Hydrogen Based Direct Reduction of Metals Oxides

A special issue of Metals (ISSN 2075-4701).

Deadline for manuscript submissions: closed (30 September 2023) | Viewed by 6306

Special Issue Editor

Special Issue Information

Dear Colleagues,

The direct reduction iron is considered the primary actor in the transition to sustainable steelmaking. Reducing iron ores with H2 yields water vapor instead of CO2 with a carbon-based reductant. H2 is currently produced from fossil fuels (natural gas, coal, oil) by biomass gasification and from non-carbon sources, such as water electrolysis. An important factor in the production of DRI in industrial practice is the dynamic control of the process in the reactors. This dynamic control, along with optimization of the process, is essential for ensuring both a smooth operation process and the quality of the products, for example the metallization degree and cementite fraction in the reduced pellets. Despite the renewed efforts in the technological research and development of hydrogen and fuel cells, the hydrogen economy is not yet developed, and several technological and non-technical barriers remain. In the industrial sector, the direct reduction of hydrogen is considered a technically viable option in Europe from 2030 onwards. This is considered one of the most innovative technologies with the highest future potential in the iron and steel sector in the long-term. DRI processes can reduce CO2 emissions using natural gas instead of coal due to the replacement of the carbon reductant by hydrogen from methane. Midrex and HYL Energiron are the processes with the highest capacities that are currently used worldwide. H2 can also be used as the reductant in conventional direct reduction reactors. One issue, though, is preventing the sticking of the DRI. If H2 is produced by water electrolysis using hydro or nuclear electricity, then CO2 emissions could be lowered to less than 300 kg/t HRC. In view of current developments with regard to GHG-neutral hydrogen-based reduction processes producing H2-reduced DRI and the subsequent melting in the EAF, there is still a need to introduce carbon into the system either to carburize the steel or to create foaming slag to improve the energy efficiency of the melting process. Therefore, in the future, if a substantial part of steel production shifts to a direct reduction and EAF-based route to reach the international goals of GHG emission reduction, there will still be a need to use alternative carbon sources to produce green and carbon neutral and/or fully circular steel. In a route based on hydrogen and direct reduction, the output after the reduction process is the porous material of DRI, or sponge iron, which can potentially be transported to an EAF in a different location (or pressed to hot briquetted iron, HBI, which is favorable for transportation). As the hydrogen content in the mixture increases, the total energy consumption in the reactor decreases. A strong decrease in electricity consumption is recorded as the hydrogen content increases, and the availability of DR-grade pellets is limited with respect to the total international steel production. Therefore, the main obstacles to the direct conversion of steel production are mainly represented by the availability of such grade raw materials. In fact, the successful and productive operation of a DR-EAF line requires the use of high-grade pellets (gangue less than 5%, possibly basic). Taking into account all the described aspects, a good solution appears to be the integration of a direct reduction with large smelting furnaces. In this way, BF-grade pellets could be reduced in the DR reactor by overcoming the problem of the availability of high-quality DR-grade pellets.

For all the described aspects, this Special Issue aims to present the latest research findings in the field of hydrogen-based direct reduction. This Special Issue is open to all the researchers involved in this field and invites them to contribute their most recent results.

Prof. Dr. Pasquale Cavaliere
Guest Editor

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Keywords

  • global warming
  • energy
  • CO2 emissions
  • energy transition
  • hydrogen
  • renewables
  • decarbonization
  • steel industry
  • hydrogen storage
  • best available technologies
  • hydrogen “color”
  • coal
  • biomass
  • nuclear
  • iron ores reduction
  • reducing gases
  • hydrogen reduction
  • kinetics of hydrogen reduction
  • thermodynamic of hydrogen reduction
  • energy efficiency
  • hydrogen metallurgy
  • direct reduced iron
  • sponge iron
  • hydrogen direct reduced iron
  • electric arc furnace
  • hot briquetted iron

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Published Papers (2 papers)

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Research

13 pages, 4687 KiB  
Article
Reduction Kinetics of Compact Hematite with Hydrogen from 600 to 1050 °C
by Junguo He, Kejiang Li, Jianliang Zhang and Alberto N. Conejo
Metals 2023, 13(3), 464; https://doi.org/10.3390/met13030464 - 23 Feb 2023
Cited by 9 | Viewed by 3012
Abstract
Reduction of iron ores with hydrogen is a solution to replace fossil fuels. For this reason, it is important to discuss previous discrepancies. Some previous studies suggest a rate minimum with respect to temperature. Our research work indicates that a rate minimum can [...] Read more.
Reduction of iron ores with hydrogen is a solution to replace fossil fuels. For this reason, it is important to discuss previous discrepancies. Some previous studies suggest a rate minimum with respect to temperature. Our research work indicates that a rate minimum can be avoided. Thermogravimetric isothermal reduction experiments were carried out from 600 to 1050 °C with pure reagent ferric oxide and hydrogen using a tubular furnace. The morphology and chemical composition of the initial sample, consisting of particulate hematite (Fe2O3), and the final product, consisting of metallic iron (Fe°), was defined using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The reduction rate for the conversion from hematite to magnetite (Fe2O3 to Fe3O4) was the highest, around 5 %/min, decreasing to around 2–5%/min for the second stage of conversion from magnetite to wüstite (Fe3O4 to FeO). This reduction rate remains almost constant from about 20–80% reduction, decreasing to 0.3–1%/min for the completion of reduction from wüstite to metallic iron (FeO to Fe°). The reduction controlling mechanism was evaluated based on the calculated apparent activation energy and fitting the experimental data to one gas-solid reaction equation. Under the experimental conditions in this work, the reduction rate of pure hematite with hydrogen linearly increased with temperatures from 600 to 1000 °C, without a rate minimum in this temperature range. Above 1000 °C, the reduction rate decreased due to sintering phenomena. This result suggests a maximum reduction temperature of 1000 °C using pure hematite and hydrogen as the reducing gas. The reduction controlling mechanisms identified using hydrogen as a reducing gas were chemical reaction for the conversion from hematite to wüstite and diffusion control for the final reduction from wüstite to metallic iron. Since the reduction rate from wüstite to metallic iron is the one that affects the overall rate of reduction, overall changes in porosity were also evaluated. Finally, the reduction of wüstite is schematically described. Full article
(This article belongs to the Special Issue Hydrogen Based Direct Reduction of Metals Oxides)
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17 pages, 6346 KiB  
Article
Reduction Kinetics of Pre-Oxidized Ilmenite Pellets by H2-H2O Gas Mixtures
by Vincent Canaguier and Eli Ringdalen
Metals 2023, 13(2), 332; https://doi.org/10.3390/met13020332 - 7 Feb 2023
Cited by 1 | Viewed by 1864
Abstract
The reduction behavior of pelletized and pre-oxidized ilmenite is investigated in H2-H2O atmospheres containing between 0 and 7% H2O and at temperatures between 983 and 1183 K (710 and 910 °C). The reduction mechanism occurs in two [...] Read more.
The reduction behavior of pelletized and pre-oxidized ilmenite is investigated in H2-H2O atmospheres containing between 0 and 7% H2O and at temperatures between 983 and 1183 K (710 and 910 °C). The reduction mechanism occurs in two stages wherein the rapid reduction of trivalent to divalent iron cations is followed by the slower metallization of iron. Both temperature and gas composition are critical to achieving high reaction rates; within the range of conditions studied, the driving force for metallization has a significant effect on the reduction rate. Based on the experimental data and thermodynamic calculations, a model is established to predict the progress of the reduction as a function of temperature, gas composition and time. The application of this model at variable temperatures permits the determination of the activation energy Ea = 51 kJ/mol for the metallization reaction. Full article
(This article belongs to the Special Issue Hydrogen Based Direct Reduction of Metals Oxides)
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