Influence of CaO-SiO2-Al2O3 Ternary Oxide System on the Reduction Behavior of Carbon Composite Pellet: Part I. Reaction Kinetics

The reduction behavior of composite pellets comprising of hematite, synthetic graphite, and several oxide binder systems was investigated in a laboratory-scale horizontal tube furnace. Three oxide binder systems using silica-rich, alumina-rich, and conventional blast furnace slag compositions were selected to examine the effect of oxide chemistry on the reduction behavior of pellets. Compositional differences in the CaO-SiO₂-Al₂O₃ ternary system were confirmed to influence the reactions occurring in composite pellets during the reduction of iron oxide. An in situ visualization approach was used to observe the oxide/iron/carbon interactions at high temperatures from 1623 K to 1773 K (1350 °C to 1500 °C). The off-gas composition was measured by means of an infrared analyzer to determine the pellet reaction rates. Changes in physical appearance during the in situ reaction experiments demonstrated a strong correlation between the oxide composition and internal reactions. Moreover, the mechanical properties of pellets were investigated by measuring compressive strength to understand the relationship between physical properties of pellets and the associated oxide binder systems selected for this study.     

The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part III. The simulation of volatile reduction in a multi-layer rotary hearth furnace process

For reduction of iron oxides by volatiles from coal, the major reductant was found to be H₂, and it can affect the overall reduction of iron oxides. In this study, the reduction by actual volatiles of composite pellets at 1000 °C was studied. The volatile reduction of the hand-packed Fe₂O₃/coal composite pellet as it is devolatilizing out of the pellet was found to be negligible. However, the reduction of iron oxide pellets at the top layer by volatiles from the bottom layers of a three-layer pellet geometry was observed to be about 15 pct. From the morphological observations of partially reduced pellets and the computed rates of bulk mass transfer, volatile reduction appears to be controlled by a mixed-controlled mechanism of bulk gas mass transfer and the limited-mixed control reduction kinetics. Using the reduction rate obtained from the single pellet experiments with pure hydrogen and extrapolating this rate to an H₂ partial pressure corresponding to the H₂ from the volatiles, an empirical relationship was obtained to approximately predict the amount of volatile reduction up to 20 pct.     

Study of the reduction of UO2 by magnesium or calcium dissolved in molten chlorides

The reduction of solid UO₂ to uranium by magnesium or calcium dissolved in their molten chlorides has been studied. The rate of reduction per unit area of UO₂ surface, at constant temperature and concentration of reductant in the molten chloride, was found to increase with time to a constant value. The rate of reduction per unit area was observed to be proportional to the concentration of reductant in the molten salt. The small increase observed in the reaction rate over the temperature range 750° to 850°C, suggests that the reduction is controlled by transport of the reductant to the reaction site. Solidified salt, containing UO₂ pellets which had been partially reduced, was sectioned, polished, and examined microscopically. The products of the reduction reaction form concentric layers around the UO₂ pellets. Layers of metallic uranium and oxide containing small amounts of dispersed salt alternated with layers of salt containing small amounts of metallic uranium and oxide. The layers ruptured, presumably because the volume of the products, uranium and oxide, is greater than the volume of the UO₂. Therefore, an impervious layer did not form on the oxide surface to inhibit the reduction reaction.     

The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H₂O generated from the reduction of Fe₂O₃ by H₂ was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.     

Design and Fabrication of Pellets for Magnesium Production by Carbothermal Reduction

For carbothermal reduction (CTR) to be an economic and clean process for magnesium metal production, operational challenges must be overcome. Strong and reactive precursor pellets are necessary to effectively and selectively produce Mg_(g) from any feedstock. In this study, the effects of ore (magnesia and dolime), carbon (petroleum coke, charcoal, algal char, and carbon black), and binder (organic and inorganic) on pellet strength and reactivity, product yield and purity, and reduction selectivity were analyzed. Theoretically and experimentally, the CTR of dolime (MgO·CaO) favored MgO reduction over CaO reduction; however, with enough carbon and heat, both oxides could be reduced. CaO carbothermal reduction produced CaC₂ and Ca_(g). The selectivity to CaC₂ remained constant (7 ± 4 pct) for all C/MgO·CaO ratios analyzed, while the selectivity to Ca_(g) increased (5 pct → 40 pct) when C/MgO·CaO was increased from 0.5 to 2.0. As the overall metal yield decreased (77.6 pct → 59.7 pct) with increasing CaO reduction (38.2 pct → 78.1 pct), Ca_(g) reverted faster than Mg_(g). Heavy metal impurities primarily remained in the residue (< 30 pct volatilized) and, when volatilized, condensed at high temperatures (700 °C to 1450 °C), relative to light metal impurities (350 °C to 1000 °C, > 78 pct volatilized). Organic binders added reducing power to the pellets but produced frail pellets (radial crush strength = 9.1 ± 0.7 N) after pyrolysis, relative to pellets with inorganic binders (15.1 ± 3.2 N). Kinetic parameters were determined for extruded pellets to predict the reaction rate as a continuous function of pressure and temperature.     

Effect of Metal Additions to the Reduction of Iron Oxide Composite Pellets with Hydrogen at Moderate Temperatures

The hydrogen reduction behavior of iron oxide composite pellets containing Ni, Fe, and Mn from 973 K to 1173 K was compared with iron oxide and Al₂O₃ containing reference composite pellets to determine the effect of metallic species on the kinetics of iron oxide reduction. The Mn and Ni containing pellets showed slightly faster initial reduction rates compared to the Fe and Al₂O₃ containing pellets. The effect of the metal phases was found to be more significant at lower temperatures when chemical reaction at the interface is a slower and more controlling factor. From the SEM of partially reduced pellets, a wide intermediate region between an O rich unreacted core and an Fe rich outer shell was observed. Although an initially short topochemical receding interface controlled region exists, the mixed control between the topochemical receding interface and pore diffusion was prevalent. For Fe₂O₃/Mn composite pellets, the thermodynamic stability of the MnO is higher and Mn can act as a reductant for iron oxide. Thus, the overall metallization of the Fe₂O₃/Mn composite pellets decreased compared to the other Fe₂O₃/metal composite pellets. From the temperature dependence of the iron‐oxide/metal composite pellets, the apparent activation energy was calculated to be approximately between 15 to 20 kJ/mol, which is typical of a mixed control reduction mechanism of gas diffusion and interface reaction.     

Dissolution Behavior of Rhodium in the Na2O-SiO2 and CaO-SiO2 Slags

To understand the behavior of rhodium during its recovery process, the dissolution behaviors of rhodium in Na₂O-SiO₂ and in CaO-SiO₂ slags at temperatures ranging from 1423 K to 1623 K (from 1150 °C to 1350 °C) and from 1773 K to 1873 K (from 1500 °C to 1600 °C), respectively, in an oxidizing atmosphere were investigated. The solubility of rhodium in the slags was found to increase with increasing oxygen partial pressure, temperature, and the basic oxide content. The correlation between the solubility of rhodium and the oxygen partial pressure suggested that rhodium dissolved into the slags as RhO_1.5. The dissolution of rhodium was slightly endothermic: the enthalpy change of the dissolution of solid rhodium was determined to be 50 ± 10 kJ/mol for the 50(mass pct)Na₂O-50SiO₂; and 188 ± 94 kJ/mol for the 56(mass pct)CaO-44SiO₂ slag systems. The increase in the solubility of rhodium with the basic oxide content indicated that rhodium exhibits acidic behavior in slags. The correlation between the solubility of rhodium and the sulfide capacity of the slags suggested that the ionic species of rhodium in slags is the rhodate ion, RhO ₂ ^? . The rhodate capacity of the slags was defined, and its application to estimate the possible rhodium content in various slag systems was proposed.     

Re-oxidation Kinetics of Flash-Reduced Iron Particles in H2-H2O(g) Atmosphere Relevant to a Novel Flash Ironmaking Process

A novel flash ironmaking process based on hydrogen-containing reduction gases is under development at the University of Utah. The goal of this work was to study the possibility of the re-oxidation of iron particles in a H₂-H₂O gas mixture in the lower part of the flash reactor from the kinetic point of view. The last stage of hydrogen reduction of iron oxide, i.e., the reduction of wustite, is limited by equilibrium. As the reaction mixture cools down, the re-oxidation of iron could take place because of the decreasing equilibrium constant and the high reactivity of the freshly reduced fine iron particles. The effects of temperature and H₂O partial pressure on the re-oxidation rate were examined in the temperature range of 823 K to 973 K (550 °C to 700 °C) and H₂O contents of 40 to 100 pct. The nucleation and growth kinetics model was shown to best describe the re-oxidation kinetics. The partial pressure dependence with respect to water vapor was determined to be of first order, and the activation energy of re-oxidation reaction was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed.     

Kinetics of Silicothermic Reduction of Manganese Oxide for Advanced High-Strength Steel Production

The kinetics of silicothermic reduction of manganese oxide from MnO–SiO₂–CaO–Al₂O₃ slags reacting with Fe-Si droplets were studied in the temperature range of 1823 K to 1923 K (1550 °C to 1650 °C). The effects of initial droplet mass, initial droplet silicon content, and initial slag manganese oxide content were studied. Data obtained for 15 pct silicon showed agreement with control by mass transport of MnO in the slag with a mass transfer coefficient (k _s) of 4.0 × 10^?5 m/s at 1873 K (1600 °C). However, when this rate-determining step was tested at different initial silicon contents, the agreement was lost, suggesting mixed control between silicon transport in the metal and manganese oxide transport in the slag. Increasing the temperature resulted in a decrease in the rate of reaction because of an increase in the favorability of SiO as a product. Significant gas generation was found during all experiments, as a result of silicon monoxide production. The ratio of silicon monoxide to silica formation was increased by factors favoring silicon transport over that of manganese, further supporting the conclusion that the reaction is under mixed control by transports of both silicon and manganese oxide.     

Study of an Energy Storage and Recovery Concept Based on the W/WO3 Redox Reaction: Part I. Kinetic Study and Modeling of the WO3 Reduction Process for Energy Storage

Energy storage and recovery using the redox reaction of tungsten/tungsten-oxide is proposed. The system will store energy as tungsten metal by reducing the tungsten oxide with hydrogen. Thereafter, steam will be used to reoxidize the metal and recover the hydrogen. The volumetric energy density of W for storing hydrogen by this process is 21 kWh/L based on the lower heating value (LHV) of hydrogen. The main objective of this investigation was to study the kinetics of the reduction process of tungsten oxide (WO₃) and determine the optimum parameters for rapid and complete reduction. Theoretical treatment of isothermal kinetics has been extended in the current work to the reduction of tungsten oxide in powder beds. Experiments were carried out using a thermogravimetric technique under isothermal conditions at different temperatures. The reaction at 1073 K (800 °C) was found to take place in the following sequence: WO₃ → WO_2.9 → WO_2.72 → WO₂ → W. Expressions for the last three reaction rate constants and activation energies have been calculated based on the fact that the intermediate reactions proceed as a front moving at a certain velocity while the first reaction occurs in the entire bulk of the oxide. The gas–solid reaction kinetics were modeled mathematically in terms of the process parameters. This model of the reduction has been found to be accurate for bed heights above 1.5 mm and hydrogen partial pressures greater than 3 pct, which is ideal for implementing the energy storage concept.     

ASSESSMENT OF REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS IN COAL FINES FOR APPLICATION IN SPONGE IRONMAKING

Studies on isothermal reduction kinetics (with F grade coal) in fired pellets of hematite iron ores, procured from four different mines of Orissa, were carried out in the temperature range of 850–1000°C to provide information for the Indian sponge iron plants. The rate of reduction in all the fired iron ore pellets increased markedly with a rise of temperature up to 950°C, and thereafter it decreased at 1000°C. The rate was more intense in the first 30 minutes. All iron ores exhibited almost complete reduction in their pellets at temperatures of 900 and 950°C in < 2 hours' heating time duration, and the final product morphologies consisted of prominent cracks. The kinetic model equation 1 ? (1 ? α)^1/3 = kt was found to fit best to the experimental data, and the values of apparent activation energy were evaluated. Reductions of D. R. Pattnaik and M. G. Mohanty iron ore pellets were characterized by higher activation energies (183 and 150 kJ mol^?1), indicating carbon gasification reaction to be the rate-controlling step. The results established lower values of activation energy (83 and 84 kJ mol^?1) for the reduction of G. M. OMC Ltd. and Sakaruddin iron ore pellets, proposing their overall rates to be controlled by indirect reduction reactions.     

Kinetics of Reduction of CaO-FeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-MgO-PbO-SiO<Subscript>2</Subscript> Slags by CO-CO<Subscript>2</Subscript> Gas Mixtures

Kinetics of the reaction of lead slags (PbO-CaO-SiO₂-FeO _x -MgO) with CO-CO₂ gas mixtures was studied by monitoring the changes in the slag composition when a stream of CO-CO₂ gas mixture was blown on the surface of thin layers of slags (3 to 10 mm) at temperatures in the range of 1453 K to 1593 K (1180 °C to 1320 °C). These measurements were carried out under conditions where mass transfer in the gas phase was not the rate-limiting step and the reduction rates were insensitive to factors affecting mass transfer in the slag phase. The results show simultaneous reduction of PbO and Fe₂O₃ in the slag. The measured specific rate of oxygen removal from the melts varied from about 1 × 10^?6 to 4 × 10^?5 mol O cm^?2 s^?1 and was strongly dependent on the slag chemistry and its oxidation state, partial pressure of CO in the reaction gas mixture, and temperature. The deduced apparent first-order rate constant increased with increasing iron oxide content, oxidation state of the slag, and temperature. The results indicate that under the employed experimental conditions, the rate of formation of CO₂ at the gas-slag interface is likely to be the rate-limiting step.     

Oxide Transformation in Cr-Mn-Prealloyed Sintered Steels: Thermodynamic and Kinetic Aspects

The main obstacle for utilization of Cr and Mn as alloying elements in powder metallurgy is their high oxygen affinity leading to oxidation risk during powder manufacturing, handling, and especially during further consolidation. Despite the high purity of the commercially available Cr- and Mn-prealloyed iron powder grades, the risk of stable oxide formation during the sintering process remains. Thermodynamic and kinetic simulation of the oxide formation/transformation on the former powder surface during heating and sintering stages using thermodynamic modeling tools (Thermo-Calc and HSC Chemistry) was performed. Simulation is based on the results from the analysis of amount, morphology, and composition of the oxide phases inside the inter-particle necks in the specimens from interrupted sintering trials utilizing advanced analysis tools (HRSEM + EDX and XPS). The effect of the processing parameters, such as sintering atmosphere composition, temperature profile as well as graphite addition on the possible scenarios of oxide reduction/formation/transformation for Fe-Cr-Mn-C powder systems, was evaluated. Results indicate that oxide transformation occurs in accordance with the thermodynamic stability of oxides as follows: Fe₂O₃ → FeO → Fe₂MnO₄ → Cr₂FeO₄ → Cr₂O₃ → MnCr₂O₄ → MnO/MnSiO _x  → SiO₂. Spinel MnCr₂O₄ was identified as the most stable oxide phase at applied sintering conditions up to 1393 K (1120 °C). Controlled conditions during the heating stage minimize the formation of stable oxide products and produce oxide-free sintered parts.     

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.     

MECHANISMS OF THE REDUCTION OF ZINC FERRITES IN H2/N2 GAS MIXTURES

The rates of reduction of dense pure zinc ferrite and zinc ferrite containing 1 wt% of CaO, MgO, MnO, and Al₂O₃ in solid solution reduced with H₂/N₂ gas mixtures have been investigated at temperatures between 500 and 1100°C. The rate measurements obtained in these studies were complemented with the structural characterization of the partially reduced zinc ferrite samples. The presence of impurity oxides in ZnFe₂O₄ solid solution influenced the conditions for formation of the porous iron morphology. Where porous iron-type microstructures were formed during the reduction reaction, the pore structure of the reduced samples was found to be dependent on reduction temperature, hydrogen partial pressure, and type of impurity oxide added into the solid solution. The reduction plots of zinc ferrite solid solutions exhibited an initial linear rate followed by a gradual decrease in rate with increased percentage reduction. The changes in growth mechanisms and reduction kinetics that occur with changing reduction conditions are discussed.     

Behavior Analysis of CaF2 in Magnesia Carbothermic Reduction Process in Vacuum

Magnesium production by carbothermic reduction of magnesia with CaF₂ in vacuum was investigated experimentally by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and thermodynamic analysis. Thermodynamic calculations indicate that magnesium was generated by a carbothermic reduction among MgO-C system, which should be above 1500 K (1227 °C) (50 Pa). According to the carbothermic reduction analysis, the CaF₂ does not participate in the carbothermic process. The experimental results demonstrated that the mass loss increased along with increasing CaF₂. The percentage was up to 92 pct with 5 pct CaF₂.The reduction degree increased with CaF₂ more than it without CaF₂ obviously. Considering the reduction degree and economic benefit, 5 pct CaF₂ was the optimal choice. The purity of metal magnesium reached 95.59 wt pct, which has perfect crystallization and lamellar structure. CaF₂ did not participate in magnesia carbothermic reduction in vacuum; instead, it played a catalytic role during the process.     

Effects of Binder on the Properties of Iron Ore-Coal Composite Pellets

Large amounts of fines and superfines are generated in Indian iron ore and coal mines due to mechanized mining and mineral dressing operations. Utilization of these fines for extracting metal is of vital concern for resource utilization and pollution control. For agglomeration of these fines, a suitable binder is required. Iron ore-coal composite pellets were prepared by cold bonding. Various binders such as lime, Ca(OH)₂, slaked lime, dextrose, molasses, and sodium polyacrylate (SPA), alone or in combination, were employed for making composite briquettes. The slaked lime–dextrose combination produced the highest strength among the various binders employed for producing composite briquettes and was therefore selected for producing composite pellets for the smelting reduction. In cold bonding, the composite pellets attain the requisite properties due to physico-chemical changes of the binder in ambient conditions. It was possible to obtain a dry strength of more than 300 N per pellet in some cases and more than 200 N per pellet in many trials. Drop strength and shatter index values of composite pellets were also measured. In the present paper an attempt has been made to evaluate the mechanical properties of cold-bonded composite pellets so as to throw some light on the capacity of these pellets to withstand stresses during handling and transportation.     

Behaviour of iron ore–fuel oil composite pellets in isothermal and non-isothermal reduction conditions

Abstract

Self-fluxing iron ore pellets as an alternative to the agglomeration process led to the use of low price fuel oil as a binder and reducing material. Composite pellets containing 5–15% fuel oil were isothermally and non-isothermally reduced at 750–1000°C in a flow of H₂ or N₂ gases. The total weight loss resulting from O₂ removal from the reduction of Fe₂ O₃ and from the thermal decomposition of fuel oil was continuously recorded as a function of time at different reduction conditions. The actual reduction extent at a given time was calculated from the chemical analysis of partially reduced samples at a given time and temperature. Microscopic examination and X-ray phase analysis were applied to characterise the reduction products. The isothermal reduction of composite pellets indicated that the reduction rate increased with the increase in fuel oil content at the early stages. At the later stages, the reduction rate increased in the order 12>10>5> 15% fuel oil containing pellets. The non-isothermal reduction of composite pellets in N₂ atmosphere showed the presence of an incubation period at initial reduction stages. The low intensity magnetic separation technique was applied with the aim of increasing the iron content at the expense of associated impurities. The magnetic and non-magnetic fractions were analysed and the overall recovery was determined.     

Study of nonisothermal reduction of iron ore-coal/char composite pellet

Cold-bonded composite pellets, consisting of iron ore fines and fines of noncoking coal or char, were prepared by steam curing at high pressure in an autoclave employing inorganic binders. Dry compressive strength ranged from 200 to 1000 N for different pellets. The pellets were heated from room temperature to 1273 K under flowing argon at two heating rates. Rates of evolution of product gases were determined from gas Chromatographie analysis, and the temperature of the sample was monitored by thermocouple as a function of time during heating. Degree of reduction, volume change, and compressive strength of the pellets upon reduction were measured subsequently. Degree of reduction ranged from 46 to 99 pct. Nonisothermal devolatilization of coal by this procedure also was carried out for comparison. It has been shown that a significant quantity (10 to 20 pct of the pellet weight) of extraneous H₂O and CO₂ was retained by dried pellets. This accounted for the generation of additional quantities of H₂ and CO during heating. Carbon was the major reductant, but reduction by H₂ also was significant. Ore-coal and ore-char composites exhibited a comparable degree of reduction. However, the former showed superior postreduction strength due to a smaller amount of swelling upon reduction. Formerly Graduate Student, Department of Metallurgical Engineering, Indian Institute of Technology, Kanpur, India     

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.