The Reaction Behavior of Direct Reduced Iron (DRI) in Steelmaking Slags: Effect of DRI Carbon and Preheating Temperature

An experimental study was conducted to quantify the rate of direct reduced iron (DRI) decarburization in a steelmaking slag using the constant volume pressure increase technique. Experiments were conducted by dropping DRI pellets into molten slag at temperatures from 1773 K to 1873 K (1500 °C to 1600 °C). Subsequent experiments were carried out in which the DRI pellets were preheated while the slag temperature remained constant. The effect of the initial carbon content and the preheating temperature of the DRI on the reaction rate was investigated. The decarburization of DRI seems to comprise two stages, a reaction between the FeO and DRI followed by decarburization through the iron oxide of slag. Carbon has a significant effect on the kinetics of both stages, whereas the preheating temperature mainly influences the rate of decarburization between FeO and carbon inside the pellet.     

Reduction of FeO in smelting slags by solid carbon: Experimental results

The reduction of CaO-SiO₂-Al₂O₃-FeO slags containing less than 10 wt pct FeO by solid carbonaceous materials such as graphite, coke, and coal char was investigated at reaction temperatures of 1400 °C to 1450 °C. The carbon monoxide evolution rate from the system was measured using stationary and rotating carbon rods, stationary horizontal carbon surfaces, and pinned stationary spheres as the reductants. The measured reaction rate ranged from 3.25 × 10^?7 mol cm^?2 s^?1 at 2.1 pct FeO under static conditions to 3.6 × 10^?6 mol cm^?2 s^?1 at 9.5 pct FeO for a rotating rod experiment. Visualization of the experiment using X-ray fluoroscopy showed that gas evolution from the reduction reaction caused the slag to foam during the experiment and that a gas film formed between the carbon surface and the slag at all times during experimentation. The reaction rate increased with increased slag FeO contents under all experimental conditions; however, this variation was not linear with FeO content. The reaction rate also increased with the rotation speed of the carbon rod at a given FeO content. A small increase in the reaction rate, at a given FeO content, was found when horizontal coke surfaces and coke spheres were used as the reductant as compared to graphite and coal char. The results of these experiments do not fit the traditional mass transfer correlations due to the evolution of gas during the experiment. The experimental results are consistent, however, with the hypothesis that liquid phase mass transfer of iron oxide is a major factor in the rate of reduction of iron oxide from slags by carbonaceous materials. In a second article, the individual rates of the possible limiting steps will be compared and a mixed control model will be used to explain the measured reaction rates.     

Reaction rate and product morphology in carbon composite iron ore pellets with and without Portland cement

Abstract

The aim of this work is to study the reaction rate and the morphology of intermediate reaction products during iron ore reduction when iron ore and carbonaceous materials are agglomerated together with or without Portland cement. The reaction was performed at high temperatures, and used small size samples in order to minimise heat transfer constraints. Coke breeze and pure graphite were the carbonaceous materials employed. Portland cement was applied as a binder, and pellet diameters were in the range 5·6–6·5 mm. The experimental technique involved the measurement of the pellet weight loss, as well as the interruption of the reaction at different stages, in order to submit the partially reduced pellet to scanning electron microscopy. The experimental temperature was in the range 1423–1623 K, and the total reaction time varied from 240 to 1200 s. It was observed that above 1523 K the formation of liquid slag occurred inside the pellets, which partially dissolved iron oxides. The apparent activation energies obtained were 255 kJ mol^–1 for coke breeze containing pellets, and 230 kJ mol^–1 for those pellets containing graphite. It was possible to avoid heat transfer control of the reaction rate up to 1523 K by employing small composite pellets.     

Kinetics and mechanism of smelting reduction of fluxed chromite Part 1 Carbon–chromite–flux composite pellets in Fe–Cr–C–Si melts

Abstract

Experimental studies on the smelting reduction of fluxed carbon–chromite composite pellets in Fe–Cr–C–Si alloys were carried out at 1520–1600°C. The reduction reaction was found to be favoured by high temperatures, a high lime addition in the pellets, a long pellet dissolution time, and a moderate melt Cr content. For a given CaO addition, however, the reduction rate initially slowed before increasing with an increasing silica addition to the pellets. A three stage reduction mechanism is proposed. The first stage is very likely to be controlled by solid state and/or gas diffusion with an apparent activation energy of 472 kJ mol^-1 for pellets fluxed with 15%CaO and 25%SiO₂ . The third stage proceeds via smelting mechanisms, with mass transfer in the slag phase possibly rate controlling.     

Reduction of Nickel Oxide Powder and Pellet by Hydrogen

Reduction of nickel oxide (NiO) powder and pellet by hydrogen was studied in a thermogravimetric apparatus. The variables studied were temperature (573, 673, 773, 873, 973?K) and hydrogen flow rate (100, 150, 200?cc?min^?1). With NiO powder 70?C80?% reduction and with NiO pellets about 95?% reduction were achieved. With both NiO powder and pellets, the rate of reduction increased with increasing temperature and hydrogen flow rate and the linear nature of the fractional reduction versus time (F vs. t) plot, for the most part of the reduction at all temperatures, supported a rate control by gas film diffusion. The activation energies for the reduction of NiO powder and NiO pellet were found to be 20.14 and 19.21?kJ?mol^?1, respectively. The SEM images showed that the grain size of nickel (Ni) produced was 1?C2???, and the XRD analysis established the presence of Ni (and the absence of NiO) in the reduced sample.     

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.     

Reduction of iron oxides from liquid slags using a graphite rotating disc

Research work has been carried out on the reduction of FeO from liquid slags of the CaO‐FeO‐SiO₂ ternary system using a graphite rotating disc technique. The investigations were conducted on slags with a basicity of CaO/SiO₂ = 1.27 and FeO contents of 20 and 60%, at temperatures of 1350 and 1420°C. The calculated viscosity range for these slags is within 2.53 – 0.43 dPa·s. It has been found that the factor controlling the reduction process is diffusion of FeO towards the disc surface, both in the case of the reduction from the slag with 20% FeO and in the case of the reduction from the slag with 60% FeO fraction. The diffusion coefficient of FeO at the reduction temperature of 1350°C is of the order of magnitudes of 10^?7 cm²/s, while at 1420°C it reaches the order of 10^?6 cm²/s. The calculated thickness values for the limiting diffusion layers range from 8.54·10^?3 to 0.70·10^?3 cm. It has been found that with increasing reduction rate also Boudouard's reaction starts to be important to the overall reduction rate. The limiting reduction rate at which Boudouard's reaction starts to be important to the entire process is dependent on temperature, being approximately 10.0·10^?6 mol FeO/cm² s at 1350°C, and approximately 15.0·10^?6 mol FeO/cm² s at 1420°C.     

Carbothermal Reduction of Quartz with Carbon from Natural Gas

Carbothermal reaction between quartz and two different carbons originating from natural gas were investigated in this paper. One of two carbons is the commercial carbon black produced from natural gas in a medium thermal production process. The other carbon is obtained from natural gas cracking at 1273 K (1000 °C) deposited directly on the quartz pellet. At the 1923 K (1650 °C) and CO atmosphere, the impact of carbon content, pellet structure, gas transfer, and heating rate are investigated in a thermo-gravimetric furnace. The reaction process can be divided into two steps: an initial SiC-producing step followed by a SiO-producing step. Higher carbon content and increased gas transfer improves the reaction rate of SiC-producing step, while the thicker carbon coating in carbon-deposited pellet hinders reaction rate. Better gas transfer of sample holder improves reaction rate but causes more SiO loss. Heating rate has almost no influence on reaction. Mass balance analysis shows that mole ratios between SiO₂, free carbon, and SiC in the SiC-producing step and SiO-producing step in CO and Ar fit the reaction SiO₂(s) + 3 C(s) = SiC(s) + 2 CO(g). SiC-particle and SiC-coating formation process in mixed pellet and carbon-deposited pellet are proposed. SiC whiskers formed in the voids of these two types of pellets.     

Dissolution behaviour of MgO based refractories in CaO–Al2O3–SiO2 slag

Abstract

Magnesium oxide (MgO) based refractories are widely used in secondary refining processes, and their dissolution into refining slag is the primary cause of their shortened lifespan. The dissolution rate was investigated for sintered MgO and commercial MgO–C and MgO–Cr₂O₃ refractories in a synthesised 50CaO–45Al₂O₃–5SiO₂ liquid (mass-%) slag. The change in slag composition was measured after a refractory sample was placed into the molten slag that was stirred by flowing argon gas at 1773?K. The dissolution rate of the sintered MgO was above those of the MgO–C and MgO–Cr₂O₃ refractories under the same gas flowrate, although the dissolution rate of all samples increased as the gas flowrate was increased from 25 to 75?mL·min^??1. The slag containing 5?mass-% FeO considerably promoted the dissolution of the MgO–C refractory because of the oxidation of carbon by FeO. The dissolution of all the refractories was greatly affected by penetration of the liquid slag, with the mass transfer of MgO in the penetrating slag at lower gas flowrates likely being the rate controlling step. At high gas flowrates, Ar bubbles covered the surface and blocked the contact between the liquid slag and the solid phase, reducing the dissolution rate.     

Effect of FeO and CaO on the Sulfide Capacity of the Ferronickel Smelting Slag

The effect of FeO and CaO on the sulfide capacity in MgO-SiO₂-FeO based slags equilibrating with Fe-Ni alloys at 1773 K and 1873 K (1500 °C and 1600 °C) was investigated. The sulfide capacity in the MgO-SiO₂-FeO and MgO-SiO₂-CaO-FeO slags increased with higher FeO content and higher temperatures due to an increase in the activity of O^2? and a decrease in the activity coefficient of sulfide ion in slag. The sulfide capacity of the MgO-SiO₂-CaO-FeO slag also increased with an increase in the CaO content due largely to the increase in the activity of O^2?. Furthermore, CaO and FeO seem to be more effective than MgO in increasing the sulfide capacity in the MgO-SiO₂-CaO-FeO slag system. In addition, the comparison of the experimental results with the theoretical estimate using the modified empirical optical basicity showed relatively good linear agreement.     

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.     

Replacement of bentonite in hematite ore pelletisation using a combination of sodium lignosulphonate and copper smelting slag

Bentonite is the most common binder used in iron ore pelletisation owing to its good bonding properties in green and dry pellets at both ambient and elevated temperatures. However, due to its high alumina and silica content, it increases the slag volume and energy consumption in downstream processes. Organic binders may be used to replace bentonite; however, they fail to provide strength at a high temperature (700–900°C) due to poor thermal stability during pellet induration. In the present study, an organic binder Na lignosulphonate (NLS) has been used along with copper smelting slag (Cu-SS). FeO in Cu-SS provides diffusion bonding at high temperature and maintains the strength of pellets even after evaporation/burning of NLS. It also enhances recrystallisation bonding at relatively lower temperature to provide good strength. The study has been carried out with hematite ore and varying amounts of NLS and Cu-SS. Copper smelting slag (1.0%) addition with 0.5%NLS has been found to be optimum to provide very good green properties and ～300?kg/pellet cold crushing strength (CCS) at 1250°C induration temperature. However, hematite pellets of similar basicity with 0.5% bentonite requires higher induration temperature (1300°C) to achieve a similar CCS. The developed pellet also shows better reducibility (80%), similar reduction degradation index (18%) and swelling index (10%) to the usual bentonite pellet. Thus, the induration temperature of hematite pellet has been lowered by 50°C using a combination of NLS and Cu-SS eliminating bentonite completely, which can provide a considerable energy and cost saving.     

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.     

The reaction behavior of Fe-C-S droplets in CaO-SiO2-MgO-FeO slags

The rate of reduction of FeO in the slag by carbon in iron droplets (2.9 wt pct C, 0.01 wt pct S) was studied for CaO-SiO₂-MgO slags containing between 3 and 35 wt pct FeO and temperatures ranging from 1643 to 1763 K. The effects of Fe₂O₃ additions to the slag and sulfur variations in the metal on the reaction rate were also studied. It was found that the behavior of the metal droplets in the slag, as observed by X-ray fluoroscopy, changed significantly with FeO content in the slag. Below 10 wt pct FeO, the droplet remained intact while reacting with the slag; however, above this FeO concentration, the droplet became emulsified within the slag. The large increase in surface area of the metal droplet due to emulsification caused the rate of reaction to be one to two orders of magnitude faster than for droplets that did not become emulsified. It was suggested that when the droplet is emulsified, the surface area and reaction kinetics are greatly increased, and the rate becomes controlled by mass transfer of FeO as Fe²⁺ and O²⁻ ions in the slag to the emulsified droplet. At low FeO contents for which the droplet does not emulsify, the rate is controlled by dissociation of CO₂ on the metal. It was also found that a critical temperature exists for a given FeO content at which point the rate of CO evolution increases dramatically. Additions of Fe₂O₃ to the slag and sulfur to the metal caused significant changes to the rate of reaction possibly by affecting the emulsification behavior of the droplet.     

Effect of Direct Reduced Iron on Oxygen Distribution between Slag and Bath in Electric Arc Furnaces

Test charges containing 40 to 95% direct reduced iron (DRI) were melted in two identical electric arc furnaces. Slag and the corresponding metal samples were collected from the furnace in the course of the steelmaking process and from the ladle after deoxidation and composition adjustment. The temperature was measured just before sampling. The activity coefficient and activity of total ferrous oxide in the slag were determined by using the theory of regular ionic solutions. The activity was used to assess the oxygen concentration in the metal. The effect of slag composition on Fe_tO activity coefficient and activity was investigated. The enthalpy of solution of total ferrous oxide in the slag was found to be 78 kJmol^?1. The ratio of activity to concentration of Fe_tO is equal to 0.0138. The effects of DRI proportion and degree of metallization on α^Fe,O were investigated. The activity coefficients of oxygen and carbon in the bath are 0.7243 and 1.0825, respectively. The activity coefficient and activity of oxygen in the metal decrease with increasing carbon concentration, carbon activity coefficient and activity. An “oxide capacity” has been developed which does not need the use of α^Fe,O. It correlates strongly with temperature over the range from 1500 to 1670°C. The basicity has only a small influence compared with the large temperature effect. The oxide capacity increases with growing DRI proportion and decreases with increasing metallization between 93.43 and 95.25%. Oxygen distribution between slag and metal was assessed by using the oxide capacity. Calculated values compare well with the corresponding data obtained from slag and metal analyses. The oxide capacity can be used in monitoring the steelmaking operation.     

Smelting reduction reactions by solid carbon using induction furnace: foaming behaviour and kinetics of FeO reduction in CaO–SiO2–FeO slag

Abstract

Smelting reduction process technology is progressing rapidly, and research to understand the reduction of FeO in molten slag and the associated foaming behaviour has gained importance. The present paper reports experimental data on the reduction of FeO in molten slag generated in a 30 kW capacity induction furnace. The influence of FeO content in the slag and temperature on the foaming and kinetics is discussed. The foaming index, a parameter describing the travel time of gas in the reactor, is shown to decrease with an increase in the superficial gas velocity. The quantitative dependence of the foaming index on slag properties viscosity, surface tension and density has been studied. The data have also been analysed to give an estimation of the activation energy for the reduction reaction. The reduction reaction, initiated by direct slag–graphite contact, produces CO gas, which spreads into the molten slag bath causing foaming of the slag; further reduction of FeO proceeds mostly via indirect reduction. The rate of reduction is found to depend directly on the initial FeO content. An increase in temperature increases the rate of reduction, which has an activation energy of 118 kJ mol^?1 of FeO. The results indicate that transport of FeO in the liquid phase is the rate controlling step. The major findings are in agreement with those reported by earlier investigators.     

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).     

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.     

Effect of the bubble size and chemical reactions on slag foaming

Slag foams have been investigated with smaller bubbles than those used in the previous studies.^[5,6,7] The bubbles were generated by argon gas injection with the nozzle of multiple small orifices and by the slag/metal interfacial reaction of FeO in the slag with carbon in the liquid iron. The foam stability in terms of the foam index for a bath-smelting type of slag (CaO-SiO₂-Al₂O₃-FeO) was determined for different bubble sizes. The average diameter of bubbles in the foam was measured by an X-ray video technique. When the foam was generated by the slag/metal interfacial reaction at 1450 °C, it was found that the average bubble diameter varied from less than 1 to more than 5 mm as a function of the sulfur activity in the carbon-saturated liquid iron. The foam index was found to be inversely proportional to the average bubble diameter. A general correlation is obtained by dimensional analysis in order to predict the foam index from the physical properties of the liquid slag and the average size of the gas bubbles in the foam. Formerly Graduate Student and Research Associate, Department of Materials Science and Engineering, Carnegie Mellon University.