Direct Reduction (blast Furnace)
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Direct reduction is the fraction of
iron oxide An iron oxide is a chemical compound composed of iron and oxygen. Several iron oxides are recognized. Often they are non-stoichiometric. Ferric oxyhydroxides are a related class of compounds, perhaps the best known of which is rust. Iron ...
reduction that occurs in a blast furnace due to the presence of coke carbon, while the remainder - indirect reduction - consists mainly of
carbon monoxide Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...
from coke
combustion Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion ...
. It should also be noted that many non-ferrous oxides are reduced by this type of reaction in a
blast furnace A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals, generally pig iron, but also others such as lead or copper. ''Blast'' refers to the combustion air being supplied above atmospheric pressure. In a ...
. This reaction is therefore essential to the operation of historical processes for the production of non-
ferrous In chemistry, iron(II) refers to the chemical element, element iron in its +2 oxidation number, oxidation state. The adjective ''ferrous'' or the prefix ''ferro-'' is often used to specify such compounds, as in ''ferrous chloride'' for iron(II ...
metals by non-steel blast furnaces (i.e. blast furnaces dedicated to the production of
ferromanganese Ferromanganese is an alloy of iron and manganese, with other elements such as silicon, carbon, sulfur, nitrogen and phosphorus. The primary use of ferromanganese is as a type of processed manganese source to add to different types of steel, such ...
,
ferrosilicon Ferrosilicon is an ferroalloy, alloy of iron and silicon. It has a typical silicon content of 15–90% by weight and a high proportion of iron silicides. Production and reactions Ferrosilicon is produced by reduction of silica or sand with coke ...
, etc., which have now disappeared). Direct-reduction
steelmaking Steelmaking is the process of producing steel from iron ore and/or scrap. Steel has been made for millennia, and was commercialized on a massive scale in the 1850s and 1860s, using the Bessemer process, Bessemer and open hearth furnace, Siemens-M ...
processes that bring metal oxides into contact with
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
(typically those based on the use of hard
coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other Chemical element, elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal i ...
or
charcoal Charcoal is a lightweight black carbon residue produced by strongly heating wood (or other animal and plant materials) in minimal oxygen to remove all water and volatile constituents. In the traditional version of this pyrolysis process, ca ...
) also exploit this chemical reaction. In fact, at first glance, many of them seem to use only this reaction. Processes that historically competed with blast furnaces, such as the
Catalan forge The Catalan forge is a set of technological processes designed to obtain iron by directly Direct reduction, reducing the Iron ore, ore—without going through the intermediary of smelting as in a blast furnace—and then shingling the resulting . ...
, have been assimilated into this reaction. But modern direct reduction processes are often based on the exclusive use of reducing gases: in this case, their name takes on the exact opposite meaning to that of the chemical reaction.


Definition

For blast furnaces,
direct reduction read online, part I, pp. 240; 250-254; 257. (capacity 650,000 t/year).(fr) Adolf Ledebur (trans. Barbary de Langlade revised and annotated by F. Valton), ''Manuel théorique et pratique de la métallurgie du fer, Tome I et Tome II'', t. 2, Librairie ...
corresponds to the reduction of oxides by the carbon in the coke. However, in practice, direct reduction only plays a significant role in the final stage of iron reduction in a blast furnace, by helping to reduce wustite (FeO) to
iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
. In this case, the chemical reaction can be trivially described as follows:(fr) Maurice Burteaux, "Haut Fourneau: théorie", in ''Techniques de l'ingénieur Traité matériaux métalliques'', Éditions techniques de l'ingénieur
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FeO + C → Fe + CO consuming 155,15 kJ/mol However, "in the solid state, there is virtually no reaction in the absence of gases, even between finely ground
iron ore Iron ores are rocks and minerals from which metallic iron can be economically extracted. The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, or deep purple to rusty red. The iron is usually found in the f ...
and coal powders. In other words, it seems certain that the reaction takes place via gases".(fr) Jacques Astier, "Réduction directe", in ''Techniques de l'ingénieur Élaboration et recyclage des métaux'', Éditions techniques de l'ingénieur, September 10th, 2005
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This means that direct reduction most probably corresponds to the following chain of reactions: FeO + CO → Fe + CO2 producing 17,45 kJ/mol (reduction by CO) CO2 + C ⇌ 2 CO consuming 172,45 kJ/mol (
Boudouard reaction The Boudouard reaction, named after Octave Leopold Boudouard, is the redox reaction of a chemical equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature. It is the disproportionation of carbon monoxide into carbon dioxide ...
)


Roles

This reaction accounts for around half of the transformation of wustite FeO into iron, and removes 30% of the total oxygen supplied, mainly in the form of iron oxide Fe2O3. This mode of wustite reduction is highly
endothermic An endothermic process is a chemical or physical process that absorbs heat from its surroundings. In terms of thermodynamics, it is a thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, ...
, whereas the reduction of iron oxides by CO is slightly
exothermic In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity (e ...
(+155.15 kJ/mol vs. -17.45 kJ/mol), so it is essential to keep it to a minimum. This reaction concerns all the iron oxides present in a blast furnace, but also manganese(II) oxides (Mno),
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
(SiO2),
chromium Chromium is a chemical element; it has Symbol (chemistry), symbol Cr and atomic number 24. It is the first element in Group 6 element, group 6. It is a steely-grey, Luster (mineralogy), lustrous, hard, and brittle transition metal. Chromium ...
,
vanadium Vanadium is a chemical element; it has Symbol (chemistry), symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an ...
and
titanium Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
, which are partially reduced in blast furnaces. These chemical reactions are described below: MnO + C → Mn + CO consuming 282,4 kJ/mol à 1 400 °C (begins above 1,000
°C The degree Celsius is the unit of temperature on the Celsius temperature scale "Celsius temperature scale, also called centigrade temperature scale, scale based on 0 ° for the melting point of water and 100 ° for the boiling point ...
and involves half of the manganese present in the charge) SiO2 + 2 C → Si + 2 CO consuming 655,5 kJ/mol (begins above 1 500 °C) Chromium and vanadium behave like manganese,
titanium Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
like silicon. As for the other iron oxides, their direct reduction is of negligible importance. This can be written as: 3 Fe2O3 + C → 2 Fe3O4 + CO consuming 118,821 kJ/mol Fe3O4 + C → 3 FeO + CO consuming 209,256 kJ/mol In non-steel blast furnaces, dedicated to the production of ferroalloys, direct reduction is fundamental. For example, for ferronickel production, both direct reduction reactions are used: NiO + C → Ni + CO above 445 °C FeO + C → Fe + CO above 800 °C So, although
nickel Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...
reduces slightly more easily than iron, it cannot be reduced and cast independently of iron.Frank K. Krundwell, Michael S. Moats, Venkoba Ramachandran, Timothy G. Robinson and William G. Davenport, ''Extractive Metallurgy of Nickel, Cobalt and Platinum Group Metals'', Elsevier, 2011, 610 p. (ISBN 978-0-08-096809-4
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, p. 51


Notes

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References

Iron Blast furnaces Metallurgy Steelmaking