Reduction Behaviour of Wüstite Doped with MgO

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

Reduction of iron-silicon-oxysulfide by CO gas injection

The reduction of liquid oxysulfide in the Fe-Si-S-O system by CO gas injection has been studied by monitoring the exit gas composition. The reduction rate of oxygen was calculated from the volume of evolved CO₂. Sulfur-bearing species such as COS were close to the detection limit of the mass spectrometer, which indicated that the reduction of sulfur was very limited. The volume of evolved CO₂ reached steady values 1 minute after CO injection. The reduction reaction was controlled by a chemical reaction. The observed maximum reduction rate of oxygen at 1250 °C was 8.3×10⁻⁶ g-O/cm² s, which was within the range of the reduction rates in other melts such as iron oxide and iron silicates.     

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

Abstract

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

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

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

The rate of formation of SiO by the reaction of CO or H2 with silica and silicate slags

The rate of formation of SiO(g) by the reaction of CO and H₂ with silica or silicate slags containing SiO₂, CaO, and A1₂O₃ has been measured. The rate with hydrogen for both pure silica and silica in slags is controlled by gas phase mass transport. The rate changed with flow conditions, sample size, and gas properties as predicted by the appropriate mass transfer equations. In particular, the rate is faster in H₂-He than in H₂-Ar gas mixtures with the same hydrogen pressure, which proves conclusively the rate is controlled by gas phase mass transport. The rate of formation of SiO by the reaction of silica with CO did not change with flow conditions or particle size and the rate was the same in CO-He and CO-Ar with the same pressure of CO. In addition, the calculated rate with CO for mass transfer is considerably faster than was observed. These observations strongly indicate the rate is controlled by chemical kinetics on the surface. Similar results were obtained for the rate of reaction of CO with silica in slags and the rate was found to be proportional to the activity of SiO₂ and CO pressure. The present results are discussed in relationship to silicon transfer in slag-metal reactions.     

Rate of reduction of Cr2O3 by carbon and carbon dissolved in liquid iron alloys

The rate of reaction of Cr₂O₃ with carbon or carbon dissolved in liquid iron alloys, and the decarburization of Fe-Cr-C alloys in Ar-O₂ gas mixtures has been investigated. The rate of reduction of dense Cr₂O₃ on the surface of Fe-Cr-C alloys was controlled by the diffusion of carbon to the surface of the melt. The chemical diffusion coefficient derived from the results (8.5 × 10^-5 cm²/s) is in agreement with previous work. The decarburization of Fe-Cr-C alloys in Ar-O₂ gas mixtures was apparently carried out by the Cr₂O₃ which formed on the surface of the melt by the reaction of the dissolved Cr with the oxygen gas and the rate of decarburization was controlled by the diffusion of carbon to the surface. The rate of reduction of Cr₂O₃ by various types of carbon was also investigated at temperatures from 1300 to 1600°C; the initial rate appears to be controlled by gas phase mass transfer of the CO away from the surface of the reactants.     

Reduction behavior and mechanism of Hongge vanadium titanomagnetite pellets by gas mixture of H2 and CO

Hongge vanadium titanomagnetite(HVTM)pellets were reduced by H_2-CO gas mixture for simulating the reduction processes of Midrex and HYL-III shaft furnaces.The influences of reduction temperature,ratio ofφ(H_2)toφ(CO),and pellet size on the reduction of HVTM pellets were evaluated in detail and the reduction reaction kinetics was investigated.The results show that both the reduction degree and reduction rate can be improved with increasing the reduction temperature and the H_2 content as well as decreasing the pellet size.The rational reduction parameters are reduction temperature of 1050°C,ratio ofφ(H_2)toφ(CO)of 2.5,and pellet diameter in the range of 8-11 mm.Under these conditions(pellet diameter of 11mm),final reduction degree of 95.51% is achieved.The X-ray diffraction(XRD)pattern shows that the main phases of final reduced pellets under these conditions(pellet diameter of 11 mm)are reduced iron and rutile.The peak intensity of reduced iron increases obviously with the increase in the reduction temperature.Besides,relatively high reduction temperature promotes the migration and coarsening of metallic iron particles and improves the distribution of vanadium and chromium in the reduced iron,which is conducive to subsequent melting separation.At the early stage,the reduction process is controlled by interfacial chemical reaction and the apparent activation energy is 60.78kJ/mol.The reduction process is controlled by both interfacial chemical reaction and internal diffusion at the final stage,and the apparent activation energy is 30.54kJ/mol.     

旋转床CO还原澳大利亚PB粉特性及动力学研究

采用自主研制的小型旋转床反应器,结合化学分析和X射线衍射分析等技术对CO还原澳大利亚PB粉进行了直接还原实验研究。结果表明:CO流量为200 mL/min,矿粉粒径范围为0.044~0.089 mm,还原时间为60 min,还原温度为1 000℃时,还原产物还原度和金属化率达到最大值,分别为92.70%和86.28%;在700~1 000℃内基于收缩未反应核模型对澳大利亚PB粉还原反应进行动力学分析,得出反应前期(t30 min)还原过程由气体内扩散和界面化学反应混合控制;反应后期(t30 min)还原反应的限制性环节为气体内扩散,指前因子A为0.006 72 s~(-1),表观活化能E为10.043 kJ/mol。     

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.     

The kinetics of formation of h2o and co2 during iron oxide reduction

The kinetics of the chemical reaction-controlled reduction of iron oxides by H₂/H₂O and CO/CO₂ gas mixtures are discussed. From an analysis of the systems it is concluded that the decomposition of the oxides takes place by the two dimensional nucleation and lateral growth of oxygen vacancy clusters at the gas/oxide interface. The rates of decomposition of the oxides under conditions of chemical reaction control are dependent not only on the partial pressures of the reacting gases at the reaction temperature but also on the oxygen activity of the prevailing atmosphere. Application of this model to the kinetic data leads to the determination of the maximum chemical reaction rate constants for the decomposition of the iron oxide surfaces. Assuming the reactions H₂ (g) + O(ads) → H₂O(g) andCO(g) + O(ads) → CO₂ (g) to be rate controlling the maximum chemical reaction rate constants for the reduction of iron oxides are given by $$\Phi _{{\text{H}}_{\text{2}} } = 10^{.00} exp \left( {\frac{{ - 69,300}}{{RT}}} \right)mol m^{ - 2} s^{ - 1} atm^{ - 1} $$ and $$\Phi _{CO} = 10^{4.40} \exp \left( {\frac{{103,900}}{{RT}}} \right)mol m^{ - 2} s^{ - 1} atm^{ - 1} $$ The maximum chemical reaction rate constants do not necessarily indicate the maximum rates which can be achieved in practice since these will depend on the limitations imposed by mass transport in the systems. The rate constants are important however since they indicate for the first time the upper limit of any reduction rate in these systems. The fractions of reaction sites which appear to be active on wüstite surfaces in equilibrium with iron are calculated. A direct relationship between chemical reaction rates on liquid iron surfaces and rates on atomically rough iron oxide surfaces is postulated.     

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

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

Mathematical Modelling and Experimental Investigation of Coke Reduction of FeO in Slag

Mathematic model development and experimental investigations were carried out for the reduction of FeO in slag by coke. Rate expressions for the reduction limited by the different steps and through different reaction routes were proposed. In the experimental investigation, the FeO reduction was found to be a first order and irreversible reaction; the reduction rate increased with increasing temperature and the FeO content in slag, and decreased with increasing ash content in the coke. Low CO₂/CO ratio in the product gas and preferential reduction of FeO over SiO₂ in slag were observed in the reaction system. The proposed reaction mechanisms were discussed with the observed kinetic phenomena. The reduction of FeO in slag by coke was found most likely to be jointly dominated by the mass transfer of FeO in slag and the chemical reactions at slag‐coke, slag‐gas or slag‐metal interfaces.     

Kinetics of carbochlorination of chromium (III) oxide

Kinetics of the carbochlorination of Cr₂O₃ has been studied with Cl₂+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 °C to 800 °C, the reaction order is about 1.34 and is independent of temperature. Changing the Cl₂+CO content from 15 to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of Cl₂/(Cl₂+CO) from 0.125 to 0.857 does not modify the carbochlorination mechanism of Cr₂O₃. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl₂/(Cl₂+CO) ratio of about 0.5.     

Reduction-Carburization of NiO-WO<Subscript>3</Subscript> Under Isothermal Conditions Using H<Subscript>2</Subscript>-CH<Subscript>4</Subscript> Gas Mixture

Ni-W-C ternary carbides were synthesized by simultaneous reduction–carburization of NiO-WO₃ oxide precursors using H₂-CH₄ gas mixtures in the temperature range of 973 to 1273 K. The kinetics of the gas–solid reaction were followed closely by monitoring the mass changes using the thermogravimetric method (TGA). As a thin bed of the precursors were used, each particle was in direct contact with the gas mixture. The results showed that the hydrogen reduction of the oxide mixture was complete before the carburization took place. The nascent particles of the metals formed by reduction could react with the gas mixture with well-defined carbon potential to form a uniform product of Ni-W-C. Consequently, the reaction rate could be conceived as being controlled by the chemical reaction. From the reaction rate, Arrhenius activation energies for reduction and carburization were evaluated. Characterization of the carbides produced was carried out using X-ray diffraction and a scanning electron microscope (SEM) combined with electron dispersion spectroscopy (SEM-EDS) analyses. The grain sizes also were determined. The process parameters, such as the temperature of the reduction–carburization reaction and the composition of the gas mixture, had a strong impact on the carbide composition as well as on the grain size. The results are discussed in light of the reduction kinetics of the oxides and the thermodynamic constraints.     

Rate of reactions between carbon dioxide and graphite

Solid graphite rods have been oxidized at temperatures between 1020 and 1510 °C using CO₂ containing gases. The activation energy was found to be 270 kJ/mol in the temperature range from 1020 to 1170 °C where the reaction is chemically controlled. At higher temperatures the reaction is controlled by external mass transfer of CO₂ with an activation energy of 86 kJ/mol. The shift from chemical to mass transfer control depends on the CO₂ pressure and the gas flow behaviour. Since per mol of carbon consumed one net mol of gas is produced, there is a net gas flow away from the graphite surface. This makes the transport of CO₂ to the surface more difficult, retarding the rate at high temperatures.     

Influence of slag and foam characteristics on reduction of FeO-containing slags by solid carbon

The present study reports experimental results on the reduction of FeO in molten CaO-SiO₂-Al₂O₃-MgO-FeO slags by solid carbon in an extended-arc plasma reactor. The reduction reaction was found to be controlled by mass transport of FeO in liquid slag. The CO gas generated stirs the bath to establish a convective mass transport system. CO also causes foaming. An analysis using dimensionless numbers provides correlations between the rate constant, k, as well as the foaming index, Σ, with some properties of the slag such as viscosity, surface tension, and density. A correlation between k and Σ is also developed using these parameters for slag characteristics.     

Analysis of Gas Thermodynamic Utilization and Reaction Kinetic Mechanism in Shaft Furnace

The technology of coal gasification in shaft furnace is an effective way to develop direct reduction iron in China.In order to clarify the process of the reduction of oxidized pellets in shaft furnace by carbon monoxide or hydrogen in two ways,i.e.thermodynamics and kinetics,the gas utilization and reaction mechanism were studied by theoretical computations and isothermal thermogravimetric experiment.The results showed that the gas utilization increased with the rise of temperature when xH 2 /xCO ≥1and with the increase of xCO /(xH 2 +xCO)when temperature is less than 1 073K.The water-gas shift reaction restrains efficient utilization of gas,particularly in high temperature and hydrogen-rich gas.The gas utilization dropped with increase of carburization quantity of direct reduction iron(DRI)and oxygen potential of atmosphere.With the increase of both temperature and content of H2 in inlet gas, the reaction rate increased.At 100% H2 atmosphere,the interfacial chemical reaction is the dominant reaction restricted step.For the H2-CO mixture atmosphere,the reduction process is controlled by both interfacial chemical reaction and internal diffusion.     

The rate of reduction of iron oxides by carbon

The rate of reduction of Fe₂O₃ and FeO by coconut charcoal, coal char and coke, in an inert atmosphere within the temperature range 900 to 1200°C was investigated. The effects of pressure, particle size, and the amount of carbon were determined. The results indicate that the reaction takes place by means of the gaseous intermediates CO and CO₂, and that the overall rate is controlled by the oxidation of the carbon by CO₂. The rates of reduction of FeO and Fe₂O₃ by CO are relatively fast, and the CO₂/CO ratio for the oxidation of carbon is determined by their equilibria. The reduction of Fe₂O₃ by carbon is accomplished in two stages, with FeO forming first. The reduction of Fe₂O₃ to FeO is faster than that of FeO to Fe because its CO₂/CO equilibrium ratio is higher and hence the rate of oxidation of carbon is faster. A direct comparison was made between the rate constants for the reduction of FeO by carbon and those for the oxidation of carbon in the appropriate CO₂-CO gas mixtures, and they are in good agreement. Apparently the iron formed by the reduction does not significantly catalyze the oxidation of carbon; whereas for the reduction of NiO by carbon, the Ni formed does catalyze the oxidation of carbon.     

Rate of reduction of FeO in slag by Fe-C drops

The rate of reduction of FeO in slags by Fe-C drops plays an important role in several metallurgical processes, including iron bath smelting. In this study, the rate of this reaction was determined by measuring the volume of CO generated as a function of time, and the reaction was observed by X-ray fluoroscopy. The drops entered the slag in a nearly spherical shape, remained as single particles, and for the major portion of the reaction remained suspended in the slag surrounded by a gas halo. The rate was found to decrease with carbon content for alloys with low sulfur contents. The rate decreased significantly with increasing the sulfur content. Based on the results and a comparison of the calculated rates, for the possible rate-controlling mechanisms, a kinetic model was developed. The model is a mixed control model including mass transfer in the slag, mass transfer in the gas halo, and chemical kinetics at the metal interface. At high sulfur contents (>0.01 pct), the rate is primarily controlled by the dissociation of CO₂ on the surface of the iron drop. At very low sulfur, the rate is controlled by the two mass-transfer steps and increases as the gas evolution from the particle increases. Formerly with Carnegie Mellon University     

Reaction mechanism of FeO reduction by solid and dissolved carbon

The reduction reactions of FeO by carbon have been studied in order to be able to understand the fundamental phenomena occurring in smelting reduction process. The reduction of pure FeO by solid carbon proceeds mostly according to the same reaction mechanism as that by dissolved carbon in iron, the rate of which was experimentally determined to be controlled by the interfacial chemical reaction between Fe-C melt and intermediate CO₂ gas. Hence, the reduction rate of pure FeO by solid carbon is also chemically controlled by the Boudouard reaction between the dissolved carbon and CO₂ at the interface of by-product Fe droplet/gas phase, the activation energy of which was found to be about 193.2 kJ/mol. In addition, the reduction reaction of FeO in CaO-SiO₂-Al₂O₃-FeO slags by the dissolved carbon in Fe melt was also investigated over the FeO mass content less than 20 %. The reduction rate shows first order dependence with respect to FeO concentration. The surface active sulphur content in iron does not affect the reduction rate, and the temperature dependence of reduction rate gives the activation energy of 24.78 kJ/mol. Therefore, the reduction rate of FeO in slags by the dissolved carbon can be safely mentioned to be controlled by the liquid phase mass transfer of FeO through the slag phase diffusion-resistant boundary layer over the limited FeO concentration range. The empirical expression for the mass transfer controlled reactioe, deren Aktivierungsenergie ca. 193.2 kJ/mol beträgt. Außerdem wurde die Reduktion von FeO in CaO-SiO₂-Al₂O₃-FeO-Schlacken mit dem in der Eisenschmelze gelöstem Kohlenstoff fär FeO-Massengehalte von weniger als 20% untersucht. Die Reduktionsgeschwindigkeit weist hinsichtlich der FeO-Konzentration eine Abhängigkeit 1. Ordnung auf. Der Anteil an oberflächenaktivemn rate was determined as r = 5.94(±0.07).10^?6.exp(-24780/RT).(%FeOP)^0.96 over the reaction conditions employed.