Calcination

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Calcination is thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), generally for the purpose of removing impurities or volatile substances and/or to incur thermal decomposition. [1]

Contents

The root of the word calcination refers to its most prominent use, which is to remove carbon from limestone (calcium carbonate) through combustion to yield calcium oxide (quicklime). This calcination reaction is CaCO3(s) → CaO(s) + CO2(g). Calcium oxide is a crucial ingredient in modern cement, and is also used as a chemical flux in smelting. Industrial calcination generally emits carbon dioxide (CO2), 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. [2]

Industrial processes

An oven for calcination of limestone LDLimeShaftKilnBasic.jpg
An oven for calcination of limestone

The process of calcination derives its name from the Latin calcinare 'to burn lime' [3] due to its most common application, the decomposition of calcium carbonate (limestone) to calcium oxide (lime) and carbon dioxide, in order to create cement. 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 kilns, multiple hearth furnaces, and fluidized bed reactors.

Examples of calcination processes include the following:

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 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

CaCO3(s) → CaO(s) + CO2(g)

Today, this reaction largely occurs in a cement kiln.

The standard Gibbs free energy of reaction in [J/mol] is approximated as ΔG°r ≈ 177,100 J/mol − 158 J/(mol*K) *T. [4] The standard free energy of reaction is 0 in this case when the temperature, T, is equal to 1121 K, or 848 °C.

Oxidation

In some cases, calcination of a metal results in oxidation of the metal to produce a metal oxide. In his essay "Formal response to the question, why Tin and Lead increase in weight when they are calcined" (1630), Jean Rey notes that "having placed two pounds six ounces of fine English tin in an iron vessel and heated it strongly on an open furnace for the space of six hours with continual agitation and without adding anything to it, he recovered two pounds thirteen ounces of a white calx". He claimed "That this increase in weight comes from the air, which in the vessel has been rendered denser, heavier, and in some measure adhesive, by the vehement and long-continued heat of the furnace: which air mixes with the calx (frequent agitation aiding) and becomes attached to its most minute particles: not otherwise than water makes heavier sand which you throw into it and agitate, by moistening it and adhering to the smallest of its grains", presumably the metal gained weight as it was being oxidized. [5]

At room temperature, tin is quite resistant to the impact of air or water, as a thin oxide film forms on the surface of the metal. In air, tin starts to oxidize at a temperature of over 150 °C: Sn + O2 → SnO2. [6]

Antoine Lavoisier explored this experiment with similar results time later. [7]

Alchemy

In alchemy, 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; silver with common salt and alkali salt; copper with salt and sulfur; iron with sal ammoniac and vinegar; tin with antimony; lead with sulfur; and mercury with nitric acid. [8]

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. [8]

According to the obsolete phlogiston theory, the 'calx' was the true elemental substance that was left after phlogiston was driven out of it in the process of combustion. [9]

Related Research Articles

<span class="mw-page-title-main">Carbonate</span> Salt of carbonic acid

A carbonate is a salt of carbonic acid (H2CO3), 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">Cement</span> Hydraulic binder used in the composition of mortar and concrete

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 mixed with fine aggregate produces mortar for masonry, or with sand and gravel, produces concrete. Concrete is the most widely used material in existence and is behind only water as the planet's most-consumed resource.

<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">Smelting</span> Use of heat and a reducing agent to extract metal from ore

Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. It is a form of extractive metallurgy that is used to obtain many metals such as iron, copper, silver, lead and zinc. Smelting uses heat and a chemical reducing agent to decompose the ore, driving off other elements as gases or slag and leaving the metal behind. The reducing agent is commonly a fossil fuel source of carbon, such as carbon monoxide from incomplete combustion of coke—or, in earlier times, of charcoal. The oxygen in the ore binds to carbon at high temperatures as the chemical potential energy of the bonds in carbon dioxide is lower than that of the bonds in the ore.

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

Calcium carbonate is a chemical compound with the chemical formula CaCO3. It is a common substance found in rocks as the minerals calcite and aragonite, most notably in chalk and limestone, eggshells, gastropod shells, shellfish skeletons and pearls. Materials containing much calcium carbonate or resembling it are described as calcareous. Calcium carbonate is the active ingredient in agricultural lime and is produced when calcium ions in hard water react with carbonate ions to form limescale. It has medical use as a calcium supplement or as an antacid, but excessive consumption can be hazardous and cause hypercalcemia and digestive issues.

<span class="mw-page-title-main">Calcium oxide</span> Chemical compound of calcium

Calcium oxide, 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 compounds, in which carbonates, oxides, and hydroxides of calcium, silicon, magnesium, aluminium, and iron predominate. By contrast, quicklime specifically applies to the single compound calcium oxide. Calcium oxide that survives processing without reacting in building products, such as cement, is called free lime.

<span class="mw-page-title-main">Lime kiln</span> Kiln used for the calcination of limestone

A lime kiln is a kiln used for the calcination of limestone (calcium carbonate) to produce the form of lime called quicklime (calcium oxide). The chemical equation for this reaction is

Calx is a substance formed from an ore or mineral that has been heated. Calx, especially of a metal, is now understood to be an oxide. The term is also sometimes used in older texts on artists' techniques to mean calcium oxide.

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

Magnesium carbonate, MgCO3, is an inorganic salt that is a colourless or white solid. Several hydrated and basic forms of magnesium carbonate also exist as minerals.

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.

Chemical decomposition, or chemical breakdown, is the process or effect of simplifying a single chemical entity into two or more fragments. Chemical decomposition is usually regarded and defined as the exact opposite of chemical synthesis. In short, the chemical reaction in which two or more products are formed from a single reactant is called a decomposition reaction.

Pyrometallurgy is a branch of extractive metallurgy. It consists of the thermal treatment of minerals and metallurgical ores and concentrates to bring about physical and chemical transformations in the materials to enable recovery of valuable metals. Pyrometallurgical treatment may produce products able to be sold such as pure metals, or intermediate compounds or alloys, suitable as feed for further processing. Examples of elements extracted by pyrometallurgical processes include the oxides of less reactive elements like iron, copper, zinc, chromium, tin, and manganese.

<span class="mw-page-title-main">Lime (material)</span> Calcium oxides and/or hydroxides

Lime is an inorganic material composed primarily of calcium oxides and hydroxides, usually calcium oxide and/or calcium hydroxide. It is also the name for calcium oxide which occurs as a product of coal-seam fires and in altered limestone xenoliths in volcanic ejecta. The International Mineralogical Association recognizes lime as a mineral with the chemical formula of CaO. The word lime originates with its earliest use as building mortar and has the sense of sticking or adhering.

<span class="mw-page-title-main">Thermal decomposition</span> Chemical decomposition caused by heat

Thermal decomposition is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is required to break chemical bonds in the compound undergoing decomposition. If decomposition is sufficiently exothermic, a positive feedback loop is created producing thermal runaway and possibly an explosion or other chemical reaction.

<span class="mw-page-title-main">Cement kiln</span> High temperature rotating oven used for producing clinker

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 cement are made per year, and cement kilns are the heart of this production process: their capacity usually defines the capacity of the cement plant. As the main energy-consuming and greenhouse-gas–emitting stage of cement manufacture, improvement of kiln efficiency has been the central concern of cement manufacturing technology. Emissions from cement kilns are a major source of greenhouse gas emissions, accounting for around 2.5% of non-natural carbon emissions worldwide.

<span class="mw-page-title-main">Oxy-fuel combustion process</span> Burning of fuel with pure oxygen

Oxy-fuel combustion is the process of burning a fuel using pure oxygen, or a mixture of oxygen and recirculated flue gas, instead of air. Since the nitrogen component of air is not heated, fuel consumption is reduced, and higher flame temperatures are possible. Historically, the primary use of oxy-fuel combustion has been in welding and cutting of metals, especially steel, since oxy-fuel allows for higher flame temperatures than can be achieved with an air-fuel flame. It has also received a lot of attention in recent decades as a potential carbon capture and storage technology.

<span class="mw-page-title-main">Carbon dioxide scrubber</span> Device which absorbs carbon dioxide from circulated gas

A carbon dioxide scrubber is a piece of equipment that absorbs carbon dioxide (CO2). It is used to treat exhaust gases from industrial plants or from exhaled air in life support systems such as rebreathers or in spacecraft, submersible craft or airtight chambers. Carbon dioxide scrubbers are also used in controlled atmosphere (CA) storage. They have also been researched for carbon capture and storage as a means of combating climate change.

<span class="mw-page-title-main">Concrete degradation</span> Damage to concrete affecting its mechanical strength and its durability

Concrete degradation may have many different causes. Concrete is mostly damaged by the corrosion of reinforcement bars due to the carbonatation of hardened cement paste or chloride attack under wet conditions. Chemical damages are caused by the formation of expansive products produced by various chemical reactions, by aggressive chemical species present in groundwater and seawater, or by microorganisms. Other damaging processes can also involve calcium leaching by water infiltration and different physical phenomena initiating cracks formation and propagation. All these detrimental processes and damaging agents adversely affects the concrete mechanical strength and its durability.

Calcium looping (CaL), or the regenerative calcium cycle (RCC), is a second-generation carbon capture technology. It is the most developed form of carbonate looping, where a metal (M) is reversibly reacted between its carbonate form (MCO3) and its oxide form (MO) to separate carbon dioxide from other gases coming from either power generation or an industrial plant. In the calcium looping process, the two species are calcium carbonate (CaCO3) and calcium oxide (CaO). The captured carbon dioxide can then be transported to a storage site, used in enhanced oil recovery or used as a chemical feedstock. Calcium oxide is often referred to as the sorbent.

References

  1. "Calcination". The IUPAC Compendium of Chemical Terminology. 2014. doi:10.1351/goldbook.C00773.
  2. "High-Temperature Processing with Calciners".
  3. Mosby's Medical, Nursing and Allied Health Dictionary, Fourth Edition, Mosby-Year Book Inc., 1994, p. 243
  4. Gilchrist, J.D. (1989). Extraction Metallurgy (3rd ed.). Oxford: Pergamon Press. p. 145. ISBN   978-0-08-036612-8.
  5. Rey, Jean (1953). Essays of Jean Rey, doctor of medicine, on an enquiry into the cause wherefore tin and lead increase in weight on calcination (1630). E. & S. Livingstone for the Alembic Club. OCLC   154124030.
  6. "Tin: its oxidation states and reactions with it".
  7. "Lavoisier tin calcination".
  8. 1 2 PD-icon.svg This article incorporates text from a publication now in the public domain :  Chambers, Ephraim, ed. (1728). "Calcination". Cyclopædia, or an Universal Dictionary of Arts and Sciences (1st ed.). James and John Knapton, et al.
  9. Daintith, John, ed. (2008). "Phlogiston theory". A Dictionary of Chemistry (6th ed.). Oxford University Press. doi:10.1093/acref/9780199204632.001.0001. ISBN   9780191726569 via Oxford Reference. In the early 18th century Georg Stahl renamed the substance phlogiston (from the Greek for 'burned') and extended the theory to include the calcination (and corrosion) of metals. Thus, metals were thought to be composed of calx (a powdery residue) and phlogiston; when a metal was heated, phlogiston was set free and the calx remained. The process could be reversed by heating the metal over charcoal (a substance believed to be rich in phlogiston, because combustion almost totally consumed it). The calx would absorb the phlogiston released by the burning charcoal and become metallic again.