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:

2 Fe
2
O
3
+ 3 C → 4 Fe + 3 CO2

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:

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

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

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">Carbonate</span> Salt or ester of carbonic acid

A carbonate is a salt of carbonic acid,, characterized by the presence of the carbonate ion, a polyatomic ion with the formula CO2−3. The word "carbonate" may also refer to a carbonate ester, an organic compound containing the carbonate groupO=C(−O−)2.

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

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

<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, and 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 chloralkali process.

In chemistry, a reducing agent is a chemical species that "donates" an electron to an electron recipient.

<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.

The Solvay process or ammonia–soda process is the major industrial process for the production of sodium carbonate (soda ash, Na2CO3). The ammonia–soda process was developed into its modern form by the Belgian chemist Ernest Solvay during the 1860s. The ingredients for this are readily available and inexpensive: salt brine (from inland sources or from the sea) and limestone (from quarries). The worldwide production of soda ash in 2005 was estimated at 42 million tonnes, which is more than six kilograms (13 lb) per year for each person on Earth. Solvay-based chemical plants now produce roughly three-quarters of this supply, with the remaining being mined from natural deposits. This method superseded the Leblanc process.

<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">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">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">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 moisture, Na2S immediately hydrates to give sodium hydrosulfide.

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">Electrometallurgy</span>

Electrometallurgy is a method in metallurgy that uses electrical energy to produce metals by electrolysis. It is usually the last stage in metal production and is therefore preceded by pyrometallurgical or hydrometallurgical operations. The electrolysis can be done on a molten metal oxide which is used for example to produce aluminium from aluminium oxide via the Hall-Hérault process. Electrolysis can be used as a final refining stage in pyrometallurgical metal production (electrorefining) and it is also used for reduction of a metal from an aqueous metal salt solution produced by hydrometallurgy (electrowinning).

<span class="mw-page-title-main">Iron(II) carbonate</span> Chemical, compound of iron carbon and oxygen

Iron(II) carbonate, or ferrous carbonate, is a chemical compound with formula FeCO
3
, that occurs naturally as the mineral siderite. At ordinary ambient temperatures, it is a green-brown ionic solid consisting of iron(II) cations Fe2+
and carbonate anions CO2−
3
.

The chloride process is used to separate titanium from its ores. The goal of the process is to win high purity titanium dioxide from ores such as ilmenite (FeTiO3) and rutile (TiO2). The strategy exploits the volatility of TiCl4, which is readily purified and converted to the dioxide. Millions of tons of TiO2 are produced annually by this process, mainly for use as white pigments. As of 2017, the chloride process is used alongside the older sulfate process, which relies on hot sulfuric acid to extract iron and other impurities from ores.

Direct reduction is the fraction of iron oxide reduction that occurs in a blast furnace due to the presence of coke carbon, while the remainder - indirect reduction - consists mainly of carbon monoxide from coke combustion.

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