248 K. The catastrophic swelling was attributed to the formation of dense metallic iron whiskers and plates in a highly porous structure. Unlike in MnO₂‐doped samples, no considerable volume changes were detected in SiO₂‐doped Fe₂O₃ and (MnO₂ + SiO₂)‐doped Fe₂O₃ compacts where the presence of silica greatly hindered the swelling phenomenon at all reduction temperatures.     

Reduction of iron oxides by wet gas in the presence of carbon

The equilibrium parameters in the reduction of iron oxides by wet gas (CO + CO₂ + H₂ + H₂O) in the presence of carbon are calculated. Graphical representation of the results is discussed, and a diagram is plotted consisting of a set of three-phase equilibrium surfaces and four-phase equilibrium curves, whose point of intersection determines the parameters of invariant five-phase equilibrium. The composition of the wet gas in equilibrium with the following mixtures is established: Fe₃O₄-C, Fe₃O₄-FeO-C, FeO-C, FeO-Fe(C)-C, Fe(C)-C, and Fe₃O₄-Fe(C)-C. A method of graphical determination of the possible wet gas compositions in equilibrium with these mixtures is proposed.     

Kinetics of reduction of ferric iron in Fe2O3-CaO-SiO2-Al2O3 slags under argon, CO-CO2, or H2-H2O

The rates of reduction of ferric iron in Fe₂O₃-CaO-SiO₂-Al₂O₃ slags containing 3 to 21 wt pct Fe₂O₃ under impinging argon, CO-CO₂, or H₂-H₂O have been studied at 1370 °C under conditions of enhanced mass transfer in the slag using a rotating alumina disc just in contact with the slag surface. For a 6 wt pct Fe slag at a stirring speed of 900 rpm the observed reduction rates by 50 pct H₂-H₂O were a factor of 2 to 3 times higher than those by 50 pct CO-CO₂ and more than one order of magnitude higher than those under pure argon. The observed rates were analyzed to determine the rate-controlling mechanisms for the present conditions. Analysis of the rate data suggests that the rates under 50 pct H₂-H₂O are predominantly controlled by the slag mass transfer. The derived values of the mass-transfer coefficient followed a square-root dependence on the stirring speed for a given slag and, at a given stirring speed, a linear function of the total iron content of the slags. The rates of oxygen evolution during reduction under pure argon were shown to be consistent with a rate-controlling mechanism involving a fast chemical reaction at the interface and relatively slow mass transfer in the gaseous and the slag phases. The rates of reduction by CO-CO₂ (pCO=0.02 to 0.82 atm) were found to be likely of a mixed control by the slag mass transfer and the interfacial reaction. A significant contribution of oxygen evolution to the overall rates was observed for more-oxidized slags and for experiments with relatively low values of pCO. Assuming a parallel reaction mechanism, the estimated net reduction rates due to CO were found to be of the first order in pCO, with the first-order rate constants being approximately a linear function of the ferric concentration. This article is based on a presentation made in the “Geoffrey Belton Memorial Symposium” held in January 2000, in Sydney, Australia, under the joint sponsorship of ISS and TMS. The original symposium appeared in the October 2000 Vol. 31B issue.     

Effect of oxide scale on carbon deposition on Fe-Ni alloys in carburizing gas

The behavior of carbon deposition on preoxidized Fe-Ni alloys containing 0 to 57.0 mass pct Ni in 10 pct CH₄-H₂ mixture at 1203 K was studied by metallography and thermogravimetry. Nickel retarded carburization and carbon deposition by lowering the solubility limit of graphite in austenite and by reducing catalytic activity for the pyrolytic reaction of CH₄. On oxidation in air, the addition of nickel to iron depressed the development of FeO and, thereby, caused a significant decrease in the thickness of the scale. The exposure of the alloys to 10 pct CH₄-H₂ mixture after the oxidation in air led to a sudden mass loss in the early stage and then a rapid mass gain. This mass change is primarily ascribed to mass loss by reduction of iron oxides and to mass gain by carbon deposition. The rapid mass gain by carbon deposition is probably due to the formation of active iron by reduction of iron oxides and to the increase in the reaction area by spallation of the scale; the active iron formed may promote filamentous carbon deposition through Fe₃C formation and decomposition. Carbon deposition on the alloys containing 27.2 mass pct Ni or more was considerably retarded because of the formation of a thin oxide scale which consists of α-Fe₂O₃ and spinel (Ni_xFe_3−xO₄) and the reduction of catalysis by enrichment of nickel in the subscale. However, the amounts of carbon deposition increased compared with those on the as-polished alloys, owing to the presence of reducible iron oxides.     

Utilization of Waste Wood for Production of Iron,Carbon Monoxide and Hydrogen without generating Carbon Dioxide

National legislation within Japan has increased the need for the development of new process technologies that will utilise waste wood materials. The present study is aimed at generating some fundamental data with respect to the reduction of iron oxide by waste wood. By using a high frequency induction furnace, mixtures of wood + Fe₂O₃ were heated very rapidly to temperatures between 1673 and 2073K in a stream of argon. Gas chromatographic technique applied on exhaust gases escaping from the furnace revealed that the gaseous reaction products consisted mainly of carbon monoxide and hydrogen. On the other hand, conventional chemical analysis and X‐ray diffraction technique made on condensed‐phase reaction products detected the presence of Fe‐C alloys, solid carbon (char) and ferrous oxide, depending upon the atomic ratio of C/O within wood + Fe₂O₃ mixture. Thus, the reaction products consisted of metallic iron, ferrous oxide, char, CO, CO₂, H₂O, H₂ and CH₄, depending upon C/O atomic ratio within the mixture and the experimental temperature. The results were in good agreement with values calculated from thermodynamic equilibrium.     

Study of a titaniferous magnetite chlorination at high temperature

The chlorination of a titaniferous magnetite with low content in Ti and Fe has been studied between 1273 and 2273 K. Most of the hercynite and ilmenite initially present are decomposed during the gas-solid phase reaction between 1273 and 1823 K. Considerable ilmenite decomposition and FeCl₃evolution already occur at 1273 K, leaving a residue consisting of TiO₂, Fe₂O₃-TiO₂ (pseudobrookite), and about 50 pct of each of the Cr and Mg initially present. X-ray diffractograms shown the formation of Al₂TiO₅ which contributes to the stabilization of TiO₂ up to 1773 K, above which temperature significant decomposition of Al₂TiO₅ is observed. At the melting point of the titaniferous magnetite sample (around 1823 K), the presence of both solid and liquid phases result in a considerable decrease in the chlorination rate. In this respect, heating the sample under helium up to the melting point, so that liquid and solid phases are obtained at equilibrium, yields two structures replacing the magnetite present just prior to melting. One of these structures is of the spinel Fe₂TiO₄ type, while the other is a combination of the spinel types MgAl₂O₄, FeAl₂O₄, and MgCr₂O₄. When the sample is chlorinated, a high proportion of the initial Cr (90 pct) and Ti (80 pct) are found in the chlorination residue at the early stages of fusion, together with 13 pct of the initial Fe. Chlorination of the liquid phase between 1823 and 2273 K shows a steady decrease of Ti and Cr in the chlorination residue, associated with an increase of Fe content.     

Reduction of solid wustite in H2/H2O/CO/CO2 gas mixtures

The reduction of dense wustite in H₂/H₂O/CO/CO₂ gas mixtures has been carried out at temperatures between 1073 and 1373 K. The critical conditions for the formation of porous iron product morphologies have been identified and the results discussed in relation to the breakdown of dense iron layers on wustite surfaces. Formerly with the University of Queensland.     

Non-isothermal reduction characteristics of roasted high alumina iron ore pellets

Non-isothermal reduction of roasted Guangxi high alumina iron ore pellets with CO and H₂ was conducted with high temperature synchronisation thermal analyser (NETZSCH STA 409C/CD) to understand the reduction characteristic of the ore. Chemical analysis, X-ray diffraction examination and scanning electron microscope analysis were adopted to analyse the roasted and reduced pellets. The results show that there are three main phases of Fe₂O₃, Al₂O₃ and Al₃Fe₅O₁₂ in the roasted pellets. During reduction process, the iron bonded in hercynite and fayalite is difficult to be reduced by CO so that the final reduction degree is only 35.62% at the setting temperature of 1573?K. But with H₂ atmosphere, the reduction degree can reach 100% at about 1520?K. It suggests that the ferric ion can completely be reduced to metallic iron by H₂.     

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.     

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.     

Characterization of Cu-SiO2 Composite Synthesized by Hydrogen Reduction of Chalcopyrite Concentrate Followed by Acid Leaching

A Ghatshila chalcopyrite concentrate (average particle size, 50 μm) containing primarily CuFeS₂ and SiO₂ (Cu 16 pct, Fe 26 pct, S 14 pct, Si 5 pct, and O 33 pct) was reduced by a stream of hydrogen in a horizontal tube furnace at 1323 K (1050 °C), producing a mixture of Cu (26 pct), SiO₂, Fe₂O₃, Fe₃O₄, Cu₂O, and Fe. Subsequent acid leaching with 1 M HCl solution of the reduction product removed all iron oxides and iron, and other impurities too, leaving a Cu (53.3 pct) + SiO₂ mixture, with a small percentage of Cu₂O in it. This result compares well with the predicted final mixture of Cu (59 pct)-SiO₂ based on a mass balance on the starting concentrate. Elemental chemical analyses were done by energy-dispersive X-ray spectroscopy, which were crosschecked by atomic absorption spectroscopy in the majority of cases. The phase identification and microstructural characterization of Cu-SiO₂ mixtures were done by X-ray diffraction, Fourier transform infrared spectroscopy, Rietveld analysis, scanning electron microscopy, and high-resolution transmission electron microscopy (HRTEM). It was found that Cu-SiO₂ composites were formed in the final product, with a copper grain size of 385 nm.     

On the relative rates of CO2—CO and H2O—H2 reactions with liquid silver at 1283 K and a liquid silicate at 1373 K

Measurements have been made of the steady-state oxygen activity in liquid silver at 1283 K in flowing CO₂—H₂ and H₂O—CO gas mixtures. It is shown that the results are consistent with the consecutive reactions CO₂ (g) → O (ad) + CO (g) and H₂ (g) + O (ad) → H₂O (g) as the rate determining steps under the limiting conditions of low coverage by adsorbed oxygen. Measurements of the steady-state oxygen activity in two iron oxide-containing lithium silicates under flowing CO₂-H₂ gas mixtures at 1373 K are in agreement with a similar mechanism. The study indicates that the rate of dissociation of H₂O is about 4.6 times higher than the rate of dissociation of CO₂ on the liquid silver surface at 1283 K and about 2.1 times higher on the lithium silicate surface at 1373 K. From the present and previous work, it appears that the ratio of the rates of dissociation of H₂O and CO₂ at high temperatures is not strongly influenced by the nature of the reaction surface, despite significant differences in absolute reaction rates.     

Establishment of product morphology during the initial stages of wustite reduction

The product morphologies obtained on the reduction of wustite in CO/CO₂ gas mixtures between 1073 and 1373 K are reported. Three types of product morphology are identified, namely, type A (porous iron), type B (porous wustite covered with dense iron), and type C (dense wustite covered with dense iron). The reactions which occur during the reduction of wustite in CO/CO₂ and H₂/H₂O systems both before and after iron nucleation are examined. The product morphologies obtained on reduction are explained qualitatively in terms of the relative rates of the chemical reaction with the gas and the mass transport processes both in and on the solid. Formerly Postdoctoral Fellow at the Department of Mining and Metallurgical Engineering, University of Queensland, St. Lucia, Brisbane, Australia An erratum to this article is available at .     

Reduction and carburization of iron-ore in a fluidized bed by CO,H2 and CH4

The reduction and carburization of fine iron-ore (100 - 200 μm, Fe₂O₃ mass content of 98%) by gas mixtures containing CO, H₂ and CH₄ was investigated in a fluidized bed at temperatures of 400 up to 700°C. In this temperature range carbon is formed from CO via the Boudouard reaction as well as by the decomposition of methane. Yet, both reactions only occur in the presence of metallic iron and therefore only at reduction degrees of the DRI (direct-reduced iron) of more than 33%. As a contribution to the development of a DRI process without a costly hot briquetting, the influence of the C- and O-content of the DRI on its tendency to reoxidize was also investigated by means of the ignition point method. It was found that reoxidation (at 20°C) of a totally reduced DRI can be suppressed by carbon mass contents of more than 7%. With decreasing reduction degrees, this value decreases, until for reduction degrees of less than 80% no carbon is needed to suppress reoxidation. With regard to the final reduction of the DRI in the electric arc furnace, the molar C to O ratio should be one. The maximal reduction degree is then about 86% to stabilize carbon rich DRI (C mass content of 4%) against reoxidation.     

Thermodynamic study of the reduction of titanium magnetite concentrate with solid carbon

In this article, a study of the thermodynamics of reduction of titanium-magnetite concentrate with solid carbon in different stoichiometric proportions (carbon-concentrate 1:1, 2:1 and 2.5:1) in the temperature range of 973 to 1273 K is presented. The Gibbs free energy ΔG° _T = f(T), log₁₀ P _{CO 2}/P _CO = f(T), and electromotive force (EMF) = f(T) of the probable reaction Fe₃O₄ + C = 3FeO + CO in the concentrate is studied by the galvanic cell with different reference electrode-air and Ni/NiO. The X-ray analysis indicates different behaviors of the reduction process with solid carbon when 1:1, 2:1, and 2.5:1 ratios of carbon/concentrate were used. The best result is obtained when the ratio is 2.5:1. Some amorphous mass (diatomite) is also observed. The highest concentration of CO (62 to 65 pct) in the gas phase was observed at a carbon-to-concentrate ratio 2:1 and the lowest concentration of CO (40 to 45 pct) at the ratio 1:1.     

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.