Carbothermic reaction

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Carbothermal reduction of molten potassium nitrate with charcoal to potassium nitrite

Carbothermic reactions involve the reduction of substances, often metal oxides (O2-), using carbon (C) as the reducing agent. The reduction is usually conducted in the electric arc furnace or reverberatory furnace, depending on the metal ore. These chemical reactions are usually conducted at temperatures of several hundred degrees Celsius. Such processes are applied for production of the elemental forms of many elements. The ability of metals to participate in carbothermic reactions can be predicted from Ellingham diagrams. [1]

Contents

Carbothermal reactions produce carbon monoxide (CO) and sometimes carbon dioxide (CO2). The facility of these conversions is attributable to the entropy of reaction: two solids, the metal oxide (and flux) and carbon, are converted to a new solid (metal) and a gas (COx), the latter having high entropy.

Applications

A prominent example is that of iron ore smelting. Many reactions are involved, but the simplified equation is usually shown as:

2Fe
2
O
3
+ 3C → 4Fe + 3CO2

On a more modest scale, about 1 million tons of elemental phosphorus is produced annually by carbothermic reactions. [2] Calcium phosphate (phosphate rock) is heated to 1,200–1,500 °C with sand, which is mostly SiO
2
, and coke (impure carbon) to produce P
4
. The chemical equation for this process when starting with fluoroapatite, a common phosphate mineral, is:

4Ca
5
(PO
4
)
3
F
+ 18SiO
2
+ 30C → 3P
4
+ 30CO + 18CaSiO
3
+ 2CaF
2

Of historic interest is the Leblanc process. A key step in this process is the reduction of sodium sulfate with coal: [3]

Na2SO4 + 2 C → Na2S + 2 CO2

The Na2S is then treated with calcium carbonate to give sodium carbonate, a commodity chemical.

Recently, development of the 'MagSonic' carbothermic magnesium process has restarted interest in its chemistry: [4]

MgO + CMg + CO

The reaction is readily reversible from its product vapors, and requires rapid cooling to prevent back-reaction.

Silicon

Metallurgical grade silicon may also be obtained by carbothermic reaction. The overall reaction is following: [5]

SiO
2
+ CSi + CO
2

The actual reaction given is more complex than it seems and includes several steps. [5]

Variations

Sometimes carbothermic reactions are coupled to other conversions. One example is the chloride process for separating titanium from ilmenite, the main ore of titanium. In this process, a mixture of carbon and the crushed ore is heated at 1000 °C under flowing chlorine gas, giving titanium tetrachloride:

2FeTiO
3
+ 7Cl
2
+ 6C → 2TiCl
4
+ 2FeCl
3
+ 6CO

For some metals, carbothermic reactions do not afford the metal, but instead give the metal carbide. This behavior is observed for titanium, hence the use of the chloride process. Carbides also form upon high temperature treatment of Cr
2
O
3
with carbon. For this reason, aluminium is employed as the reducing agent.

Related Research Articles

<span class="mw-page-title-main">Magnesium</span> Chemical element, symbol Mg and atomic number 12

Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals it occurs naturally only in combination with other elements and it almost always has an oxidation state of +2. It reacts readily with air to form a thin passivation coating of magnesium oxide that inhibits further corrosion of the metal. The free metal burns with a brilliant-white light. The metal is obtained mainly by electrolysis of magnesium salts obtained from brine. It is less dense than aluminium and is used primarily as a component in strong and lightweight alloys that contain aluminium.

<span class="mw-page-title-main">Oxide</span> Chemical compound where oxygen atoms are combined with atoms of other elements

An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.

<span class="mw-page-title-main">Alkaline earth metal</span> Group of chemical elements

The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). The elements have very similar properties: they are all shiny, silvery-white, somewhat reactive metals at standard temperature and pressure.

<span class="mw-page-title-main">Sodium carbonate</span> Chemical compound

Sodium carbonate is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, odourless, water-soluble salts that yield alkaline solutions in water. Historically, it was extracted from the ashes of plants grown in sodium-rich soils. Because the ashes of these sodium-rich plants were noticeably different from ashes of wood, sodium carbonate became known as "soda ash". It is produced in large quantities from sodium chloride and limestone by the Solvay process, as well as by carbonating sodium hydroxide which is made using the Chlor-alkali process.

<span class="mw-page-title-main">Manganese dioxide</span> Chemical compound

Manganese dioxide is the inorganic compound with the formula MnO
2
. This blackish or brown solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a component of manganese nodules. The principal use for MnO
2
is for dry-cell batteries, such as the alkaline battery and the zinc–carbon battery. MnO
2
is also used as a pigment and as a precursor to other manganese compounds, such as KMnO
4
. It is used as a reagent in organic synthesis, for example, for the oxidation of allylic alcohols. MnO
2
has an α-polymorph that can incorporate a variety of atoms in the "tunnels" or "channels" between the manganese oxide octahedra. There is considerable interest in α-MnO
2
as a possible cathode for lithium-ion batteries.

<span class="mw-page-title-main">Sodium percarbonate</span> Chemical compound

Sodium percarbonate, or sodium carbonate peroxide is a chemical substance with formula Na
2
H
3
CO
6
. It is an adduct of sodium carbonate and hydrogen peroxide whose formula is more properly written as 2 Na
2
CO
3
 · 3 H
2
O
2
. It is a colorless, crystalline, hygroscopic and water-soluble solid. It is sometimes abbreviated as SPC. It contains 32.5% by weight of hydrogen peroxide.

<span class="mw-page-title-main">Industrial processes</span> Process of producing goods

Industrial processes are procedures involving chemical, physical, electrical, or mechanical steps to aid in the manufacturing of an item or items, usually carried out on a very large scale. Industrial processes are the key components of heavy industry.

<span class="mw-page-title-main">Barium carbonate</span> Chemical compound

Barium carbonate is the inorganic compound with the formula BaCO3. Like most alkaline earth metal carbonates, it is a white salt that is poorly soluble in water. It occurs as the mineral known as witherite. In a commercial sense, it is one of the most important barium compounds.

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as “tickle” or “tickle 4”, as a phonetic representation of the symbols of its molecular formula.

<span class="mw-page-title-main">Titanium diboride</span> Chemical compound

Titanium diboride (TiB2) is an extremely hard ceramic which has excellent heat conductivity, oxidation stability and wear resistance. TiB2 is also a reasonable electrical conductor, so it can be used as a cathode material in aluminium smelting and can be shaped by electrical discharge machining.

The Kroll process is a pyrometallurgical industrial process used to produce metallic titanium from titanium tetrachloride. The Kroll process replaced the Hunter process for almost all commercial production.

<span class="mw-page-title-main">Vanadium(V) oxide</span> Precursor to vanadium alloys and industrial catalyst

Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V2O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.

<span class="mw-page-title-main">Calcium sulfide</span> Chemical compound of formula CaS

Calcium sulfide is the chemical compound with the formula CaS. This white material crystallizes in cubes like rock salt. CaS has been studied as a component in a process that would recycle gypsum, a product of flue-gas desulfurization. Like many salts containing sulfide ions, CaS typically has an odour of H2S, which results from small amount of this gas formed by hydrolysis of the salt.

<span class="mw-page-title-main">Chromium(III) oxide</span> Chemical compound

Chromium(III) oxide is an inorganic compound with the formula Cr
2
O
3
. It is one of the principal oxides of chromium and is used as a pigment. In nature, it occurs as the rare mineral eskolaite.

<span class="mw-page-title-main">Pidgeon process</span>

The Pidgeon process is a practical method for smelting magnesium. The most common method involves the raw material, dolomite being fed into an externally heated reduction tank and then thermally reduced to metallic magnesium using 75% ferrosilicon as a reducing agent in a vacuum. Overall the processes in magnesium smelting via the Pidgeon process involve dolomite calcination, grinding and pelleting, and vacuum thermal reduction. Besides the Pidgeon process, electrolysis of magnesium chloride for commercial production of magnesium is also used, at one point in time accounting for 75% of the world's magnesium production.

<span class="mw-page-title-main">Sodium sulfide</span> Chemical compound

Sodium sulfide is a chemical compound with the formula Na2S, or more commonly its hydrate Na2S·9H2O. Both the anhydrous and the hydrated salts in pure crystalline form are colorless solids, although technical grades of sodium sulfide are generally yellow to brick red owing to the presence of polysulfides and commonly supplied as a crystalline mass, in flake form, or as a fused solid. They are water-soluble, giving strongly alkaline solutions. When exposed to moist air, Na2S and its hydrates emit hydrogen sulfide, an extremely toxic, flammable and corrosive gas which smells like rotten eggs.

<span class="mw-page-title-main">Zirconium carbide</span> Chemical compound

Zirconium carbide (ZrC) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering.

An Ellingham diagram is a graph showing the temperature dependence of the stability of compounds. This analysis is usually used to evaluate the ease of reduction of metal oxides and sulfides. These diagrams were first constructed by Harold Ellingham in 1944. In metallurgy, the Ellingham diagram is used to predict the equilibrium temperature between a metal, its oxide, and oxygen — and by extension, reactions of a metal with sulfur, nitrogen, and other non-metals. The diagrams are useful in predicting the conditions under which an ore will be reduced to its metal. The analysis is thermodynamic in nature and ignores reaction kinetics. Thus, processes that are predicted to be favourable by the Ellingham diagram can still be slow.

<span class="mw-page-title-main">Oxygen compounds</span>

The oxidation state of oxygen is −2 in almost all known compounds of oxygen. The oxidation state −1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: −12 (superoxides), −13 (ozonides), 0, +12 (dioxygenyl), +1, and +2.

References

  1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8. "Figure 8.19 Ellingham diagram for the free energy of formation of metallic oxides" p. 308
  2. Diskowski, Herbert; Hofmann, Thomas (2005). "Phosphorus". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_505. ISBN   9783527306732.
  3. Christian Thieme (2000). "Sodium Carbonates". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a24_299. ISBN   978-3527306732.
  4. Prentice, Leon; Nagle, Michael (2012). "Carbothermal Production of Magnesium: CSIRO's MagSonic Process". In Mathaudhu (ed.). Magnesium Technology 2012. Cham: Springer. doi:10.1007/978-3-319-48203-3_6. ISBN   9783319482033.
  5. 1 2 Lee, J. G.; Miller, P. D.; Cutler, I. B. (1977), Wood, John; Lindqvist, Oliver; Helgesson, Claes; Vannerberg, Nils-Gösta (eds.), "Carbothermal Reduction of Silica", Reactivity of Solids, Boston, MA: Springer US, pp. 707–711, doi:10.1007/978-1-4684-2340-2_102, ISBN   978-1-4684-2342-6 , retrieved 2023-06-04