Coking is the heating of
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 elements, chiefly hydrogen, sulfur, oxygen, and nitrogen.
Coal is formed when dea ...
in the absence of
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
to a temperature above 600 °C to drive off the volatile components of the raw coal, leaving a hard, strong, porous material of high
carbon
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent
In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
content called
coke. Coke consists almost entirely of
hydrocarbons
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...
. The porosity gives it a high surface area, which makes it burn faster (as does a sheet of paper versus a wooden log). When a kilogram of coke is burned it releases more heat than a kilogram of the original coal.
Coke is used as fuel 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 "forced" or supplied above atmospheric ...
. In a continuous process, coke,
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 fo ...
, and
limestone
Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms whe ...
are mixed together and placed in the top of the blast furnace, and at the bottom liquid
iron
Iron () is a chemical element with symbol Fe (from la, ferrum) 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, right in f ...
and waste
slag
Slag is a by-product of smelting (pyrometallurgical) ores and used metals. Broadly, it can be classified as ferrous (by-products of processing iron and steel), ferroalloy (by-product of ferroalloy production) or non-ferrous/base metals (by-prod ...
are removed. The raw materials continuously move down the blast furnace. During this continuous process more raw materials are placed at the top, and as the coke moves down, it must withstand the ever-increasing weight of the materials above it. It is the ability to withstand this crushing force, in addition to its high energy content and rapid combustion, that makes coke ideal for use in blast furnaces.
Petroleum coking
“Coking is a refinery unit operation that upgrades material called bottoms from the atmospheric or vacuum distillation column into higher-value products and produces petroleum coke—a coal-like material.”. In
heterogeneous catalysis
In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Ph ...
, the process is undesirable because the
clinker blocks the catalytic sites. Coking is characteristic of high temperature reactions involving hydrocarbon feedstocks. Typically coking is reversed by combustion, provided that the catalyst will tolerate such.
A simplified equation for coking is shown in the case of
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
:
: 3 C
2H
4 → 2 C ("coke") + 2 C
2H
6
A more realistic but complex view involves the
alkylation
Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting ...
of an aromatic ring of a coke nucleus.
Acidic
In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
catalysts are thus especially prone to coking because they are effective at generating
carbocation
A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium , methanium and vinyl cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountere ...
s (i.e., alkylating agents).
Coking is one of several mechanisms for the deactivation of a
heterogeneous catalyst
In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Ph ...
. Other mechanisms include
sintering
Clinker nodules produced by sintering
Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction.
Sintering happens as part of a manufacturing ...
,
poisoning
A poison can be any substance that is harmful to the body. It can be swallowed, inhaled, injected or absorbed through the skin. Poisoning is the harmful effect that occurs when too much of that substance has been taken. Poisoning is not to ...
, and
solid-state transformation of the catalyst.
[{{cite journal, last1=Bartholomew, first1=Calvin H, title=Mechanisms of Catalyst Deactivation, journal=Applied Catalysis A: General, volume=212, issue=1–2, pages=17–60, doi=10.1016/S0926-860X(00)00843-7, year=2001]
References
Coking works
Catalysis