Metal production, and especially iron ore-based steel production, is characterized by high fossil CO2 emissions due of the use of coal and coke in the blast furnace. Steel companies around the world ...are striving to reduce the CO2 emissions in different ways, e.g., by use of hydrogen in the blast furnace or by production of iron via direct reduction. To partially replace fossil coal and coke with climate neutral bio-coal products that are adapted for use in the metal industry, e.g., at the blast furnace, is a real and important opportunity to significantly lower the climate impact in a short-term perspective. Top-charging of bio-coal directly to the blast furnace is difficult due to its low strength but can be facilitated if bio-coal is added as an ingredient in coke or to the mix when producing residue briquettes. Bio-coal can also be injected into the lower part of the blast furnace and thereby replace a substantial part of the injected pulverized coal. Based on research work within Swerim, where the authors have been involved, this paper will describe the opportunities and limitations of using bio-coal as a replacement for fossil coal as part of coke, as a constituent in residue briquettes, or as replacement of part of the injected pulverized coal. Results from several projects studying these opportunities via technical scale, as well as pilot and industrial scale experiments and modelling will be presented.
The blast furnace still dominates the production and supply of metallic units for steelmaking. Coke and coal used in the blast furnace contribute substantially to CO2 emissions from the steel sector. ...Therefore, blast furnace operators are making great efforts to lower the fossil CO2 emissions and transition to fossil-free steelmaking. In previous studies the use of pre-treated biomass has been indicated to have great potential to significantly lower fossil CO2 emissions. Even negative CO2 emission can be achieved if biomass is used together with carbon capture and storage. Blast furnace conditions will change at substantial inputs of biomass but can be defined through model calculations when using a model calibrated with actual operational data to define the key blast furnace performance parameters. To understand the effect, the modelling results for different biomass cases are evaluated in detail and the overall performance is visualised in Rist- and carbon direct reduction rate (CDRR) diagrams. In this study injection of torrefied biomass or charcoal, top charging of charcoal as well as the use of a combination of both methods are evaluated in model calculations. It was found that significant impact on the blast furnace conditions by the injection of 142 kg/tHM of torrefied biomass could be counteracted by also top-charging 30 kg/tHM of charcoal. With combined use of the latter methods, CO2-emissions can be potentially reduced by up to 34% with moderate change in blast furnace conditions and limited investments.
Super-hot acid leach residue is generated during zinc production in the roasting–leaching–electrowinning route, where both primary and secondary resources are used as feed material. This residue may ...contain valuable metals, such as lead, zinc, and iron, as well as precious metals, such as gold and silver. Four materials, namely super-hot acid leach residue, a residue formed when super-hot acid leach residue is selectively leached for lead with triethylenetetramine, as well as flotation concentrate, and flotation tailings formed in a selective silver flotation process with super-hot acid leach residue as the feed material were characterized to obtain a deeper understanding of possible further metal extraction. These four materials were characterized for chemical composition, mineralogy, and mineral distribution via chemical analyses, X-ray diffraction, and energy-dispersive scanning electron microscopy, respectively. The scanning electron microscope images showed that the materials have large variations in particle size distribution and composition. The results showed that the main lead phase in super-hot acid leach residue is lead sulfate, whereas it is mostly converted to lead sulfide during the selective lead leaching of the super-hot acid leach residue. The remaining lead sulfate is found in a solid solution with barium sulfate. Extracting lead from super-hot acid leach residue via triethylenetetramine leaching resulted in increased concentrations of gold and silver by 41% and 42%, respectively. The identified silver phases in super-hot acid leach residue may correspond to silver sulfide, silver chloride, and elementary silver, where silver sulfide was the most commonly occurring silver phase. After leaching this selectively for lead with triethylenetetramine, similar silver phases were identified, but silver sulfide and silver chloride occurred to a similar extent. Additionally, silver copper sulfide was detected. The presence of different silver phases might pose a challenge to reaching high silver recovery during leaching as the optimum leaching conditions differ somewhat. Furthermore, elemental sulfur, with a tendency to coat gold and silver particle surfaces, which is indicated to be present in all materials except the silver flotation tailings, may hinder metal extraction.
Ore-based steelmaking generates various residues including dusts, sludges, scales and slags. Recycling of these residues within the process or via other applications is essential for sustainable ...production of steel. In blast furnace (BF) ironmaking, the gas-cleaning equipment generally recovers the particles in the off-gas as dust and sludge. Traditionally, the dry dust is recycled via the sinter or, in the case of pellet-based BF operation, via cold-bonded briquettes and injection. As the BF sludge mainly consists of iron and carbon, this residue is of interest to recycle together with the BF dust. However, depending on how the BF is operated, these two residues are more or less the major outlet of zinc from the furnace. Thus, to limit the recycled load of zinc, both materials cannot be recycled without dezincing the sludge prior to recycling. Dezincing and recycling of the low-zinc fraction of BF sludge via sinter have been reported whereas recycling via cold-bonded briquettes has not been performed. In the present study, cold-bonded briquettes containing the low-zinc fraction of dezinced BF sludge were charged as basket samples to the LKAB Experimental Blast Furnace (EBF). The excavated basket samples from the quenched EBF suggested that additions of up to 20 wt.% of upgraded BF sludge was feasible in terms of reducibility and strength. Based on these results, BF sludge were added to cold-bonded briquettes and charged in industrial-scale trials. The trials indicated that the annual generation of BF sludge, after dezincing, could be recycled to the BF.
COURSE50 (CO2 ultimate reduction in steelmaking process by innovative technology for Cool Earth 50) carried out COG and reformed COG (RCOG) injection operation trials at LKAB’s experimental blast ...furnace in Luleå in cooperation with LKAB and Swerea MEFOS. Operation trials were successfully carried out. Input of C in both COG and RCOG injection periods decreased comparing the base period, because of increase in H2 reduction instead of C direct reduction that is a huge endothermic reaction. However poor penetration depth of injected gas from shaft tuyere made furnace efficiency worse. Hot top gas injection increased temperature of top gas and upper part of the furnace. Efficiency of hot top gas injection was not clear as sinter degradation did not occur in the base period.
The presence of halogens has an adverse effect on the zinc extraction process through electrowinning, the last phase of the RLE (Roasting, Leaching and Electrowinning) zinc extraction route. Fluoride ...(F−) may be present as calcium fluoride (CaF2) and this is, for example, the case in double leached Waelz oxide (DLWO). Efficient removal of F− from primary and secondary raw materials for zinc extraction results in a simplified process and increases flexibility in the selection of raw materials. Understanding of the solubility behavior of pure CaF2 can give valuable information on treatment for maximized halogen removal. Dissolution of CaF2 was studied with the addition of sodium carbonate (Na2CO3) and sodium bicarbonate (NaHCO3). Dissolution studies were combined with thermodynamic calculations to understand the solubility behavior of CaF2 under different conditions. Results from the experiments and the thermodynamic calculations show that Na2CO3 and NaHCO3 have similar behavior if the pH is controlled at the same value. The available carbonate (CO32−) ion in the system limits the concentration of calcium (Ca2+) ion by precipitation of CaCO3, which enhances the dissolution of CaF2. At higher temperatures and pH, calcite, vaterite, and aragonite were formed and co-precipitation of CaF2 along with calcium carbonate (CaCO3) was observed. At lower temperatures and lower pH levels, only calcite and vaterite were formed and a coating by CaCO3 on CaF2 was found to hinder complete dissolution reaction. The results of this study indicate that the temperature along with the reagents used for the dissolution tests have a significant impact on the CaCO3 polymorph mixture (calcite, vaterite and aragonite) formation.
Metallurgical coke with high strength and low reactivity is used in the ironmaking blast furnace. Replacement of some coking coal with bio-coal was shown to result in lower strength and higher ...reactivity of produced coke due to introduction of reactive bio-coal carbon and ash components catalyzing the Boudouard reaction, but also due to lowering of the coking coal blend fluidity, which influences coke strength and reactivity negatively. The current study aims to investigate the possibility to counteract negative impact from bio-coal addition on fluidity and coke reactivity by using high-fluidity coking coal and by agglomeration of bio-coal before addition. Original bio-coal and micro-agglomerate of bio-coal was added at 10%, 15% and 20% to the coking coal blend. The influence of bio-coals on the coke reactivity was measured by using CO2 in a thermogravimetric analyzer. Selected cokes and bio-cokes were produced in technical scale, and their reactivity and strength were measured in standard tests. The effect on dilatation of adding bio-coal or crushed agglomerates of bio-coal to the coking coal blends was measured in an optical dilatometer. The results show that by using a coking coal blend containing high-fluidity coal with agglomerated bio-coal, the max. contraction is increased, whereas the opposite occurs by using original bio-coal. The results show overlapping between contraction occurring before dilatation and during dilation, which affects max. dilatation. The bio-coke containing high-fluidity coal with agglomerated bio-coal has lower reactivity in comparison to bio-cokes with original bio-coal or bio-coke with agglomerated bio-coal produced from a coking coal blend without high-fluidity coal. The reactivity of coke produced in technical scale, as measured in CRI/CSR tests, shows a similar trend regarding reactivity, as measured by thermogravimetric analysis, on coke produced in laboratory scale.
Knowing the distribution of the materials in the blast furnace (BF) is believed to be of great interest for BF operation and process optimization. In this paper calibration samples (ferrous pellets ...and coke) and samples from LKAB’s experimental blast furnace (probe samples, excavation samples and core-drilling samples) were measured by the muon scattering tomography detector to explore the capability of using the muon scattering tomography to image the components in the blast furnace. The experimental results show that it is possible to use this technique to discriminate the ferrous pellets from the coke and it is also shown that the measured linear scattering densities (LSD) linearly correlate with the bulk densities of the measured materials. By applying the Stovall’s model a correlation among the LSD values, the bulk densities and the components of the materials in the probe samples and excavation samples was established. The theoretical analysis indicates that it is potential to use the present muon scattering tomography technique to image the components in various zones of the blast furnace.
Carbothermic reduction of chromite is an important industrial process for extracting chromium from the chromite. To have a better understanding of the effect of iron on the carbothermic reduction of ...chromite, the reduction of synthetic chromite (FeCr2O4) by graphite with/without the addition of iron powder was investigated in this paper by Thermogravimetric Analysis (TGA) in argon atmosphere. The fractional reduced samples were examined by SEM/EDS and XRD analysis, and the reduction process was thermodynamically and kinetically evaluated. The experimental results show that the iron powder addition enhances the reduction of FeCr2O4 and this effect increases when increased amounts of iron powder are added. This phenomenon is attributed to the in situ dissolution of chromium into the iron and mixed carbide (Cr,Fe)7C3, which can decrease the activity of the nascent chromium formed by the reduction of the FeCr2O4. The experimental results indicate that the reduction of FeCr2O4 with up to 80 wt.% iron powder addition is likely to be a single-step process and the kinetic analysis suggests that the reduction reaction is likely to be either (a) chemical reaction at the surface of FeCr2O4 or (b) diffusional dissolution of the product (FeCr2) into the iron/alloy particles or the mixed control of (a) and (b).
Highlights • Surveillance systems not harmonised across EU/EEA countries. • Analysis indicates a common trend of increased case numbers on Western EU/EEA countries. • Knowledge of testing algorithms ...and clinical diagnosis is variable. • Autochthonous cases harbour genotype 3 viruses which are also found in pigs. • Sharing of human and animal data needed to understand transmission/epidemiology.
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