Coke corresponds to 2/3–3/4 of the reducing agents in BF, and by the partial replacement of coking coals with 5–10% of bio-coal, the fossil CO2 emissions from the BF can be lowered by ~4–8%. Coking coal blends with 5% and 10% additions of bio-coals (pre-treated biomass) of different origins and pre-treatment degrees were carbonized at laboratory scale and with a 5% bio-coal addition at technical scale, aiming to understand the impact on the bio-coal properties (ash amount and composition, volatile matter content) and the addition of bio-coke reactivity. A thermogravimetric analyzer (TGA) connected to a quadrupole mass spectroscope monitored the residual mass and off-gases during carbonization. To explore the effect of bio-coal addition on plasticity, optical dilatometer tests were conducted for coking coal blends with 5% and 10% bio-coal addition. The plasticity was lowered with increasing bio-coal addition, but pyrolyzed biomass had a less negative effect on the plasticity compared to torrefied biomasses with a high content of oxygen. The temperature for starting the gasification of coke was in general lowered to a greater extent for bio-cokes produced from coking coal blends containing bio-coals with higher contents of catalyzing oxides. There was no significant difference in the properties of laboratory and technical scale produced coke, in terms of reactivity as measured by TGA. Bio-coke produced with 5% of high temperature torrefied pelletized biomass showed a similar coke strength as reference coke after reaction.
Fe 2 O 3 /C compacts prepared by mixing of nanosized Fe 2 O 3 (40-150 nm) with charcoal in a molar ratio of 1 : 4 were isothermally reduced at 950-1100uC in argon gas flow. The rate of reduction was calculated from the direct measurements of the mass-loss using TG technique. In addition, the QMS gas analyser was used to monitor CO and CO 2 concentrations in the off gases. The different phases developed in the composites were identified by X-ray diffraction and their structures were microscopically examined. The effect of temperature and particle size of Fe 2 O 3 on the reduction rates was studied. The reduction of Fe 2 O 3 was found to proceed in a stepwise manner up to metallic iron. Alternatively, the carbon solution loss reaction resulted from the gasification of charcoal plays a significant role in the carbothermic reduction process. Incubation periods were detected in QMS analysis at the beginning of reduction process. The charcoal volatiles interfered with the O 2 weight loss measurements, upon applying TG technique, resulting higher values of total weight loss than that measured by QMS. Comparison of the reduction testing techniques shows the differences in the actual reduction extents. The reduction kinetics were correlated with the microstructure of the reduced products and directed to the elucidation of the reduction mechanism.
Lowering the carbon consumption and fossil CO 2 emissions is a priority in blast furnace (BF) ironmaking. Renewable biomass is one option that can play an important role in future low-carbon ironmaking particularly in the countries rich in biomass resources. In this study, full-scale trials to investigate the impact of briquettes containing torrefied sawdust on the BF efficiency and process stability have been conducted. Briquettes containing 1.8% of torrefied pelletized sawdust (TPS), 86.2% of steel mill residues, and 12% cement with sufficient mechanical strength have been produced on industrial scale. The bio-briquettes were charged at two different rates: 37% (~ 39 kg/tHM) and 55% (~ 64 kg/tHM) bio-briquettes to the SSAB BF No. 4 in Oxelösund. The gas utilization was higher during bio-briquette-charging periods without change in pressure drop up to 55% bio-briquettes, indicating sustained shaft permeability. BF dust generation or properties did not change significantly. Measurements of the top gas composition using mass spectrometry did not indicate release of hydrocarbon from TPS in connection to the charging of bio-briquettes. Evaluation of process data has been carried out using a heat and mass balance model. The evaluation of operational data in the model indicated lowering of thermal reserve zone temperature by 45 °C and reduction in carbon consumption by ~ 10 kg/tHM when charging 55% bio-briquettes compared to the reference case. The total CO 2 emission was reduced by about 33-40 kg/tHM when using 55% bio-briquettes. Keywords Ironmaking • Blast furnace • Bio-briquettes • CO 2 emission • Torrefied sawdust Abbreviations B2 CaO SiO 2 BF Blast furnace EBF Experimental blast furnace Fe met Metallic iron Fe tot Total iron EtaCO Carbon monoxide efficiency, EtaCO = %CO 2 %CO+%CO 2 EtaH 2 Hydrogen efficiency, EtaH 2 = %H 2 O %H 2 +%H 2 O HM Hot metal The contributing editor for this article was I. Sohn.
The interest of the steel industry in utilizing bio-coal (pre-treated biomass) as CO2-neutral carbon in iron-making is increasing due to the need to reduce fossil CO2 emission. In order to select a suitable bio-coal to be contained in agglomerates with iron oxide, the current study aims at investigating the thermal devolatilization of different bio-coals. A thermogravimetric analyzer (TGA) equipped with a quadrupole mass spectrometer (QMS) was used to monitor the weight loss and off-gases during non-isothermal tests with bio-coals having different contents of volatile matter. The samples were heated in an inert atmosphere to 1200 °C at three different heating rates: 5, 10, and 15 °C/min. H2, CO, and hydrocarbons that may contribute to the reduction of iron oxide if contained in the self-reducing composite were detected by QMS. To explore the devolatilization behavior for different materials, the thermogravimetric data were evaluated by using the Kissinger– Akahira–Sonuse (KAS) iso-conversional model. The activation energy was determined as a function of the conversion degree. Bio-coals with both low and high volatile content could produce reducing gases that can contribute to the reduction of iron oxide in bio-agglomerates and hot metal quality in the sustained blast furnace process. However, bio-coals containing significant amounts of CaO and K2O enhanced the devolatilization and released the volatiles at lower temperature.
The utilization of CO2 neutral carbon instead of fossil carbon is one way to mitigate CO2 emissions in the steel industry. Using reactive reducing agent, e.g., bio-coal (pre-treated biomass) in iron ore composites for the blast furnace can also enhance the self-reduction. The current study aims at investigating the self-reduction behavior of bio-coal containing iron ore composites under inert conditions and simulated blast furnace thermal profile. Composites with and without 10% bio-coal and sufficient amount of coke breeze to keep the C/O molar ratio equal to one were mixed and Portland cement was used as a binder. The self-reduction of composites was investigated by thermogravimetric analyses under inert atmosphere. To explore the reduction progress in each type of composite vertical tube furnace tests were conducted in nitrogen atmosphere up to temperatures selected based on thermogravimetric results. Bio-coal properties as fixed carbon, volatile matter content and ash composition influence the reduction of iron oxide. The reduction of the bio-coal containing composites begins at about 500 °C, a lower temperature compared to that for the composite with coke as only carbon source. The hematite was successfully reduced to metallic iron at 850 °C by using bio-coal, whereas with coke as a reducing agent temperature up to 1100 °C was required.
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