A study on isothermal reduction kinetics of titaniferous magnetite ore using coke dust,an industrial waste

In the present study, isothermal reduction kinetics of titaniferous magnetite ore (TMO) fines (below 75?µm particle size) using coke dust, an industrial waste, in the form of briquettes have been performed at temperatures ranging from 1273 to 1473?K over varying reduction times: 5, 10, 20, 30, 40 & 60 min. This process aims at the efficient utilisation of TMO which can serve as an alternate potential source of iron, titanium and vanadium. Chemical analysis of the briquette reduced at 1473?K for 60 min, yields a maximum of 89.56% degree of metallisation. Contracting geometry (CG3) is found to be the dominant driving mechanism involved and the activation energy of the reaction is evaluated as 59.52?KJ?mol^?1.     

Disintegration of Northern Cape iron ores under reducing conditions

Abstract

Cracking occurs in the first step of gaseous reduction of hematite iron ore, to magnetite, and can lead to the formation of fine material, with deleterious effects on operation of shaft furnaces. To study this, samples of three ore types from the Northern Cape iron ore field in South Africa, and one blended ore from this region, were studied. The methods were high temperature microscopy (during reduction) and quantification of fines formation following reduction disintegration tests. The ore types do differ significantly with regards to their propensity to form fines. Although disintegration is clearly triggered by reduction, no direct correlation could be established between the degree of reduction and the amount of fines generated. Reduction disintegration increased with higher hydrogen percentages (>5%) in the reduction gas, and at higher temperatures (in the 500–700°C range). Disintegration of the samples decreased at temperatures >750°C. There was no correlation between the presence of gangue minerals and fines formation.     

Effect of Microwave Treatment Upon Processing Oolitic High Phosphorus Iron Ore for Phosphorus Removal

Influence of microwave treatment on the previously proposed phosphorus removal process of oolitic high phosphorus iron ore (gaseous reduction followed by melting separation) has been studied. Microwave treatment was carried out using a high-temperature microwave reactor (Model: MS-WH). Untreated ore fines and microwaved ore fines were then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and thermogravimetric analysis (TGA). Thereafter, experiments on the proposed phosphorus removal process were conducted to examine the effect of microwave treatment. Results show that microwave treatment could change the microstructure of the ore fines and has an intensification effect on its gaseous reduction by reducing gas internal resistance, increasing chemical reaction rate and postponing the occurrence of sintering. Results of gaseous reduction tests using tubular furnace indicate both microwave treatment and high reduction temperature high as 1273 K (1000 °C) are needed to totally break down the dense oolite and metallization rate of the ore fines treated using microwave power of 450 W could reach 90 pct under 1273 K (1000 °C) and for 2 hours. Results of melting separation tests of the reduced ore fines with a metallization rate of 90 pct show that, in addition to the melting conditions in our previous studies, introducing 3 pct Na₂CO₃ to the highly reduced ore fines is necessary, and metal recovery rate and phosphorus content of metal could reach 83 pct and 0.31 mass pct, respectively.     

Characterisation of low-grade Barsua iron ore fines and identification of possible beneficiation strategies

The consumption of iron ore has increased rapidly over the past decade due to the tremendous growth of the iron and steel industry. The depletion of high-grade iron ore resources makes it inevitable to utilise the existing low-grade iron ores/fines/tailings with proper beneficiation to meet the present specification and demand. Beneficiation and utilisation of these fines/tailings still remains a challenging task. In order to find out an effective way of utilisation of these fines, an in-depth characterisation study is essential. A detailed insight into the different mineralogical attributes involving microscopic (both optical and electron), X-ray diffraction, Fourier Transform Infrared Spectroscopy, Thermo Gravimetric Analysis, physical and chemical characterisation, are undertaken on the Barsua iron ore fines. These studies revealed that haematite and goethite are the major iron-bearing minerals with gibbsite, kaolinite and quartz present as gangue. Traces of magnetite are also observed. The liberation size of the sample is found to be below 150?µm. The bulk chemical composition shows around 57.67% Fe, 6.29% Al₂O₃, 3.52% SiO₂ and 6.93% LOI. Based on the detailed characterisation, a possible route of beneficiation of these iron ore fines is discussed and successful implementation of the beneficiation strategies is envisaged.     

STUDIES ON THE REDUCTION KINETICS OF HEMATITE IRON ORE PELLETS WITH NONCOKING COALS FOR SPONGE IRON PLANTS

In the present investigation, fired pellets were made by mixing hematite iron ore fines of ?100, ?16 + 18, and ?8 + 10 mesh size in different ratios and studies on their reduction kinetics in Lakhanpur, Orient OC-2 and Belpahar coals were carried out at temperatures ranging from 850°C to 1000°C with a view toward promoting the massive utilization of fines in ironmaking. The rate of reduction in all the fired iron ore pellets increased markedly with an increase in temperature up to 1000°C, and it was more intense in the first 30 min. The values of activation energy, calculated from integral and differential approaches, for the reduction of fired pellets (prepared from iron ore fines of ?100 mesh size) in coals were found to be in the range 131–148 and 130–181 kJ mol^?1 (for α = 0.2 to 0.8), indicating the process is controlled by a carbon gasification reaction. The addition of selected larger size particles in the matrix of ?100 mesh size fines up to the extent studied decreased the activation energy and slightly increased the reduction rates of resultant fired pellets. In comparison to coal, the reduction of fired pellets in char was characterized by significantly lower reduction rates and higher activation energy.     

Reduction and Swelling of Fired Hematite Iron Ore Pellets by Non-coking Coal Fines for Application in Sponge Ironmaking

In the present investigation, the reduction and swelling behaviors (in low grade coal) of fired iron ore pellets, prepared by blending hematite iron ore fines of ?100, ?18 + 25, and ?10 + 16 mesh sizes in different proportions, have been studied in the temperature range of 850–1000°C with an objective to promote massive utilization of fines in sponge ironmaking. An increase in temperature up to the range studied (850–1000°C) substantially enhanced the reduction rate and the rate was found to be highest in the first 15–30 min at all these temperatures. All the fired pellets, made by mixing iron ore particles of ± 100 mesh size, have shown approximately the same reduction rates and slightly higher swelling indices than those made from fines of ?100 mesh size only. In all the fired pellets reduced at temperatures of 850°C and 900°C, the results indicated an increase in the extent of swelling with reduction time. Reduction of fired pellets at temperatures of 950°C and 1000°C exhibited shrinkage in their reduced products, and the extent of this shrinkage increased with increase in exposure time.     

Experimental study of phase equilibria in the systems Fe-Zn-O and Fe-Zn-Si-O at metallic iron saturation

The reported experimental work on the systems Fe-Zn-O and Fe-Zn-Si-O in equilibrium with metallic iron is part of a wider research program that combines experimental and thermodynamic computer modeling techniques to characterize zinc/lead industrial slags and sinters in the system PbO-ZnO-SiO₂-CaO-FeO-Fe₂O₃. Extensive experimental investigations using high-temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA) were carried out. Special experimental procedures were developed to enable accurate measurements in these ZnO-containing systems to be performed in equilibrium with metallic iron. The systems Fe-Zn-O and Fe-Zn-Si-O were experimentally investigated in equilibrium with metallic iron in the temperature ranges 900 °C to 1200 °C (1173 to 1473 K) and from 1000 °C to 1350 °C (1273 to 1623 K), respectively. The liquidus surface in the system Fe-Zn-Si-O in equilibrium with metallic iron was characterized in the composition ranges 0 to 33 wt pct ZnO and 0 to 40 wt pct SiO₂. The wustite (Fe,Zn)O, zincite (Zn,Fe)O, willemite (Zn,Fe)₂SiO₄, and fayalite (Fe,Zn)₂SiO₄ solid solutions in equilibrium with metallic iron were measured.     

Synthesis of Titanium Oxycarbide from Titanium Slag by Methane-Containing Gas

In this study, reaction steps of a process for synthesis of titanium oxycarbide from titanium slag were demonstrated. This process involves the reduction of titanium slag by a methane-hydrogen-argon mixture at 1473 K (1200 °C) and the leaching of the reduced products by hydrofluoric acid near room temperature to remove the main impurity (Fe₃Si). Some iron was formed by disproportionation of the main M₃O₅ phase before gaseous reduction started. Upon reduction, more iron formed first, followed by reduction of titanium dioxide to suboxides and eventually oxycarbide.     

Studies on the Reduction–Swelling Behaviors of Hematite Iron Ore Pellets with Noncoking Coal

Studies on the reduction and swelling behaviors of fired pellets, made by mixing hematite iron ore fines of ?100, ?18 + 25, and ?10 + 16 mesh sizes in different proportions, were carried out with low-grade coal in the temperature range of 850–1000°C with an aim to promote the massive utilization of fines in ironmaking. The rate of reduction in all the fired iron ore pellets increased markedly with an increase in temperature up to 1000°C and it was more intense in the first 15-min soak time. Relatively higher reduction rates and swellings/shrinkage were observed in the pellets made by the addition of larger size (+100 mesh) particles in the matrix of ?100 mesh size fines. In general, highest swelling was observed in the fired pellets at a reduction temperature of 850°C, followed by a decrease at 900°C. At both these temperatures, the percentage of swelling increased with reduction time up to the range studied (120 min). The fired pellets reduced at temperatures of 950°C and 1000°C, showed shrinkage, and the extent of this shrinkage increased with increase in exposure time at 950°C. The percentage swelling/shrinkage in the fired pellets was found to be related to their crushing strengths and porosities.     

Hydrogen Reduction Kinetics of Magnetite Concentrate Particles Relevant to a Novel Flash Ironmaking Process

A novel ironmaking technology is under development at the University of Utah. The purpose of this research was to determine comprehensive kinetics of the flash reduction reaction of magnetite concentrate particles by hydrogen. Experiments were carried out in the temperature range of 1423 K to 1673 K (1150 °C to 1400 °C) with the other experimental variables being hydrogen partial pressure and particle size. The nucleation and growth kinetics expression was found to describe the reduction rate of fine concentrate particles and the reduction kinetics had a 1/2-order dependence on hydrogen partial pressure and an activation energy of 463 kJ/mol. Unexpectedly, large concentrate particles reacted faster at 1423 K and 1473 K (1150 °C and 1200 °C), but the effect of particle size was negligible when the reduction temperature was above 1573 K (1300 °C). A complete reaction rate expression incorporating all these factors was formulated.     

Silico-ferrite of Calcium and Aluminum (SFCA) Iron Ore Sinter Bonding Phases: New Insights into Their Formation During Heating and Cooling

The formation of silico-ferrite of calcium and aluminum (SFCA) and SFCA-I iron ore sinter phases during heating and cooling of synthetic iron ore sinter mixtures in the range 298?K to 1623?K (25?°C to 1350?°C) and at oxygen partial pressure of 5?×?10^?3 atm has been characterized using in situ synchrotron X-ray diffraction. SFCA and SFCA-I are the key bonding phases in iron ore sinter, and an improved understanding of their formation mechanisms may lead to improved efficiency of industrial sintering processes.?During heating, SFCA-I formation at 1327?K to 1392?K (1054?°C to 1119?°C) (depending on composition) was associated with the reaction of Fe₂O₃, 2CaO·Fe₂O₃, and SiO₂. SFCA formation (1380?K to 1437?K [1107?°C to 1164?°C]) was associated with?the reaction of CaO·Fe₂O₃, SiO₂, and a phase with average composition 49.60, 9.09, 0.14, 7.93, and 32.15?wt pct Fe, Ca, Si, Al, and O, respectively. Increasing Al₂O₃ concentration in the starting sinter mixture increased the temperature range over which SFCA-I was stable before the formation of SFCA, and it stabilized SFCA to a higher temperature before it melted to form a Fe₃O₄?+?melt phase assemblage (1486?K to 1581?K [1213?°C to 1308?°C]). During cooling, the first phase to crystallize from the melt (1452?K to 1561?K [1179?°C to 1288?°C]) was an Fe-rich phase, similar in composition to SFCA-I, and it had an average composition 58.88, 6.89, 0.82, 3.00, and 31.68?wt pct Fe, Ca, Si, Al, and O, respectively. At lower temperatures (1418?K to 1543?K [1145?°C to 1270?°C]), this phase reacted with melt to form SFCA. Increasing Al₂O₃ increased the temperature at which crystallization of the Fe-rich phase occurred, increased the temperature at which crystallization of SFCA occurred, and suppressed the formation of Fe₂O₃ (1358?K to 1418?K [1085?°C to 1145?°C]) to lower temperatures.     

Direct Reduction of Mixtures of Manganese Ore and Iron Ore

This paper presents recent results of direct reduction investigation of different combination of blends of manganese ore, iron ore and coal at the Department of Ferrous Metallurgy (IEHK) of RWTH Aachen University. A mixture of iron and manganese ore in a ratio of 75/25 is a good raw material for steelmaking of high Mn‐alloyed grades. The experimental studies consisting of reduction of (a) fine material and (b) agglomerated material (briquettes) were carried out in the range of 1273 to 1673 K. The behaviour of combined reduction of manganese ore and iron ore and the employment in the direct reduction on a coal and gas basis for production of steels with high Mn content were investigated. It was found that a high metallization degree for Mn can be reached at 1273 K with the reduction of manganese ore by hydrogen‐containing gas. Addition of carbon monoxide to the reducing gas retarded the reduction process. The addition of coal to manganese ore and iron ore blends increased the degree of reduction. The results of carbothermic reduction of briquettes consisting of a mixture of manganese ore and iron ore combined with coal as reducing agent show that a high temperature, a low Mn/Fe ratio and a high Fe₂O₃ content have a favourable effect on the degree of reduction. In order to obtain a high degree of metallization, the temperature should be higher than 1473 K. The reduction of briquettes at higher temperatures (up 1573 K) has shown a molten phase and the separation of slag and metal.     

The two-high blast furnace: A twenty-first-century system

In the twenty-first century, reduction in coke consumption during blast-furnace smelting to the theoretical minimum (160 kg/t of hot metal) is the key factor in improving the technology. One possibility is to include a cyclone reactor when using a 1: 1 mixture of coal-dust fuel and ore fines (concentrate) with an intense blast (1200°C, 30–40% O₂).     

Design of strong tough Fe/Mo/C martensitic steels and the effects of cobalt

The microstructures and mechanical properties of a series of vacuum melted Fe/(2 to 4) Mo/(0.2 to 0.4) C steels with and without cobalt have been investigated in the as-quenched fully martensitic condition and after quenching and tempering for 1 h at 673 K (400°C) and 873 K (600°C); austenitizing was done at 1473 K (1200°C) in argon. Very good strength and toughness properties were obtained with the Fe/2 Mo/0.4 C alloy in the as-quenched martensitic condition and this is attributed mainly to the absence of internal twinning. The slightly inferior toughness properties compared to Fe/Cr/C steels is attributed to the absence of interlath retained austenite. The two 0.4 pct carbon steels having low Mo contents had approximately one-half the amount of transformation twinning associated with the two 0.4 pct carbon steels having high Mo contents. The plane strain fracture toughness of the steels with less twinning was markedly superior to the toughness of those steels with similar alloy chemistry which had more heavily twinned microstructures. Experiments showed that additions of Co to a given Fe/Mo/C steel raised M_s but did not decrease twinning nor improve toughness. Molybdenum carbide particles were found in all specimens tempered at 673 K (400°C). The Fe/Mo/C system exhibits secondary hardening after tempering at 873 K (600°C). The precipitate is probably Mo₂C. This secondary hardening is associated with a reduction in toughness. Additions of Co to Fe/Mo/C steels inhibited or eliminated the secondary hardening effect normally observed. Toughness, however, did not improve and in fact decreased with Co additions.     

Sintering Characteristics of Indian Chrome Ore Fines

Chrome ore concentrate consists of high-temperature melting oxides such as Cr₂O₃, MgO, and Al₂O₃. The presence of these refractory constituents makes the ore a very high melting mineral. Hence, it is difficult to produce sinter from chrome ore by a pyrometallurgical route. Currently, chrome ore is ground to below 75 μm, pelletized, heat hardened through carbothermic reaction at 1300 °C to 1400 °C, and then charged into a submerged electric arc furnace (EAF), along with lumpy ore for ferrochrome/charge-chrome production. Electricity is a major cost element in this extraction process. This work explores the sinterability of chrome ore. The objective of this study was to: (1) determine whether chrome ore is sinterable and, if so, (2) ascertain ways of achieving satisfactory properties at a low temperature of sintering. Sintering of the raw material feed could be a way to reduce electricity consumption, because during sintering a partial reduction of minerals is expected along with agglomeration. Studies carried out by the authors show that it is possible to agglomerate chrome ore fines through sintering. The chrome ore sinter thus produced was found to be inferior in strength, comparable to that of an iron ore sinter, but strength requirements may not be the same for both. Because the heat generation during chrome ore sintering is high owing to some exothermic reactions, compared with iron ore, and because chrome ore contains a high amount of fines, shallow-bed-depth sinter cake production was attempted in the laboratory-scale pot-sintering machine. The sintered product was found to be a good conductor of electricity because of the presence of phases such as magnetite and maghemite. This characteristic of the chrome ore sinter will subsequently have a favorable impact in terms of power consumption during the production of ferrochrome in a submerged EAF. The sinter made was melted in the arc furnace and it was found that the specific melting energy is comparable to that of heat-hardened chrome ore pellets but lower than briquettes and lump ore.     

Reduction of Iron Oxide Fines to Wustite with CO/CO<Subscript>2</Subscript> Gas of Low Reducing Potential

The reduction of iron oxide fines to wustite between 590 °C and 1000 °C with a CO–CO₂ gas mixture of low reducing potential was studied. The reduction kinetics and the dominating reaction mechanism varied with the temperature, extent of reduction, and type of iron oxide. Reduction from hematite to wustite proceeded in two consecutive reaction steps with magnetite as an intermediate oxide. The first reduction step (hematite to magnetite) was fast and controlled by external gas mass transfer independently of the oxide type and the temperature employed. The second reduction step (magnetite to wustite) was the overall reaction-controlling step, and the reduction mechanism varied with the temperature and the oxide type. Moderately porous oxide fines followed the uniform internal reaction for the temperature range studied. For highly porous oxides, the second reduction step was controlled by external gas mass transfer above 700 °C. Below that temperature, a mixed regime that involves external gas mass transfer and limited mixed control, which comprises pore diffusion and chemical reaction, takes place. The rate equations for this mixed control reaction mechanism were developed, and the limited mixed control rate constant (k_lm) was computed. For denser oxides under uniform internal reaction, the product of the rate constant and pore surface area (k·S) was calculated.     

Dephosphorisation of high phosphorus oolitic hematite by carbon composite pre-reduction and fast melting separation

High phosphorus oolitic hematite deposit is a kind of refractory iron ore resource of huge amount. At present, it is difficult to be utilised by traditional physical and chemical technology efficiently and economically. A novel process for utilisation of the high phosphorus oolitic hematite based on carbon composite pre-reduction and fast melting separation has been put forward in the paper. High grade pig iron nugget of low phosphorus could be obtained in the present research. The influence of experimental conditions, such as pre-reduction temperature, C/O (molar ratio) and basicity, on the dephosphorisation behaviours was studied in detail. The thermodynamic basis and reduction and melting separation process were also analysed. The phosphorus content in the iron nugget decreased with the increasing of basicity and increased with the increasing of C/O. The optimum parameters were pre-reduction temperature of 1200°C for 30?min, C/O of 0.95 and basicity of 1.7. After melting separation of molten iron and slag at 1400°C for 10?min, the iron nugget containing 0.02?wt-% [P] would be obtained. The dephosphorisation degree and iron yield in the form of iron nugget were 97.5% and 96.9% respectively. The iron nugget may be directly used as the raw materials of steelmaking from the view point of its high grade.     

Study on Phosphorus Removal of High-Phosphorus Oolitic Hematite by Coal-Based Direct Reduction and Magnetic Separation

In this article, mineralogical phase changes and structural changes of iron oxides and phosphorus-bearing minerals during the direct reduction roasting process were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). It has been found that the reduction of hematite follows the following general pathway: Fe₂O₃ → Fe₃O₄ → FeO → Fe. The last step of the reduction process contains two side reactions: either FeO → Fe₂SiO₄ → Fe or FeO → FeAl₂O₄ → Fe depending on the micro mineralogical makeup of the ore. In the reduction process of FeO → Fe, oolitic structure was destroyed completely and fluorapatite was diffused into gangue while metallic phase is coarsening at temperatures below 1200°C. Therefore, the separation of phosphorus-bearing gangue and metallic iron can be achieved by wet grinding and magnetic separation, and low phosphorus content metallic iron powder can be obtained. However, when the temperature reached 1250°C and beyond, some of the fluorapatite was reduced to elemental P and diffused into the metallic iron phase, making the P content higher in the metallic iron powder.     

Age Hardening of the Al0.5CoCrNiTi0.5 High-Entropy Alloy

Al_0.5CoCrNiTi_0.5 high-entropy alloy was synthesized by vacuum arc melting in a copper mold. This alloy was aged at 773 K to 1473 K (500 °C to 1200 °C) for 24 hours to investigate the microstructure and hardness. The hardness of the as-cast alloy is HV743, and it exhibits a dendritic structure, in which dendrite is composed of body-centered cubic (bcc), face-centered cubic (fcc), and σ phases, and interdendrite is an eutectic structure consisting of bcc and order bcc phases. Apparent age hardening appears at 873 K to 1173 K (600 °C to 900 °C), and no age softening occurs even after 1473 K (1200 °C) aging. The age hardening of this alloy is attributed to the transformation of the bcc phase to σ phase. Detailed variations of hardness and the microstructure of aged alloys are reported in this article.     

Reduction Behavior of Panzhihua Titanomagnetite Concentrates with Coal

The reduction behavior of the Panzhihua titanomagnetite concentrates (PTC) briquette with coal was investigated by temperature-programmed heating under argon atmosphere in a vertical tube electric furnace. The mass loss behavior of the PTC-coal mixture was checked by thermogravimetric analysis method in argon with a heating rate of 5 K (5 °C)/ min. It was found that there are five stages during the carbothermic reduction process of the PTC. The devolatilization of coal occurred in the first stage, and reductions of iron oxides mainly occurred in the second and third stages. The reduction rate of iron oxide in the third stage was much higher than that in the second stage because of the significant rate of carbon gasification reaction. The iron in the ilmenite was reduced in the fourth stage. In the final stage, the rutile was partially reduced to lower valence oxides. The phase transformation of the briquette reduced at different temperatures was investigated by X-ray diffraction (XRD). The main phases of sample reduced at 1173 K (900 °C) are metallic iron, ilmenite (FeTiO₃), and titanomagnetite (Fe_3–x Ti _x O₄). The traces of rutile (TiO₂) were observed at 1273 K (1000 °C). The iron carbide (Fe₃C) and ferrous-pseudobrookite (FeTi₂O₅) appeared at 1473 K (1200 °C). The titanium carbide was found in the sample reduced at 1623 K (1350 °C). The shrinkages of reduced briquettes, which increased with increase in the temperature, were found to depend greatly on the temperature. With increasing the reduction temperature to 1573 K (1300 °C), the iron nuggets were observed outside of the samples reduced. The nugget formation can indicate a new process of ironmaking with titanomagnetite similar to ITmk3 (Ironmaking Technology Mark 3).