In the pre-reduction cyclone of the HIsarna process, both thermal decomposition and gas reduction of the injected iron ores occur simultaneously at gas temperatures of 1723–1773 K. In this study, the kinetics of the thermal decomposition of three iron ores (namely OreA, OreB and OreC) for HIsarna ironmaking were analysed as an isolated process with a symmetrical thermogravimetric analyser (TGA) under an inert atmosphere. Using various methods, the chemical and mineralogical composition, particle size distribution, morphology and phase distribution of the ores were analysed. The ores differ in their mineralogy and morphology, where OreA only contains hematite as iron-bearing phase and OreB and OreC include goethite and hematite. To obtain the kinetic parameters in non-isothermal conditions, the Coats–Redfern Integral Method was applied for heating rates of 1, 2 and 5 K/min and a maximum temperature of 1773 K. The TGA results indicate that goethite and hematite decomposition occur as a two-stage process in an inert atmosphere of Ar. The proposed reaction mechanism for the first stage of goethite decomposition is chemical reaction with an activation energy ranging from 46.55 to 60.38 kJ/mol for OreB and from 69.90 to 134.47 kJ/mol for OreC. The proposed reaction mechanism for the second stage of goethite decomposition is diffusion, showing an activation energy ranging between 24.43 and 44.76 kJ/mol for OreB and between 3.32 and 23.29 kJ/mol for OreC. In terms of hematite decomposition, only the first stage was analysed. The proposed reaction mechanism is chemical reaction control. OreA shows an activation energy of 545.47 to 670.50 kJ/mol, OreB one of 587.68 to 831.54 kJ/mol and OreC one of 424.31 to 592.32 kJ/mol.@en

A three-dimensional computational fluid dynamics (CFD) model for the HIsarna off-gas system is set up and validated by real plant data. In the model detailed reaction mechanism and kinetic data for post-combustion of CO-H2 mixture and carbon particles are incorporated. The results are presented and discussed in another study (Part 1) by the same authors. In the present paper, the focus will be on geometry modification of the off-gas system and the effects on the operating parameters. The effect of this modification on heat loss, temperature profile, carbon conversion and gaseous phase composition across the off-gas system is investigated. It is shown that the modified geometry leads to a higher heat loss through the reflux chamber walls which can change the temperature profile and consequently species composition. The modified geometry also offers possibility of higher CO-H2 mixture and carbon particles conversion rate and reduce unwanted emission from the reflux chamber.

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The HIsarna process is a new and breakthrough smelting reduction process for hot metal (liquid iron) production from iron ores and coal directly fed into the reactor. The flue gas from the main reactor enters the off-gas system containing small amounts of H₂, CO and carbon particles which need to be removed before further treatment by post combustion oxygen injection. A three-dimensional Computational Fluid Dynamics (CFD) simulation of the HIsarna off-gas system is performed and validated using a detailed reaction mechanism and kinetic data for post-combustion of a CO–H₂ mixture and carbon particles. Using the validated model, a series of simulations were performed to investigate the effect of water quenching and post combustion oxygen injection. It was found that water quenching can significantly reduce the off-gas temperature. It is also possible to reduce oxygen injection during operations where inlet CO content of the off-gas system is low.

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Galvanized steel scrap flow and injection into the HIsarna reactor are investigated using discrete element method (DEM). The scrap particle is fed into the reactor through an inclined chute and hits the slag surface where the zinc content is evaporated and solid particles melt. A DEM model is setup and validated using experimental data obtained from the exact plant-scale chute geometry and scrap particles. Using the DEM model, the effect of chute inclination, injection elevation, injection mode (batch and continuous), batch size, and flowrate on particle distribution and exerted pressure on the slag surface are investigated. It is found that continuous mode of injection is the most suitable method to increase the spread of particles and also to reduce the exerted pressure on the slag surface. Placing dent-like obstacles at the tip of the chute significantly increases the impact area, especially for batchwise injection, thus reducing force and pressure on the slag surface that minimizes the risk of liquid splash. Larger particle impact area is also beneficial to obtain higher zinc evaporation rate from particle surface and also to minimize the slag surface temperature disturbance.

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In order to understand the pre-reduction behaviour of fine hematite particles in the HIsarna process, change of morphology, phase and crystallography during the reduction were investigated in the high temperature drop tube furnace. Polycrystalline magnetite shell formed within 200 ms during the reduction. The grain size of the magnetite is in the order of magnitude of 10 µm. Lath magnetite was observed in the partly reduced samples. The grain boundary of magnetite was reduced to molten FeO firstly, and then the particle turned to be a droplet. The Johnson-Mehl-Avrami-Kolmogorov model is proposed to describe the kinetics of the reduction process. Both bulk and surface nucleation occurred during the reduction, which leads to the effect of size on the reduction rate in the nucleation and growth process. As a result, the reduction rate constant of hematite particles increases with the increasing particle size until 85 µm. It then decreases with a reciprocal relationship of the particle size above 85 µm.

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Suspension reduction kinetics of hematite ore particles at 1710 K to 1785 K was described by the Johnson-Mehl-Avrami-Kolmogorov model with Avrami exponent of 1.405. The apparent activation energy is 105.5 kJ mol⁻¹ with the rate determining step of nucleation and growth. The reduction degree of the hematite at the endpoint is a linear function of temperature and the logarithmic oxygen potential of the reacting gas. A peak function of reaction rate constant with particle size has been verified in this work, and the maximum value of the reaction rate is located at around 85 µm particle size. The influence of heat transfer on the reaction process has been evaluated. The results suggest that the heating-up process for large particles, 244 µm particles, for instance, cannot be ignored. It can retard the reaction rate compared to small particles. Normally, the reaction rate constant decreases linearly with the increase of ln[p(O₂)] of the reacting gas mixture. However, 95 vol pct CO₂ in the reacting gas can accelerate the reaction rate of thermal decomposition of hematite due to the emissivity of CO₂ gas. It results in a higher reaction rate of 110 µm particles in 95 vol pct CO₂-containing gas than that in other less CO₂-containing gases.

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In order to understand the thermal decomposition kinetics of hematite particles in inert atmosphere, thermogravimetriy was employed for isoconversional analysis. The kinetic triplet was estimated from the experimental data and the isothermal reaction kinetics was predicted. The results indicated that the thermal decomposition could be divided into two stages, of which the activation energies were 636 kJ/mol and 325 kJ/mol, respectively. The exponential form of pre-exponential factor, ln(A/s⁻¹), for the two stages were estimated to be 42.9±6.6 and 14.1±3.08. At last, the kinetic mechanism of the first stage was suggested to match Sestak-Berggren model as f(α)=(1−α)^1.38. The relatively slow reaction rate of the second stage was due to the slag formation during the reaction.

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High-temperature reduction processes of iron oxide particles suspension are promising in carbon emission abatement. Recently, researchers have contributed abundant knowledge of the reaction mechanism and kinetics of iron oxide particles above 1473 K, while there was very limited information 10 years ago. Although the understanding of the high-temperature reduction of iron oxide particles is still not comprehensive, a brief review of the academic reports is helpful for the future work on this topic. The high-temperature reduction of iron oxide suspension is characterized by having: rapid reaction, obvious thermal decomposition and melting process. Evaluation of the kinetic data shows that the reduction process of single particles is not rate-determined by the diffusion process at the studied temperatures. The reaction rate constant is within 10⁻²–10 s⁻¹ in these studies. Furthermore, comparing previous studies in iron oxide reduction field, the phase transformation and effect of gangue minerals to the reduction of iron oxide particles above 1473 K requires more input and research.

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HIsarna is a promising ironmaking technology to reduce CO ₂ emission. Information of phase transformation is essential for reaction analysis of the cyclone reactor of the HIsarna process. In addition, data of density and volume of the ore particles are necessary for estimation of the residence time of the particles in the cyclone reactor. Phase transformation of iron ore particles was experimentally studied in a drop-tube furnace under simulated cyclone conditions and compared with thermodynamic calculation. During the pre-reduction process inside the reactor, the mineralogy of iron ore particles transforms sequentially from hematite to sub-oxides. The density changes of the particles during the melting and reduction can be predicted based on the phase composition and temperature. Therefore, density models in the studies were evaluated with reported experimental data of slag. As a result, a more reliable density model was developed to calculate the density of the formed slag containing mainly FeO–Fe ₂ O ₃ . The density and volume of the partially reduced ore particles or melt droplets were estimated based on this model. The results show that the density of the ore particles decreases by 15.1% at most along the progressive reduction process. Furthermore, the model results also indicate that heating, melting and reduction of the ore could lead to 6.63–9.37% swelling of the particles, which is mostly contributed by thermal expansion. It would result in corresponding variation in velocity of the ore particles or melt droplets during the flight inside the reactor.

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Melting and reduction of fine iron ore particles in the gas environment of a HIsarna smelting cyclone is a critically important topic, but very limited information is currently available except for some experimental data from high temperature drop tube furnace (HTDF). This work discusses the equilibrium state of reacting iron ore in the HTDF environment by thermodynamic calculations to strengthen the understanding of the HIsarna process. The limit of reduction termination of the ore particles was estimated in the calculation for the thermal decomposition and topochemical gas reduction. The theoretical calculation results are compared with the experimental data from the previous studies. Furthermore, variation of slag composition and iron valence states were estimated theoretically to understand the effects of post combustion ratio value and hydrogen/carbon ratio on the equilibrium state of the ore particles in the reducing gas.

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