Reduction of Chromite in Liquid Fe-Cr-C-Si Alloys

The kinetics and the mechanism of the reduction of chromite in Fe-Cr-C-Si alloys were studied in the temperature range of 1534 °C to 1702 °C under an inert argon atmosphere. The rotating cylinder technique was used. The melt consisted of 10 and 20 wt Pct chromium, the carbon content varied from 2.8 wt Pct to saturation, and the silicon content varied from 0 to 2 wt Pct. The rotational speed of the chromite cylinder ranged from 100 to 1000 rpm. The initial chromium to iron ratios of the melts varied between 0.11 and 0.26. In Fe-C melts, the effect of rotational speed on the reduction of chromite was very limited. Carbon saturation (5.4 wt Pct) of the alloy caused the reduction to increase 1.5 times over the reduction observed in the unsaturated (4.87 wt Pct) alloy at a given rotational speed. The addition of chromium to the carbon-saturated Fe-C alloy increased the reduction rate. The addition of silicon to the liquid phase increased the reduction rate drastically. The reduction of chromite in Fe-Cr-C melts is hindered because of the formation of, approximately, a 1.5-mm-thick M₇C₃-type carbide layer around the chromite cylinders. This carbide layer did not form when silicon was present in the melt. It was found that the reduction rate is controlled by the liquid-state mass transfer of oxygen. The calculated apparent activation energies for diffusion were 102.9 and 92.9 kJ/mol of oxygen in the Si-O and C-O systems, respectively.     

Kinetics of solid state silica fluxed reduction of chromite with coal

Abstract

Solid state reduction of an Australian chromite with black coal and silica addition was studied thermogravimetrically in the temperature range 1000–1400°C under an argon atmosphere. Reduction was found to occur in two stages. In the first stage, reduction is initiated by the nucleation of metallic iron, and the rate is likely to be controlled by the diffusion of cations in the outer zone of the chromite particles. The Zhuravlev–Lesokhin–Tempel'man equation was determined to fit closest to the experimental data, giving an activation energy of 194 kJ mol^-1. The second stage involves the reduction of chromium, iron, and some silicon ions through the slag. The rate of reduction is proposed to be controlled by dissolution of the chromite into the slag with an activation energy of 256 kJ mol^-1. Silica addition was found to enhance significantly the rate and degree of reduction at 1300 and 1400°C.     

Application of thermodynamic and kinetic principles in the reduction of metal oxides by carbon in a plasma environment

The application of plasma technology to metal oxide reduction is discussed with reference to established thermodynamic and kinetic principles. ΔG°-T diagrams for the corresponding metal oxide, metal carbide, and C-CO reactions are presented and the important role played by thep _CO/P _{CO 2} ratio examined. On the basis of these theoretical considerations, supported by some earlier experimental results conducted on the reduction of iron and chromium oxide concentrates in the form of taconite and chromite by carbon within a plasma reactor, the tendency to form either elemental metals or carbides is discussed. It is also suggested that the reduction of taconite by carbon takes place in two stages within the plasma medium. In the first stage, ferric oxide is reduced to wustite by carbon, and in the second stage wustite is reduced to metal. It is also postulated that in the first stage of reduction, ferric oxide may also be reduced to wustite through an exchange reaction between ferric oxide and iron, without CO evolution. The rate controlling step for the first stage of taconite reduction is thought to lie at the gas/slag interface generated within the plasma environment, while the second stage of reduction is controlled by carbon gasification by CO₂. Formerly Postdoctoral Fellow with Mineral Research Center, University of Minnesota     

Thermodynamics of iron alumino-chromite spinel inclusions in steel

The effect of chromium on the oxygen concentration of iron melts in equilibrium with various spinel reaction products has been determined. Alumina crucibles were used and experiments were performed at 1550, 1600, and 1650°C. Thermodynamic relationships between the equilibrium concentrations of chromium and oxygen in the iron melts have been established for chromium concentrations ranging up to 20 wt pct. Results from X-ray and electron microprobe analyses for the composition of the deoxidation products, together with solute activity relationships, indicate that the composition of the equilibrium spinel phase changes progressively from iron aluminate in the absence of chromium, through a series of aluminate-chromite solid solutions, FeO (Al _x Cr_1−x )₂O₃, (<0.5 pct chromium), to a complex chromite spinel, Fe₂Cr₇O₁₂, (0.5 to 3 pct chromium), and finally chromium oxide, Cr₃O₄ (>3 pct chromium). Deoxidation diagrams have been constructed and the effects of small amounts of alloying elements on the deoxidation behavior of aluminum interpreted in terms of buffered reactions which maintain oxygen concentrations in the melt at levels in excess of those normally associated with aluminum killed steel in equilibrium with alumina alone.     

Aspects of smelting reduction of chromite ore fines in CaO-FeO-Cr2O3-SiO2-Al2O3 slag system by carbon dissolved in high carbon ferrochromium alloy bath

Abstract

Chromite reduction by carbon dissolved in a high carbon ferrochromium alloy melt has been investigated in the temperature range 1580-1640°C using a slag system based on CaO₂-FeO-Cr₂O₃-SiO₂-Al₂O₃. Although the reduction is essentially first order with respect to Cr₂O₃ concentration, it exhibits both zero order and first order reaction kinetics. The zero order period is occupied by the preferential reduction of iron oxide, during which time there is no significant change in the concentration of Cr₂O₃. The predominance of the divalent chromium oxide in the slag phase is seen to provide further evidence that the reduction of chromite occurs by a stagewise process, involving the thermodynamically stable CrO species. While high basicity slags may be recommended to minimise the generation of CrO, and hence improve reaction kinetics and the extent of Cr₂O₃ reduction, there is a limitation imposed by chemical erosion of the alumina crucible as the slag basicity is increased above unity, with the dissolving Al₂O₃ further retarding the reduction kinetics. There is also evidence to suggest the participation of a reductant other than carbon (possibly silicon) in the reduction of chromite.     

The reduction mechanism of chromite in the presence of a silica flux

The reduction behavior of a natural chromite from the Bushveld Complex of South Africa was studied at 1300 °C to 1500 °C. Reduction was by graphite in the presence of silica. Thermo-gravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two-stage reduction mechanism was established. The first stage, up to a reduction level of about 40 pct, is primarily confined to iron metallization, and zoning is observed in partially reduced chromites. In this stage, silica does not interfere with the reduction, which proceeds by an outward diffusion of Fe²⁺ ions and an inward diffusion of Mg²⁺ and Cr²⁺ ions. The second stage is primarily confined to chromium metallization, and formation of a silicate slag alters the reduction mechanism. The slag phase agglomerates and even embeds partially reduced chromite particles. An ion-exchange reaction between the re-ducible cations (Cr³⁺ and Fe²⁺) in the spinel and the dissolved cations (Al³⁺ and Mg²⁺) in the slag allows further reduction. Once the reducible cations are dissolved in the slag phase, they are reduced to the metallic state at sites where there is contact with the reductant.     

The reduction mechanism of a natural chromite at 1416 °C

The behavior of a natural chromite from the Bushveld Complex, Transvaal, South Africa, during reduction at 1416 °C by graphite was studied by means of thermogravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis. Experimental runs were allowed to proceed up to 120 minutes, resulting in 99 pct reduction. The specific objective of this study was to delineate the reduction mechanism of chromite by graphite. Zoning was observed in partially reduced chromites with degrees of reduction of up to about 70 pct. The inner cores were rich in iron, while the outer cores were depleted of iron. Energy-dispersive X-ray analysis revealed that Fe²⁺ and Cr³⁺ ions had diffused outward, whereas Cr²⁺, Al³⁺, and Mg²⁺ ions had diffused inward. The following mechanism of reduction, which is based on the assumption that the composition of the spinel phase remains stoichiometric with increasing degree of reduction, is proposed, (a) Initially, Fe³⁺ and Fe²⁺ ions at the surface of the chromite particle are reduced to the metallic state. This is followed immediately by the reduction of Cr³⁺ ions to the divalent state, (b) Cr²⁺ ions diffusing toward the center of the particle reduce the Fe³⁺ ions in the spinel under the surface of the particle to Fe²⁺ at the interface between the inner and outer cores. Fe²⁺ ions diffuse toward the surface, where they are reduced to metallic iron, (c) After the iron has been completely reduced, Cr³⁺ and any Cr²⁺ that is present are reduced to the metallic state, leaving an iron- and chromium-free spinel, MgAl₂O₄. Formerly Postgraduate Student, Department of Metallurgy and Materials Engineering, University of the Witwatersrand. Formerly with the Department of Metallurgy and Materials Engineering, University of the Witwatersrand.     

Formation of a Network Structure in the Gaseous Reduction of Magnetite Doped with Alumina

Reduction of un-doped magnetite is developed topochemically with the formation of a dense iron shell. However, the reduction of alumina-doped magnetite to wüstite proceeds with the formation of a network-like structure which consists of criss-crossed horizontal and vertical plates of wüstite. Reduction of magnetite includes the conversion of Fe³⁺ to Fe²⁺ and the movement of iron cations from the tetrahedral sites on the {400} and {220} planes of magnetite to the octahedral sites on the {200} planes of wüstite. Alumina has a negligibly small solubility in wüstite. In the reduction of magnetite doped with Al₂O₃, rejected Al³⁺ cations from wüstite diffuse to the magnetite–hercynite solid solution. Enrichment of the Fe₃O₄–FeAl₂O₄ solution with alumina in the vicinity of the reduction interface restricts the growth of {220} planes of wüstite and nucleation of {220} planes adjusted to the existing planes, preventing the merging of wüstite plates during the reduction process. Reduction of magnetite from the magnetite–hercynite solid solution practically stops when the Al³⁺ content at the interface approaches the solubility limit. Wüstite in the separated plates is reduced further to iron.     

Separation of aluminium and preparation of powdered DRI from lateritic iron ore based on direct reduction process

Lateritic iron ore has not been used effectively due to excess content of multiple metals. In this work, separation of aluminium from a high-aluminium lateritic iron ore was achieved by the process of ‘direct reduction with sodium sulfate-magnetic separation’, with a powdered direct reduced iron (DRI) produced. It is found that the presence of 12% sodium sulphate during reductive roasting significantly improves separation of iron and aluminium in magnetic separation: the total iron grade (TFe) of powdered DRI increases from 80.6 to 92.0% and the Al₂O₃ content decreases from 9.8 to 1.3% correspondingly. The presence of sodium sulphate results in formation of sodium aluminosilicates instead of FeAlO₂. Moreover, sodium sulphate significantly promotes growth of metallic iron grains which is beneficial to sufficient liberation and separation of metallic iron grains from gangue minerals in grinding and magnetic separation.     

Solid-state reduction of chromium oxide by methane-containing gas

Reduction of chromium oxide, Cr₂O₃, was investigated in a fixed bed laboratory reactor in the temperature range 900 °C to 1200 °C using CH₄-H₂-Ar gas mixture. The extent and rate of reduction as functions of gas composition and temperature were determined by on-line off-gas analysis using a mass spectrometer. Samples at different stages of reduction were examined by scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. The chromium oxide was reduced to chromium carbide Cr₃C₂ with a degree of reduction close to 100 pct. The rate of reduction increased with temperature and methane content in the reducing gas. Carbon monoxide, added to the reducing gas, strongly retarded the rate of Cr₂O₃ reduction. The hydrogen content had a slight effect on the reduction rate. High extent and rate of reduction by methane-containing gas in comparison with carbothermal reduction were attributed to high carbon activity in the reducing gas—15 to 50 (relative to graphite).     

An ionic diffusion mechanism of chromite reduction

The occurrence of the various phases that form during the solid-state carbothermic reduction of chromite is explained by the use of a point-defect model. In this model each chromite particle is considered to be comprised of concentric layers of spinel unit cells (Fe²+and Mg²+ occupy tetrahedral sites, Cr³+, Al³+, and Fe³+ occupy octahedral sites). The phases that form are a result of the interchange of cations between unit cells within the particle effected by the presence of carbon monoxide at the surface of the particle. Four stages of reduction are identified: (1) the formation of a slightly iron-enriched core comprising distorted spinel unit cells surrounded by a region of normal spinel unit cells, effected by the reduction of Fe³+ to Fe²+; (2) the formation of Cr-Al sesquioxide and Mg-Cr-Al spinel phases effected by the metallization of Fe²+ ions and subsequent production of Cr²+ ions; (3) reduction of Fe²+ interstitials in the spinel core; and (4) metallization of chromium ionsvia the Cr²+ intermediate. The non-appearance of the sesquioxide phase at high temperatures is explained by considering the effect of temperature on the magnitudes of the diffusion coefficients of Cr²+, Mg²+, and interstitial Fe²+ ions.     

不锈钢渣熔融还原中铬在铁浴和熔渣间的分配行为研究

通过正交试验考察不锈钢渣铁浴熔融还原中反应温度、炉渣碱度、渣中Al2O3含量及铁水初始铬含量对铬在铁浴和碱性炉渣间分配行为的影响。试验在石墨坩埚内进行,还原剂为碳饱和铁水中的碳。试验结果表明,对影响渣中铬还原因素的显著性顺序依次为:炉渣碱度>渣中Al2O3含量>铁水初始铬含量>反应温度。此外采用模式识别方法对试验样本进行聚类分析和优化,以获得对渣中氧化铬还原的最佳参数。     

Direct chromium alloying by smelting reduction of mill scale and low grade chromite ore

Direct alloying is the process in which all of the elements needed for alloying can be reduced from their oxides in a furnace or a ladle. This process is one way of reducing the amounts of energy and materials, reducing the loss of alloying elements, and improving working condition. Mill scale produced in rolling mills is considered a rich iron source (> 67% Fe) with minimum impurities. In this paper, iron high-Cr alloy was produced by a direct alloying with chromium in carbo- thermal reduction using fine of low grade chromites ore and mill scale. The smelting experimental heats were carried out in a 5?kg pilot plant submerged electric arc furnace. The charging materials and reduction parameters were varied and the optimum conditions for obtaining alloy with the highest metallic yield and the highest iron and chromium recovery were determined. When using coke as the reducing agent in stoichiometric amounts, for a mixture of mill scale (55%) and chromite ore (45%), 89.1% of the iron and 72.5% of the chromium were recovered, producing iron high-Cr alloy containing 17.9%Cr, 3.73%C, 0.46%Mn and 1.47%Si. The maximum iron and chromium recoveries obtained were 99.3% and 72.5%, respectively when using excess carbon. The present study clarifies the possibility of using a mixture of chromite ore , mill scale and coke as the precursor for direct chromium alloying. This method offers an alternative process route with cheaper raw materials and fewer process steps (by avoiding the step of ferrochrome production) for producing high chromium iron or steel alloys.     

Microwave reduction of Black Thor chromite ore

Black Thor chromite ore from the Ring of Fire deposit in Northern Ontario was carbothermically reduced in a microwave system to produce a ferrochromium alloy. The as-received ore contained 43.0% Cr₂O₃, 19.9% Fe₂O₃, 14.5% MgO, 13.4% Al₂O_3, and 7.0% SiO₂. Activated charcoal was utilised as the reducing agent. First, thermogravimetric analysis/differential thermal analysis (TGA/DTA) and permittivity studies were carried out in order to determine the relationship between the reduction process and the microwave susceptibility. Second, microwave reduction experiments were performed on the chromite ore. The variables investigated were; the amount of carbon, processing time, input power, and type of atmosphere. A maximum chromium grade of 76.1% and a chromium metallisation of 82.7% were obtained for a processing time of 20?min, a power input of 800?W and a carbon addition of 15% in an argon atmosphere.     

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.     

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.     

An ionic diffusion mechanism of chromite reduction

The occurrence of the various phases that form during the solid-state carbothermic reduction of chromite is explained by the use of a point-defect model. In this model each chromite particle is considered to be comprised of concentric layers of spinel unit cells (Fe²+and Mg²+ occupy tetrahedral sites, Cr³+, Al³+, and Fe³+ occupy octahedral sites). The phases that form are a result of the interchange of cations between unit cells within the particle effected by the presence of carbon monoxide at the surface of the particle. Four stages of reduction are identified: (1) the formation of a slightly iron-enriched core comprising distorted spinel unit cells surrounded by a region of normal spinel unit cells, effected by the reduction of Fe³+ to Fe²+; (2) the formation of Cr-Al sesquioxide and Mg-Cr-Al spinel phases effected by the metallization of Fe²+ ions and subsequent production of Cr²+ ions; (3) reduction of Fe²+ interstitials in the spinel core; and (4) metallization of chromium ionsvia the Cr²+ intermediate. The non-appearance of the sesquioxide phase at high temperatures is explained by considering the effect of temperature on the magnitudes of the diffusion coefficients of Cr²+, Mg²+, and interstitial Fe²+ ions. C. W. P. Finn, formerly Associate Professor, University of the Witwatersrand     

Investigations on the carbothermic reduction of chromite ores

Experimental studies were carried out on the reducibility of two different chromite ores using different reducing carbonaceous reducing agents in the temperature range 1173 to 1573 K. “Friable lumpy” ores and “hard lumpy” ores were used in the experiments. Petroleum coke, devolatilized coke, (DVC) and graphite were used as reducing agents. It was found that iron was practically completely reduced before the commencement of the reduction of chromium in the ore. The reduction of iron was controlled by diffusion. The activation energy for this process was estimated to be 130 kJ/mole. The reduction of chromium was controlled by either chemical reaction or nucleation. Rate of reduction was highest when raw petroleum coke was used as the reducing agent. The DVC was less effective compared to raw coke, whereas the rate of reduction was lowest when graphite was used as the reducing agent.     

Formation of Fe3N, Fe4N and Fe16N2 on the surface of iron

In order to clarify the phenomenon of nitride formation on the surface of iron, highly polished specimens of well refined and coarsened iron grains have nitrided in flowing H2 + NH3 gas. The morphology and the conditions for formation of Fe₃N are clarified; it forms only on the surface of {lll}_α or near {lll}_α grains and grows in {112}_α directions during nitriding treatment at temperatures between 450 and 550°C. Fe₁₆N₂ and Fe₄N are also formed preferentially on the surfaces of {00l}_α and {210}_α grains, respectively. It is suggested that these iron surfaces are those satisfying the coherency relationships between nitrides and iron matrices. The morphologies and the formation temperature regions of Fe₁₆N₂ and Fe₄N on the surface of iron are quite different to those observed in iron. In particular, Fe₁₆N₂, which has been generally accepted as metastable in bulk iron below 200°C, can exist even at temperatures from 450 to 500°C when it is formed on the surface of iron.