Enrichment of phosphorus in reduced iron during coal based reduction of high phosphorus-containing oolitic hematite ore

With the objective of phosphorus enrichment in the metallic iron during coal based reduction, high phosphorus oolitic hematite ore was reduced in the presence of coal with the coal/ore molar ratio (C/O, the molar ratio of fixed carbon in coal to oxygen in iron oxides of ore) varying from 1·0 to 2·5 at temperatures ranging from 1473 to 1548 K. The metallic iron was beneficiated from reduction products by magnetic separation. The results showed that the enrichment of phosphorus in the metallic iron improved with increasing temperature and C/O molar ratio. The phosphorus content and the phosphorus enrichment could reach 2·5 and 77·5%, respectively, with a C/O molar ratio of 2·5 at 1548 K and after 60 min reduction. The high phosphorus-containing metallic iron so obtained could then be converted to steel and high phosphorus steelmaking slag that can be used as a phosphate fertiliser. Kinetic analysis demonstrated that the process of phosphorus enrichment in the metallic iron could be divided into two stages, early and late, described by phase boundary controlled reaction and diffusion controlled, respectively. At the early stage, the apparent activation energy and pre-exponential factor of phosphorus enrichment decreased from 182·12 kJ mol^?1 and 9509·06 min^?1 to 132·60 kJ mol^?1 and 395·44 min^?1, respectively, when the C/O molar ratio was increased from 1·0 to 2·5. At the later stage, the apparent activation energy and pre-exponential factor were 245·87 kJ mol^?1 and 172?818·99 min^?1 at a C/O molar ratio of 1·0, respectively, whilst those were reduced to 210·73 kJ mol^?1 and 13?930·28 min^?1 at a C/O molar ratio of 2·5.     

Sintering characteristics and kinetics of acidic haematite ore pellets with and without mill scale addition

Haematite ore pellets require very high induration temperature (>1573?K) while, magnetite ore pellets require much lower temperature due to the oxidation of magnetite during induration. Mixing of some magnetite in haematite ore can improve the sintering property of pellets during induration. Mill scale is a waste material of steel plant which contains mainly FeO and Fe₃O₄. It can also be blended in haematite ore pellet mix which can enhance diffusion bonding and recrystallisation bonding and facilitate sintering at the lower temperature like magnetite ore. The extent of improvement in sintering property, sintering mechanism and its kinetics in the presence of mill scale is very imperative to study. In current study, the sintering characteristics of acidic iron ore pellet with 15% mill scale and without mill scale has been studied separately through microstructure observation, apparent porosity measurement and volume change. The volume changes due to heating at varying temperature and time has been measured by mercury displacement method and the data has been exploited for sintering kinetics study, wherein, extent of sintering α has a power relation with time. Several kinetics parameters such as time exponent (n), rate constant (k) and activation energies have been estimated for above two pellets and compared. While acidic pellet without mill scale requires 385?k?cal?mol^?1, acidic pellet with 15% mill scale requires only 310?k?cal?mol^?1 activation energy.     

Study of grain growth during austenitisation of a pearlitic steel with two starting conditions

A pearlitic steel was subjected to isothermal austenitisation treatments at various temperatures and time lengths at each temperature. The steel was under two different starting conditions, namely, cast?+?forged condition and wire rod condition with 8?mm diameter. For the two different starting conditions, there was a significant difference in grain growth kinetics and activation energy values. Also, there was a significant drop of activation energy value at higher temperature range. The activation energy values were determined to be 161 and 108?kJ?mol^?1, respectively, for the temperature ranges 850–950 and 950–1050°C, in case of cast?+?forged sample and these were 225 and 170?kJ?mol^?1, respectively, for the fully processed rod sample. Self-diffusion and grain boundary diffusion were the most likely processes that governed the austenite grain growth.     

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.     

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.     

Volatilisation behaviour of iron,silicon and magnesium during vacuum carbothermal reduction of ilmenite concentrate

The non-isothermal reduction kinetics and volatilisation behaviour of iron (Fe), silicon (Si), and magnesium (Mg) during the vacuum carbothermal reduction of ilmenite concentrate were investigated from 1350°C to 1550°C. Mg species was reduced to metallic Mg before volatilisation. Some Si elements were reduced to Si, which entered into the Fe phase to form ferrosilicon alloy, and others were reduced to SiO before volatilisation. The volatilisation of Fe came from the metallic Fe phase. For the comprehensive consideration of ?atava–?esták and Coats–Redfern methods, the rate-limiting factors of Fe, Mg, and Si were diffusion control. The integral mechanism functions of Fe, Mg, and Si were G(α)?=?[1?(1?α)^1/3]², G(α)?=?1?2α/3?(1?α)^2/3, and G(α)?=?(1?α)ln(1?α)?+?α, respectively. The apparent activation energy for volatilisation processes of Fe, Mg, and Si were 1043.02?±?12.29, 253.15?±?7.63, and 314.46?±?6.04?kJ?mol^?1, respectively.     

Reduction swelling behaviour of haematite/magnetite agglomerates with addition of MgO and CaO

Abstract

The influence of three kinds of CaO and MgO additives (dolomite, burnt lime and serpentine) on the reduction swelling behaviour of haematite–magnetite (H–M) concentrates pellets was studied. Burnt lime and dolomite increased the reduction swelling index of H–M oxidised pellets, while the reduction swelling index was able to be reduced when serpentine was added. CaO accelerated the formation and growth of metallic iron whiskers and led to abnormal swelling of the magnetite briquettes, while MgO was able to be dissolved in wüstite and reduced the migration rate of Fe²⁺; therefore, there was no catastrophic swelling in either the haematite or magnetite briquettes. As far as H–M concentrate pellets were concerned, because the solubility of CaO in magnetite was greater than that in the primary haematite and the secondary haematite generated from magnetite during the oxidation was easy to be reduced to wüstite, there was abnormal swelling in the reduced H–M pellets with CaO addition.     

Reduction kinetics of carbon containing pellets made from metallurgical dust

Abstract

Reduction experiments of carbon containing pellets made from metallurgical dust were conducted under a weak oxidising atmosphere in the temperature range of 1348–1573 K. Analysis of kinetics and the reduction mechanism revealed that the rate determining step of the reduction of the pellets is the interfacial or local reaction with the activation energy 111·66 kJ mol^?1. The reduction rate can be expressed by the McKewan equation 1?(1?R)^1/3?=?kt. In addition, temperature is an important factor influencing the reaction rate as dezincification and metallisation increase with the increased temperature. The amount of dezincification and metallisation could be up to 97·8 and 79·9% respectively at 1573 K compared to a minimum of 75·3 and 60·2% at 1348 K.     

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.     

Determination of the Rate of CO2–CO Reaction with Magnetite by Isotope Exchange Technique

To clarify the mechanism and get the accurate kinetic parameters of CO₂–CO reaction with magnetite, ¹³CO₂–CO isotope exchange technique was used to determine the rate constants of CO₂ dissociation on the surface of magnetite from 1073 to 1373 K. The real interfacial rate constant was estimated by considering the gas phase mass transfer along a plate. The relationship of the rate constant and CO₂/CO ratio was expressed by the formula of k_c = k₀ (CO₂/CO)^?1?m, m represents the effect of CO₂/CO ratio on the activity of oxygen in iron oxide. The apparent activation energy of the reaction between CO₂–CO gas and magnetite was calculated to 161, 175 ± 15, 198, and 197 ± 16 kJ mol^?1 for CO₂/CO ratios of 4.0, 5.0, 6.0, and 10.0, respectively. This dependence relationship may be caused by the decrease of free electron in magnetite phase with the increase of CO₂/CO ratio.     

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.     

Cupric chloride leaching of a complex copper/zinc/lead ore

A complex Cu/Zn/Pb ore from Cayeli, Turkey, was reacted with cupric chloride solutions under different conditions. Energies of activation were calculated for dissolution of copper (37 kJ mol^?1), iron (33 kJ mol^?1, zinc (26 kJ mol^?1) and lead (7.5 kJ mol^?1, values which indicate diffusion control of the reaction, probably through the sulphur layer formed round each particle. Particle size/leaching relationships corroborated microscopic assessments and indicated that chalcopyrite dissolved at a very low rate. Calculation of Fe:Cu ratios of metal leached showed considerable dissolution of pyrite from finely-ground ($\text{d}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{≈ 3?5 μ}\text{m}$) ore. Examination of residues using SEM X-ray fluorescence line scan techniques revealed little attack of large pyrite crystals, suggesting that fine pyrite particles in complex relationship with the sphalerite and chalcopyrite were dissolving.     

Kinetic study on the metallothermic reduction of chromite ore using magnesium scrap

A study on the metallothermic reduction of chromite ore is presented and discussed, using magnesium scrap as reducing agent. Microstructural analysis corroborated the distribution of phases inside the particles, where Fe and Cr were located at the centre surrounded by layers of reaction products, mainly MgO. The maximum conversion efficiency of Fe and Cr was 38% at 1050°C, after a reaction time of 3 hours, using 75% excess of magnesium scrap. A kinetic study was performed fitting the experimental data to available kinetic models, where the data adjusted to the chemical reaction model, especially at the beginning of reaction. A second reaction stage was confirmed once the experimental data was adjusted to the Jander diffusion model. For the chemical reaction model, the constant rate and the activation energy were 0.32?h^?1 and 60.12?kJ?mol^?1, respectively. For the diffusion model, the rate constant was 0.20?h^?1 and the activation energy 47.04?kJ?mol^?1.     

Reduction Kinetics of Cold-Bonded Briquette Prepared from Return Fines of Sinter with Carbon Monoxide and Coke

The reduction kinetics of cold-bonded briquette prepared from return fines of sinter is studied. The results reveal that cold-bonded briquettes with coke (CBBC) have a higher reduction velocity index (RVI) value than cold-bonded briquettes without coke (CBB). Interfacial chemical reaction controls the early stages of the CBB reduction process at 900 and 950 °C, followed by both interfacial chemical reaction and internal diffusion. At 1000, 1050, and 1100 °C, the early and final stages of the CBB reduction process are controlled by interfacial chemical reaction and internal diffusion, respectively, while both interfacial chemical reaction and internal diffusion control middle stage. The apparent activation energies of the different stages are 46.20, 56.74, 38.24, and 40.74 kJ mol⁻¹, respectively. The gasification of carbon reaction controls the reduction process of CBBC, and the apparent activation energy is 32.42 kJ mol⁻¹. According to the Friedman method, the apparent activation energy of CBB and CBBC is reasonable. Coke promotes the phase transformation in CBBC. Scanning electron microscopy results show that the CBBC sample is more fully reduced than the CBB sample and that it has smoother corners and edges of the iron-bearing phase or the metallic iron phase than the CBB sample.     

Investigation of kinetics of coal based reduction of oolitic iron ore

Abstract

An oolitic iron ore was isothermally reduced by coal at 1423–1573 K, and the reduction kinetics was investigated in detail. The degree of reduction and reduction rate increased with increasing temperature and C/O molar ratio to some extent at the same reduction time. In the entire reduction process, the reduction mechanism changes with changing experimental conditions. The degree of reduction under different experimental conditions should be represented by different reduction kinetic models. The reduction rate curves are similar in shape and could be analytically divided into initial, intermediate and final stages. The apparent activation energies of the three stages are 48·26, 69·80 and 127·58 kJ mol^?1 respectively. The rate controlling mechanism in the reduction process was determined by analysing the reduction process and apparent activation energy. The rate controlling steps of these stages are combined gas diffusion and interfacial chemical reaction, surface chemical reaction and combined solid state diffusion and boundary reaction.     

Decomposition kinetics of industrial jarosite in alkaline media for the recovery of precious metals by cyanidation

In the present study, the aqueous-slurry decomposition kinetics of industrial jarosite in alkaline media for the recovery of silver by cyanidation was investigated. For this purpose, aqueous-slurry decomposition experiments, using both NaOH and Ca(OH)₂ as alkalinising agents, were carried out in order to (1) study the effect of pH (i.e. 8, 9, 10 and11), contact time and temperature (i.e. 30, 40, 60 and 70°C) on jarosite decomposition; (2) elucidate the rate-determining step of the process kinetics when using NaOH or Ca(OH)₂, by applying the shrinking core model and Arrhenius equation and (3) study the effect of the aqueous-slurry decomposition on the recovery of silver by cyanidation. Results showed that when NaOH was used, the decomposition process was controlled by the chemical reaction with an activation energy of 40.42?kJ?mol^?1, whereas when Ca(OH)₂ was used, the decomposition was controlled by diffusion through a porous layer of CaCO₃ with an activation energy of 21.72?kJ?mol^?1. The alkaline decomposition emerges as a necessary step in order to recover up to 74% of the silver contained in the jarosite by cyanidation.     

Cyanidation kinetics of silver telluride (Ag2Te)

The extraction of precious metals from tellurides by cyanidation is more difficult than when they are in their native form, nevertheless the reason for their refractory nature has not been adequately supported. In this study, the mechanism of the cyanidation kinetics of silver telluride (Ag₂Te) was investigated. For this purpose, cyanidation experiments were carried out to: (1) study the difference between the cyanidation kinetics of elemental silver and silver telluride; (2) study the effect of temperature (i.e. 20, 25, 27, 30, 35 and 40°C) on silver telluride dissolution; and (3) elucidate the kinetic mechanism of the silver telluride cyanidation. The results obtained showed that: (1) while 83.5% of elemental silver was dissolved in 8?h, only 13.2% of silver from silver telluride was dissolved in the same time; (2) temperature has an important effect on silver extraction from silver telluride, but a minor effect on tellurium dissolution; and (3) at temperatures between 20 and 27°C, the process was controlled by the chemical reaction with an apparent activation energy of 191.9?kJ?mol^?1, whereas at temperatures between 30 and 40°C, the process was controlled by diffusion through a Ag₅Te₃ layer of products with an apparent activation energy of 25.2?kJ?mol^?1.     

Study on Roast Reaction Kinetics and Crystal Behavior of Ceria-Based Rare Earth Polishing Powder

The TG-DTA curve of the thermal decomposition process of hydrous cerium carbonate was tested in the air. The roasting process was investigated by means of DTA thermal analysis technique. The kinetics of thermal decomposition process was calculated by means of Freeman-Carroll was proved. The apparent activation energy of the dehydrating to hydrous cerium carbonate was E = 7.40 kJ · mol⁻¹, the chemical reaction series was n = 2.28 and the apparent activation energy of the thermal decomposition reaction of cerium carbonate was E = 334.4 kJ · mol⁻¹, and the chemical reaction series n = 3.67. Connected with the kinetics calculation, the influence of different temperature on the ceria crystal structure was studied by means of XRD.     

Kinetics of Alkaline Decomposition and Cyaniding of Argentian Rubidium Jarosite in NaOH Medium

The alkaline decomposition of Argentian rubidium jarosite in NaOH media is characterized by an induction period and a progressive conversion period in which the sulfate and rubidium ions pass to the solution, leaving an amorphous iron hydroxide residue. The process is chemically controlled and the order of reaction with respect to hydroxide concentration in the range of 1.75 and 20.4?mol OH^? m^?3 is 0.94, while activation energy in the range of temperatures of 298?K to 328?K (25?°C to 55?°C) is 91.3?kJ mol^?1. Cyaniding of Argentian rubidium jarosite in NaOH media presents a reaction order of 0 with respect to NaCN concentration (in the range of 5 to 41?mol m^?3) and an order of reaction of 0.62 with respect to hydroxide concentration, in the range of 1.1 and 30?mol [OH^?] m^?3. In this case, the cyaniding process can be described, as in other jarosites, as the following two-step process: (1) a step (slow) of alkaline decomposition that controls the overall process followed by (2) a fast step of silver complexation. The activation energy during cyaniding in the range of temperatures of 298?K to 333?K (25?°C to 60?°C) is 43.5?kJ mol^?1, which is characteristic of a process controlled by chemical reaction. These results are quite similar to that observed for several synthetic jarosites and that precipitated in a zinc hydrometallurgical plant (Industrial Minera México, San Luis Potosi).     

Preparation and properties of fine hematite powders by hydrolysis of iron carboxylate solutions

Submicrometer, crystalline hematite (α-Fe₂O₃) particles were prepared by hydrolysis of organic iron carboxylate solutions using water at 175 °C for 30 minutes. The particle size of hematite was significantly dependent on the liquid-phase stirring speed and the organic compositions. The precipitation rate of hematite from the organic solution followed first-order kinetics. The precipitation rate increased markedly with increasing temperature, and the activation energy for the process was 94.6 kJ mol⁻¹. At 220 °C, the hydrolysis of iron carboxylate solution led to a mixture of hematite and magnetite (Fe₃O₄). The iron oxides prepared at 175 °C to 220 °C were found to be free from organic contamination by the starting material.