Calcination refers to
thermal treatment
Thermal treatment is any waste treatment technology that involves high temperatures in the processing of the waste feedstock. Commonly this involves the combustion of waste materials.
Systems that are generally considered to be thermal treatment ...
of a solid chemical compound (e.g. mixed
carbonate
A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate g ...
ore
Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 April ...
s) whereby the compound is raised to high temperature without melting under restricted supply of ambient
oxygen (i.e. gaseous O
2 fraction of air), generally for the purpose of removing impurities or
volatile substances and/or to incur
thermal decomposition.
The root of the word calcination refers to its most prominent use, which is to remove carbon from
limestone (calcium carbonate) through
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 ...
to yield
calcium oxide (quicklime). This calcination reaction is CaCO
3(s) → CaO(s) + CO
2(g). Calcium oxide is a crucial ingredient in modern
cement
A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel ( aggregate) together. Cement mi ...
, and is also used as a chemical
flux in
smelting
Smelting is a process of applying heat to ore, to extract a base metal. It is a form of extractive metallurgy. It is used to extract many metals from their ores, including silver, iron, copper, and other base metals. Smelting uses heat and a c ...
. Industrial calcination generally emits
carbon dioxide (), making it a major contributor to
climate change.
A calciner is a steel cylinder that rotates inside a heated furnace and performs indirect high-temperature processing (550–1150 °C, or 1000–2100 °F) within a controlled atmosphere.
Industrial processes
The process of calcination derives its name from the Latin ''calcinare'' (to burn lime) due to its most common application, the decomposition of calcium carbonate (
limestone) to
calcium oxide
Calcium oxide (CaO), commonly known as quicklime or burnt lime, is a widely used chemical compound. It is a white, caustic, alkaline, crystalline solid at room temperature. The broadly used term "''lime''" connotes calcium-containing inorganic ...
(
lime) and
carbon dioxide, in order to create
cement
A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel ( aggregate) together. Cement mi ...
. The product of calcination is usually referred to in general as "calcine", regardless of the actual minerals undergoing thermal treatment. Calcination is carried out in
furnaces or reactors (sometimes referred to as
kilns or calciners) of various designs including shaft furnaces,
rotary kiln
A rotary kiln is a pyroprocessing device used to raise materials to a high temperature (calcination) in a continuous process. Materials produced using rotary kilns include:
* Cement
* Lime
* Refractories
* Metakaolin
* Titanium dioxide
* Alum ...
s,
multiple hearth furnace A sketch of a Herreshoff multiple-hearth furnace, 400x400px
A multiple hearth furnace also known as a vertical calciner, is used for continuous preparation and calcining of materials.
Working
The multiple hearth furnaces consist of several cir ...
s, and
fluidized bed reactor
A fluidized bed reactor (FBR) is a type of reactor device that can be used to carry out a variety of multiphase chemical reactions. In this type of reactor, a fluid (gas or liquid) is passed through a solid granular material (usually a catalyst ...
s.
The process involves the burning of the metal ore in limited oxygen to extract the ores.
Examples of calcination processes include the following:
*decomposition of carbonate ores, as in the calcination of
limestone to drive off
carbon dioxide;
*decomposition of hydrated minerals, as in the calcination of
bauxite
Bauxite is a sedimentary rock with a relatively high aluminium content. It is the world's main source of aluminium and gallium. Bauxite consists mostly of the aluminium minerals gibbsite (Al(OH)3), boehmite (γ-AlO(OH)) and diaspore (α-AlO(OH ...
and
gypsum
Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywa ...
,
carbonate ore
A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonate g ...
to remove
water of crystallization as water vapor;
*decomposition of volatile matter contained in raw
petroleum coke
Petroleum coke, abbreviated coke or petcoke, is a final carbon-rich solid material that derives from oil refining, and is one type of the group of fuels referred to as cokes. Petcoke is the coke that, in particular, derives from a final crackin ...
;
*heat treatment to effect phase transformations, as in conversion of
anatase
Anatase is a metastable mineral form of titanium dioxide (TiO2) with a tetragonal crystal structure. Although colorless or white when pure, anatase in nature is usually a black solid due to impurities. Three other polymorphs (or mineral forms) ...
to
rutile
Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common natural form of TiO2. Rarer polymorphs of TiO2 are known, including anatase, akaogiite, and brookite.
Rutile has one of the highest refractive indices at visibl ...
or
devitrification
Devitrification is the process of crystallization in a formerly crystal-free (amorphous) glass. The term is derived from the Latin ''vitreus'', meaning ''glassy'' and '' transparent''.
Devitrification in glass art
Devitrification occurs in glass a ...
of
glass materials;
*removal of
ammonium ions in the
synthesis
Synthesis or synthesize may refer to:
Science Chemistry and biochemistry
* Chemical synthesis, the execution of chemical reactions to form a more complex molecule from chemical precursors
**Organic synthesis, the chemical synthesis of organ ...
of
zeolites;
*defluorination of uranyl fluoride to create
uranium dioxide
Uranium dioxide or uranium(IV) oxide (), also known as urania or uranous oxide, is an oxide of uranium, and is a black, radioactive, crystalline powder that naturally occurs in the mineral uraninite. It is used in nuclear fuel rods in nuclear react ...
and
hydrofluoric acid
Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colourless, acidic and highly corrosive. It is used to make most fluorine-containing compounds; examples include the commonly used pharmaceutical antidepress ...
gas.
Reactions
Calcination reactions usually take place at or above the thermal decomposition temperature (for decomposition and volatilization reactions) or the transition temperature (for phase transitions). This temperature is usually defined as the temperature at which the standard
Gibbs free energy
In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature and p ...
for a particular calcination reaction is equal to zero.
Limestone calcination
In limestone calcination, a decomposition process that occurs at 900 to 1050°C, the chemical reaction is
: CaCO
3(s) → CaO(s) + CO
2(g)
Today, this reaction largely occurs in a
cement kiln
Cement kilns are used for the pyroprocessing stage of manufacture of portland and other types of hydraulic cement, in which calcium carbonate reacts with silica-bearing minerals to form a mixture of calcium silicates. Over a billion tonnes of ...
.
The standard Gibbs free energy of reaction in
/molis approximated as Δ''G''°
''r'' ≈ 177,100 J/mol − 158 J/(mol*K) *''T''.
The standard free energy of reaction is 0 in this case when the temperature, ''T'', is equal to 1121K, or 848 °C.
Oxidation
In some cases, calcination of a metal results in
oxidation of the metal to produce a
metal oxide. In the seventeenth century,
Jean Rey noted that
lead and
tin when calcinated gained mass, presumably as they were being oxidized.
Alchemy
In
alchemy
Alchemy (from Arabic: ''al-kīmiyā''; from Ancient Greek: χυμεία, ''khumeía'') is an ancient branch of natural philosophy, a philosophical and protoscientific tradition that was historically practiced in China, India, the Muslim worl ...
, calcination was believed to be one of the
12 vital processes required for the transformation of a substance.
Alchemists distinguished two kinds of calcination, ''actual'' and ''potential''. Actual calcination is that brought about by actual fire, from wood, coals, or other fuel, raised to a certain temperature. Potential calcination is that brought about by ''potential'' fire, such as corrosive chemicals; for example, gold was calcined in a
reverberatory furnace with
mercury and
salammoniac
Salammoniac, also sal ammoniac or salmiac, is a rare naturally occurring mineral composed of ammonium chloride, NH4Cl. It forms colorless, white, or yellow-brown crystals in the isometric-hexoctahedral class. It has very poor cleavage and is ...
; silver with common salt and
alkali salt
Alkali salts or basic salts are salts that are the product of incomplete neutralization of a strong base and a weak acid.
Rather than being neutral (as some other salts), alkali salts are bases as their name suggests. What makes these compound ...
;
copper with salt and
sulfur;
iron with sal ammoniac and
vinegar; tin with
antimony; lead with sulfur; and mercury with
nitric acid.
There was also ''philosophical calcination'', which was said to occur when horns, hooves, etc., were hung over boiling water, or other liquor, until they had lost their
mucilage, and were easily reducible into powder.
References
{{Extractive metallurgy
Chemical processes
Metallurgical processes
Alchemical processes