Methane Pyrolysis For Hydrogen
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Methane ( , ) is a
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
with the
chemical formula A chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, such as pare ...
(one
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
atom bonded to four
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
atoms). It is a
group-14 hydride Group 14 hydrides are chemical compounds composed of hydrogen atoms and group 14 atoms (the elements of group 14 are carbon, silicon, germanium, tin, lead and flerovium). Tetrahydrides The tetrahydride series has the chemical formula , with X ...
, the simplest
alkane In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in whi ...
, and the main constituent of
natural gas Natural gas (also fossil gas, methane gas, and gas) is a naturally occurring compound of gaseous hydrocarbons, primarily methane (95%), small amounts of higher alkanes, and traces of carbon dioxide and nitrogen, hydrogen sulfide and helium ...
. The abundance of methane on
Earth Earth is the third planet from the Sun and the only astronomical object known to Planetary habitability, harbor life. This is enabled by Earth being an ocean world, the only one in the Solar System sustaining liquid surface water. Almost all ...
makes it an economically attractive
fuel A fuel is any material that can be made to react with other substances so that it releases energy as thermal energy or to be used for work (physics), work. The concept was originally applied solely to those materials capable of releasing chem ...
, although capturing and storing it is difficult because it is a
gas Gas is a state of matter that has neither a fixed volume nor a fixed shape and is a compressible fluid. A ''pure gas'' is made up of individual atoms (e.g. a noble gas like neon) or molecules of either a single type of atom ( elements such as ...
at
standard temperature and pressure Standard temperature and pressure (STP) or standard conditions for temperature and pressure are various standard sets of conditions for experimental measurements used to allow comparisons to be made between different sets of data. The most used ...
. In the Earth's atmosphere methane is transparent to visible light but absorbs
infrared radiation Infrared (IR; sometimes called infrared light) is electromagnetic radiation (EMR) with wavelengths longer than that of visible light but shorter than microwaves. The infrared spectral band begins with the waves that are just longer than those ...
, acting as a
greenhouse gas Greenhouse gases (GHGs) are the gases in the atmosphere that raise the surface temperature of planets such as the Earth. Unlike other gases, greenhouse gases absorb the radiations that a planet emits, resulting in the greenhouse effect. T ...
. Methane is an
organic Organic may refer to: * Organic, of or relating to an organism, a living entity * Organic, of or relating to an anatomical organ Chemistry * Organic matter, matter that has come from a once-living organism, is capable of decay or is the product ...
compound Compound may refer to: Architecture and built environments * Compound (enclosure), a cluster of buildings having a shared purpose, usually inside a fence or wall ** Compound (fortification), a version of the above fortified with defensive struc ...
, and among the simplest of organic compounds. Methane is also a
hydrocarbon 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 Hydrophobe, hydrophobic; their odor is usually fain ...
. Naturally occurring methane is found both below ground and under the
seafloor The seabed (also known as the seafloor, sea floor, ocean floor, and ocean bottom) is the bottom of the ocean. All floors of the ocean are known as seabeds. The structure of the seabed of the global ocean is governed by plate tectonics. Most of ...
and is formed by both geological and biological processes. The largest
reservoir A reservoir (; ) is an enlarged lake behind a dam, usually built to water storage, store fresh water, often doubling for hydroelectric power generation. Reservoirs are created by controlling a watercourse that drains an existing body of wa ...
of methane is under the seafloor in the form of
methane clathrate Methane clathrate (CH4·5.75H2O) or (4CH4·23H2O), also called methane hydrate, hydromethane, methane ice, fire ice, natural gas hydrate, or gas hydrate, is a solid clathrate compound (more specifically, a clathrate hydrate) in which a large a ...
s. When methane reaches the surface and the
atmosphere An atmosphere () is a layer of gases that envelop an astronomical object, held in place by the gravity of the object. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. A stellar atmosph ...
, it is known as
atmospheric methane Atmospheric methane is the methane present in Earth's atmosphere. The concentration of atmospheric methane is increasing due to methane emissions, and is causing climate change. Methane is one of the most potent greenhouse gases. Methane's radiati ...
. The Earth's atmospheric methane concentration has increased by about 160% since 1750, with the overwhelming percentage caused by human activity. It accounted for 20% of the total
radiative forcing Radiative forcing (or climate forcing) is a concept used to quantify a change to the balance of energy flowing through a planetary atmosphere. Various factors contribute to this change in energy balance, such as concentrations of greenhouse gases ...
from all of the long-lived and globally mixed
greenhouse gas Greenhouse gases (GHGs) are the gases in the atmosphere that raise the surface temperature of planets such as the Earth. Unlike other gases, greenhouse gases absorb the radiations that a planet emits, resulting in the greenhouse effect. T ...
es, according to the 2021
Intergovernmental Panel on Climate Change The Intergovernmental Panel on Climate Change (IPCC) is an intergovernmental body of the United Nations. Its job is to "provide governments at all levels with scientific information that they can use to develop climate policies". The World Met ...
report. Strong, rapid and sustained reductions in methane emissions could limit near-term warming and improve air quality by reducing global surface ozone. Methane has also been detected on other planets, including
Mars Mars is the fourth planet from the Sun. It is also known as the "Red Planet", because of its orange-red appearance. Mars is a desert-like rocky planet with a tenuous carbon dioxide () atmosphere. At the average surface level the atmosph ...
, which has implications for
astrobiology Astrobiology (also xenology or exobiology) is a scientific field within the List of life sciences, life and environmental sciences that studies the abiogenesis, origins, Protocell, early evolution, distribution, and future of life in the univ ...
research.


Properties and bonding

Methane is a
tetrahedral In geometry, a tetrahedron (: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular Face (geometry), faces, six straight Edge (geometry), edges, and four vertex (geometry), vertices. The tet ...
molecule with four equivalent C–H bonds. Its
electronic structure Quantum chemistry, also called molecular quantum mechanics, is a branch of physical chemistry focused on the application of quantum mechanics to chemical systems, particularly towards the quantum-mechanical calculation of electronic contributions ...
is described by four bonding molecular orbitals (MOs) resulting from the overlap of the valence orbitals on C and H. The lowest-energy MO is the result of the overlap of the 2s orbital on carbon with the in-phase combination of the 1s orbitals on the four hydrogen atoms. Above this energy level is a triply degenerate set of MOs that involve overlap of the 2p orbitals on carbon with various linear combinations of the 1s orbitals on hydrogen. The resulting "three-over-one" bonding scheme is consistent with photoelectron spectroscopic measurements. Methane is an odorless, colourless and transparent gas at
standard temperature and pressure Standard temperature and pressure (STP) or standard conditions for temperature and pressure are various standard sets of conditions for experimental measurements used to allow comparisons to be made between different sets of data. The most used ...
. It does absorb visible light, especially at the red end of the spectrum, due to
overtone band In vibrational spectroscopy, an overtone band is the spectral band that occurs in a vibrational spectrum of a molecule when the molecule makes a transition from the ground state (v=0) to the second excited state (v=2), where v is the vibrational ...
s, but the effect is only noticeable if the light path is very long. This is what gives
Uranus Uranus is the seventh planet from the Sun. It is a gaseous cyan-coloured ice giant. Most of the planet is made of water, ammonia, and methane in a Supercritical fluid, supercritical phase of matter, which astronomy calls "ice" or Volatile ( ...
and
Neptune Neptune is the eighth and farthest known planet from the Sun. It is the List of Solar System objects by size, fourth-largest planet in the Solar System by diameter, the third-most-massive planet, and the densest giant planet. It is 17 t ...
their blue or bluish-green colors, as light passes through their atmospheres containing methane and is then scattered back out. The familiar smell of natural gas as used in homes is achieved by the addition of an
odorant An aroma compound, also known as an odorant, aroma, fragrance, flavoring or flavor, is a chemical compound that has a smell or odor. For an individual chemical or class of chemical compounds to impart a smell or fragrance, it must be sufficien ...
, usually blends containing ''tert''-butylthiol, as a safety measure. Methane has a boiling point of −161.5 
°C The degree Celsius is the unit of temperature on the Celsius temperature scale "Celsius temperature scale, also called centigrade temperature scale, scale based on 0 ° for the melting point of water and 100 ° for the boiling point ...
at a pressure of one
atmosphere An atmosphere () is a layer of gases that envelop an astronomical object, held in place by the gravity of the object. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. A stellar atmosph ...
. As a gas, it is
flammable A combustible material is a material that can burn (i.e., sustain a flame) in air under certain conditions. A material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort ...
over a range of concentrations (5.4%–17%) in air at
standard pressure Standard temperature and pressure (STP) or standard conditions for temperature and pressure are various standard sets of conditions for experimental measurements used to allow comparisons to be made between different sets of data. The most used ...
. Solid methane exists in several modifications, of which nine are known. Cooling methane at normal pressure results in the formation of methane I. This substance crystallizes in the cubic system (
space group In mathematics, physics and chemistry, a space group is the symmetry group of a repeating pattern in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of the pattern that ...
Fmm). The positions of the hydrogen atoms are not fixed in methane I, i.e. methane molecules may rotate freely. Therefore, it is a
plastic crystal A plastic crystal is a crystal composed of weakly interacting molecules that possess some orientational or conformational degree of freedom. The name plastic crystal refers to the mechanical softness of such phases: they resemble waxes and are easil ...
.


Chemical reactions

The primary chemical reactions of methane are
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 ...
,
steam reforming Steam reforming or steam methane reforming (SMR) is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly, natural gas is the feedstock. The main purpose of this technology is often hydrogen ...
to
syngas Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide in various ratios. The gas often contains some carbon dioxide and methane. It is principally used for producing ammonia or methanol. Syngas is combustible and can be used as ...
, and
halogenation In chemistry, halogenation is a chemical reaction which introduces one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drug ...
. In general, methane reactions are difficult to control.


Selective oxidation

Partial
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
of methane to
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical compound and the simplest aliphatic Alcohol (chemistry), alcohol, with the chemical formula (a methyl group linked to a hydroxyl group, often ab ...
( C H3 O H), a more convenient, liquid fuel, is challenging because the reaction typically progresses all the way to
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
and
water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...
even with an insufficient supply of
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
. The
enzyme An enzyme () is a protein that acts as a biological catalyst by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different mol ...
methane monooxygenase Methane monooxygenase (MMO) is an enzyme capable of oxidizing the C-H bond in methane as well as other alkanes. Methane monooxygenase belongs to the class of oxidoreductase enzymes (). There are two forms of MMO: the well-studied soluble form (s ...
produces methanol from methane, but cannot be used for industrial-scale reactions. Some homogeneously
catalyzed Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
systems and heterogeneous systems have been developed, but all have significant drawbacks. These generally operate by generating protected products which are shielded from overoxidation. Examples include the Catalytica system, copper
zeolite Zeolites are a group of several microporous, crystalline aluminosilicate minerals commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ・y where is either a meta ...
s, and iron zeolites stabilizing the alpha-oxygen active site. One group of
bacteria Bacteria (; : bacterium) are ubiquitous, mostly free-living organisms often consisting of one Cell (biology), biological cell. They constitute a large domain (biology), domain of Prokaryote, prokaryotic microorganisms. Typically a few micr ...
catalyze methane oxidation with
nitrite The nitrite polyatomic ion, ion has the chemical formula . Nitrite (mostly sodium nitrite) is widely used throughout chemical and pharmaceutical industries. The nitrite anion is a pervasive intermediate in the nitrogen cycle in nature. The name ...
as the
oxidant An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ''electr ...
in the absence of
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
, giving rise to the so-called
anaerobic oxidation of methane Anaerobic oxidation of methane (AOM) is a methane-consuming microbial process occurring in anoxic marine and freshwater sediments. AOM is known to occur among mesophiles, but also in psychrophiles, thermophiles, halophiles, acidophiles, and al ...
.


Acid–base reactions

Like other
hydrocarbon 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 Hydrophobe, hydrophobic; their odor is usually fain ...
s, methane is an extremely
weak acid Acid strength is the tendency of an acid, symbolised by the chemical formula , to dissociate into a proton, , and an anion, . The dissociation or ionization of a strong acid in solution is effectively complete, except in its most concentrated s ...
. Its p''K''a in
DMSO Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula . This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds and is ...
is estimated to be 56. It cannot be
deprotonated Deprotonation (or dehydronation) is the removal (transfer) of a proton (or hydron, or hydrogen cation), (H+) from a Brønsted–Lowry acid in an acid–base reaction.Henry Jakubowski, Biochemistry Online Chapter 2A3, https://employees.csbsju.ed ...
in solution, but the
conjugate base A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid gives a proton () to a base—in other words, it is a base with a hydrogen ion added to it, as it loses a hydrogen ion in the reve ...
is known in forms such as
methyllithium Methyllithium is the simplest organolithium reagent, with the empirical formula LiCH3. This s-block organometallic compound adopts an oligomeric structure both in solution and in the solid state. This highly reactive compound, invariably used i ...
. A variety of
positive ions An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
derived from methane have been observed, mostly as unstable species in low-pressure gas mixtures. These include
methenium In organic chemistry, methenium (also called methylium, carbenium, methyl cation, or protonated methylene) is a cation with the formula . It can be viewed as a methylene radical (:) with an added proton (), or as a methyl radical (•) with one ...
or methyl cation , methane cation , and
methanium In chemistry, methanium is a complex positive ion with formula (metastable transitional form, a carbon atom covalently bonded to five hydrogen atoms) or (fluxional form, namely a molecule with one carbon atom covalently bonded to three hydro ...
or protonated methane . Some of these have been detected in outer space. Methanium can also be produced as diluted solutions from methane with
superacid In chemistry, a superacid (according to the original definition) is an acid with an acidity greater than that of 100% pure sulfuric acid (), which has a Hammett acidity function (''H''0) of −12. According to the modern definition, a superacid i ...
s.
Cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s with higher charge, such as and , have been studied theoretically and conjectured to be stable. Despite the
strength Strength may refer to: Personal trait *Physical strength, as in people or animals *Character strengths like those listed in the Values in Action Inventory *The exercise of willpower Physics * Mechanical strength, the ability to withstand ...
of its C–H bonds, there is intense interest in
catalysts Catalysis () is the increase in reaction rate, rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst ...
that facilitate C–H bond activation in methane (and other lower numbered
alkanes In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in whi ...
).


Combustion

Methane's
heat of combustion The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it. The ''calorific value'' is the total energy relea ...
is 55.5 MJ/kg.
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 ...
of methane is a multiple step reaction summarized as follows: : :Δ''H'' = −802 kJ/ mol, at standard conditions (for water vapor, Δ''H'' = −891 kJ/ mol for liquid water)
Peters four-step chemistry Peters four-step chemistry is a systematically reduced mechanism for methane combustion, named after Norbert Peters, who derived it in 1985. The mechanism reads as :\begin & \text && \ce \\ & \text && \ce \\ & \text && \ce \\ & \text && \ce ...
is a systematically reduced four-step chemistry that explains the burning of methane.


Methane radical reactions

Given appropriate conditions, methane reacts with
halogen The halogens () are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would ...
radicals Radical (from Latin: ', root) may refer to: Politics and ideology Politics *Classical radicalism, the Radical Movement that began in late 18th century Britain and spread to continental Europe and Latin America in the 19th century *Radical politics ...
as follows: : : where X is a
halogen The halogens () are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would ...
:
fluorine Fluorine is a chemical element; it has Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard temperature and pressure, standard conditions as pale yellow Diatomic molecule, diatomic gas. Fluorine is extre ...
(F),
chlorine Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
(Cl),
bromine Bromine is a chemical element; it has chemical symbol, symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between th ...
(Br), or
iodine Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at , and boils to a vi ...
(I). This mechanism for this process is called
free radical halogenation In organic chemistry, free-radical halogenation is a type of halogenation. This chemical reaction is typical of alkanes and alkyl-substituted aromatics under application of UV light. The reaction is used for the industrial synthesis of chloroform ...
. It is initiated when
UV light Ultraviolet radiation, also known as simply UV, is electromagnetic radiation of wavelengths of 10–400 nanometers, shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight and constitutes about 10% of t ...
or some other
radical initiator In chemistry, radical initiators are substances that can produce radical species under mild conditions and promote radical reactions. These substances generally possess weak bonds—bonds that have small bond dissociation energies. Radical in ...
(like
peroxides In chemistry, peroxides are a group of compounds with the structure , where the R's represent a radical (a portion of a complete molecule; not necessarily a free radical) and O's are single oxygen atoms. Oxygen atoms are joined to each other and ...
) produces a halogen
atom Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
. A two-step
chain reaction A chain reaction is a sequence of reactions where a reactive product or by-product causes additional reactions to take place. In a chain reaction, positive feedback leads to a self-amplifying chain of events. Chain reactions are one way that sys ...
ensues in which the halogen atom abstracts a hydrogen atom from a methane molecule, resulting in the formation of a
hydrogen halide In chemistry, hydrogen halides (hydrohalic acids when in the aqueous phase) are diatomic, inorganic compounds that function as Arrhenius acids. The formula is HX where X is one of the halogens: fluorine, chlorine, bromine, iodine, astatine, or ...
molecule and a
methyl radical Methyl radical is an organic compound with the chemical formula (also written as •). It is a metastable colourless gas, which is mainly produced ''in situ'' as a precursor to other hydrocarbons in the petroleum cracking industry. It can act as ...
(). The methyl radical then reacts with a molecule of the halogen to form a molecule of the halomethane, with a new halogen atom as byproduct. Similar reactions can occur on the halogenated product, leading to replacement of additional hydrogen atoms by halogen atoms with
dihalomethane The dihalomethanes are organic compounds in which two hydrogen atoms in methane are replaced by halogen atoms. They belong to the haloalkanes, specifically the subgroup of halomethanes, and contains ten members. There are four members with only one ...
,
trihalomethane In chemistry, trihalomethanes (THMs) are chemical compounds in which three of the four hydrogen atoms of methane () are replaced by halogen atoms. Trihalomethanes with all the same halogen atoms are called haloforms. Many trihalomethanes find uses ...
, and ultimately,
tetrahalomethane Tetrahalomethanes are fully halogenated methane derivatives of general formula CFkCllBrmInAtp, where:k+l+m+n+p=4Tetrahalomethanes are on the border of inorganic and organic chemistry, thus they can be assigned both inorganic and organic names by I ...
structures, depending upon reaction conditions and the halogen-to-methane ratio. This reaction is commonly used with chlorine to produce
dichloromethane Dichloromethane (DCM, methylene chloride, or methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odor is widely used as a solvent. Although it is not miscible with ...
and
chloroform Chloroform, or trichloromethane (often abbreviated as TCM), is an organochloride with the formula and a common solvent. It is a volatile, colorless, sweet-smelling, dense liquid produced on a large scale as a precursor to refrigerants and po ...
via
chloromethane Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula . One of the haloalkanes, it is a colorless, sweet-smelling, flammable gas. Methyl chloride is a crucial reagent in indu ...
.
Carbon tetrachloride Carbon tetrachloride, also known by many other names (such as carbon tet for short and tetrachloromethane, also IUPAC nomenclature of inorganic chemistry, recognised by the IUPAC), is a chemical compound with the chemical formula CCl4. It is a n ...
can be made with excess chlorine.


Uses

Methane may be transported as a refrigerated liquid (liquefied natural gas, or
LNG Liquefied natural gas (LNG) is natural gas (predominantly methane, CH4, with some mixture of ethane, C2H6) that has been cooled to liquid form for ease and safety of non-pressurized storage or transport. It takes up about 1/600th the volume o ...
). While leaks from a refrigerated liquid container are initially heavier than air due to the increased density of the cold gas, the gas at ambient temperature is lighter than air. Gas pipelines distribute large amounts of natural gas, of which methane is the principal component.


Fuel

Methane is used as a
fuel A fuel is any material that can be made to react with other substances so that it releases energy as thermal energy or to be used for work (physics), work. The concept was originally applied solely to those materials capable of releasing chem ...
for ovens, homes, water heaters, kilns, automobiles, turbines, etc. As the major constituent of
natural gas Natural gas (also fossil gas, methane gas, and gas) is a naturally occurring compound of gaseous hydrocarbons, primarily methane (95%), small amounts of higher alkanes, and traces of carbon dioxide and nitrogen, hydrogen sulfide and helium ...
, methane is important for
electricity generation Electricity generation is the process of generating electric power from sources of primary energy. For electric utility, utilities in the electric power industry, it is the stage prior to its Electricity delivery, delivery (Electric power transm ...
by burning it as a fuel in a
gas turbine A gas turbine or gas turbine engine is a type of Internal combustion engine#Continuous combustion, continuous flow internal combustion engine. The main parts common to all gas turbine engines form the power-producing part (known as the gas gene ...
or
steam generator Steam is water vapor, often mixed with air or an aerosol of liquid water droplets. This may occur due to evaporation or due to boiling, where heat is applied until water reaches the enthalpy of vaporization. Saturated or superheated steam is inv ...
. Compared to other hydrocarbon fuels, methane produces less
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
for each unit of heat released. At about 891 kJ/mol, methane's
heat of combustion The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it. The ''calorific value'' is the total energy relea ...
is lower than that of any other hydrocarbon, but the ratio of the heat of combustion (891 kJ/mol) to the molecular mass (16.0 g/mol, of which 12.0 g/mol is carbon) shows that methane, being the simplest hydrocarbon, produces more heat per mass unit (55.7 kJ/g) than other complex hydrocarbons. In many areas with a dense enough population, methane is piped into homes and businesses for
heating In thermodynamics, heat is energy in transfer between a thermodynamic system and its surroundings by such mechanisms as thermal conduction, electromagnetic radiation, and friction, which are microscopic in nature, involving sub-atomic, atom ...
, cooking, and industrial uses. In this context it is usually known as
natural gas Natural gas (also fossil gas, methane gas, and gas) is a naturally occurring compound of gaseous hydrocarbons, primarily methane (95%), small amounts of higher alkanes, and traces of carbon dioxide and nitrogen, hydrogen sulfide and helium ...
, which is considered to have an energy content of 39
megajoule The joule ( , or ; symbol: J) is the unit of energy in the International System of Units (SI). In terms of SI base units, one joule corresponds to one kilogram- metre squared per second squared One joule is equal to the amount of work don ...
s per cubic meter, or 1,000
BTU The British thermal unit (Btu) is a measure of heat, which is a form of energy. It was originally defined as the amount of heat required to raise the temperature of one pound of water by one degree Fahrenheit. It is also part of the United Stat ...
per
standard cubic foot A standard cubic foot (scf) is a unit representing the amount of gas (such as natural gas) contained in a volume of one cubic foot at reference temperature and pressure conditions. It is the unit commonly used when following the United States ...
.
Liquefied natural gas Liquefied natural gas (LNG) is natural gas (predominantly methane, CH4, with some mixture of ethane, C2H6) that has been cooled to liquid form for ease and safety of non-pressurized storage or transport. It takes up about 1/600th the volume o ...
(LNG) is predominantly methane () converted into liquid form for ease of storage or transport.


Rocket propellant

Refined liquid methane as well as LNG is used as a
rocket fuel Rocket propellant is used as reaction mass ejected from a rocket engine to produce thrust. The energy required can either come from the propellants themselves, as with a chemical rocket, or from an external source, as with ion engines. Overvi ...
, when combined with
liquid oxygen Liquid oxygen, sometimes abbreviated as LOX or LOXygen, is a clear cyan liquid form of dioxygen . It was used as the oxidizer in the first liquid-fueled rocket invented in 1926 by Robert H. Goddard, an application which is ongoing. Physical ...
, as in the
TQ-12 The TQ-12 (, lit. ''Sky Lark 12'') is a gas-generator cycle rocket engine burning liquid methane and liquid oxygen (methalox) developed by LandSpace. TQ-12 is the first Chinese liquid rocket engine developed with private funding. The engine has b ...
,
BE-4 The BE-4 (Blue Engine 4) is a liquid rocket engine developed by Blue Origin. It uses an oxygen-rich, liquefied natural gas, liquefied methane fuel and operates on a staged combustion cycle. The BE-4 produces of thrust at sea level. Developmen ...
,
Raptor Raptor(s) or RAPTOR may refer to: Animals The word "raptor" refers to several groups of avian and non-avian dinosaurs which primarily capture and subdue/kill prey with their talons. * Raptor (bird) or bird of prey, a bird that primarily hunt ...
,
YF-215 The YF-215 is a liquid cryogenic rocket engine burning liquid methane and liquid oxygen in a full-flow staged combustion cycle The staged combustion cycle (sometimes known as topping cycle, preburner cycle, or closed cycle) is a Liquid-propel ...
, and
Aeon The word aeon , also spelled eon (in American and Australian English), originally meant "life", "vital force" or "being", "generation" or "a period of time", though it tended to be translated as "age" in the sense of "ages", "forever", "timele ...
engines. Due to the similarities between methane and LNG such engines are commonly grouped together under the term ''methalox''. As a
liquid rocket propellant The highest specific impulse chemical rockets use liquid propellants (liquid-propellant rockets). They can consist of a single chemical (a monopropellant) or a mix of two chemicals, called bipropellants. Bipropellants can further be divided into ...
, a methane/
liquid oxygen Liquid oxygen, sometimes abbreviated as LOX or LOXygen, is a clear cyan liquid form of dioxygen . It was used as the oxidizer in the first liquid-fueled rocket invented in 1926 by Robert H. Goddard, an application which is ongoing. Physical ...
combination offers the advantage over
kerosene Kerosene, or paraffin, is a combustibility, combustible hydrocarbon liquid which is derived from petroleum. It is widely used as a fuel in Aviation fuel, aviation as well as households. Its name derives from the Greek (''kērós'') meaning " ...
/
liquid oxygen Liquid oxygen, sometimes abbreviated as LOX or LOXygen, is a clear cyan liquid form of dioxygen . It was used as the oxidizer in the first liquid-fueled rocket invented in 1926 by Robert H. Goddard, an application which is ongoing. Physical ...
combination, or kerolox, of producing small exhaust molecules, reducing coking or deposition of
soot Soot ( ) is a mass of impure carbon particles resulting from the incomplete combustion of hydrocarbons. Soot is considered a hazardous substance with carcinogenic properties. Most broadly, the term includes all the particulate matter produced b ...
on engine components. Methane is easier to store than hydrogen due to its higher boiling point and density, as well as its lack of
hydrogen embrittlement Hydrogen embrittlement (HE), also known as hydrogen-assisted cracking or hydrogen-induced cracking (HIC), is a reduction in the ductility of a metal due to absorbed hydrogen. Hydrogen atoms are small and can Permeation, permeate solid metals. O ...
. The lower
molecular weight A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
of the exhaust also increases the fraction of the heat energy which is in the form of kinetic energy available for propulsion, increasing the
specific impulse Specific impulse (usually abbreviated ) is a measure of how efficiently a reaction mass engine, such as a rocket engine, rocket using propellant or a jet engine using fuel, generates thrust. In general, this is a ratio of the ''Impulse (physics), ...
of the rocket. Compared to
liquid hydrogen Liquid hydrogen () is the liquid state of the element hydrogen. Hydrogen is found naturally in the molecule, molecular H2 form. To exist as a liquid, H2 must be cooled below its critical point (thermodynamics), critical point of 33 Kelvins, ...
, the
specific energy Specific energy or massic energy is energy per unit mass. It is also sometimes called gravimetric energy density, which is not to be confused with energy density, which is defined as energy per unit volume. It is used to quantify, for example, st ...
of methane is lower but this disadvantage is offset by methane's greater density and temperature range, allowing for smaller and lighter tankage for a given fuel mass. Liquid methane has a temperature range (91–112 K) nearly compatible with
liquid oxygen Liquid oxygen, sometimes abbreviated as LOX or LOXygen, is a clear cyan liquid form of dioxygen . It was used as the oxidizer in the first liquid-fueled rocket invented in 1926 by Robert H. Goddard, an application which is ongoing. Physical ...
(54–90 K). The fuel currently sees use in operational launch vehicles such as
Zhuque-2 Zhuque-2 (, ''ZQ-2'') is a Chinese medium-class orbital launch vehicle developed by LandSpace. It is a liquid-fuelled rocket powered by liquid oxygen and liquid methane (methalox) and was the first methane-fueled rocket to reach orbit. Des ...
, Vulcan and
New Glenn New Glenn is a heavy-lift launch vehicle developed and operated by the American company Blue Origin. The rocket is designed to have a Reusable launch vehicle, partially reusable, two-stage design with a diameter of . The first stage is powered ...
as well as in-development launchers such as
Starship A starship, starcraft, or interstellar spacecraft is a theoretical spacecraft designed for interstellar travel, traveling between planetary systems. The term is mostly found in science fiction. Reference to a "star-ship" appears as early as 1 ...
,
Neutron The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The Discovery of the neutron, neutron was discovered by James Chadwick in 1932, leading to the discovery of nucle ...
,
Terran R Terran R is a Heavy-lift launch vehicle, heavy-lift two-stage, partially reusable launch vehicle under development by Relativity Space. The vehicle is partially constructed with 3D printing technologies, like its predecessor, the small-lift Terra ...
,
Nova A nova ( novae or novas) is a transient astronomical event that causes the sudden appearance of a bright, apparently "new" star (hence the name "nova", Latin for "new") that slowly fades over weeks or months. All observed novae involve white ...
, and
Long March 9 Long March 9 (, LM-9 or Changzheng 9, CZ-9) is a Chinese Super heavy-lift launch vehicle, super-heavy carrier rocket that is currently under development. It is the ninth iteration of the Long March (rocket family), Long March rocket family, named ...
.


Chemical feedstock

Natural gas Natural gas (also fossil gas, methane gas, and gas) is a naturally occurring compound of gaseous hydrocarbons, primarily methane (95%), small amounts of higher alkanes, and traces of carbon dioxide and nitrogen, hydrogen sulfide and helium ...
, which is mostly composed of methane, is used to produce hydrogen gas on an industrial scale.
Steam methane reforming Steam reforming or steam methane reforming (SMR) is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly, natural gas is the feedstock. The main purpose of this technology is often hydrogen ...
(SMR), or simply known as steam reforming, is the standard industrial method of producing commercial bulk hydrogen gas. More than 50 million metric tons are produced annually worldwide (2013), principally from the SMR of natural gas. Much of this hydrogen is used in
petroleum Petroleum, also known as crude oil or simply oil, is a naturally occurring, yellowish-black liquid chemical mixture found in geological formations, consisting mainly of hydrocarbons. The term ''petroleum'' refers both to naturally occurring un ...
refineries A refinery is a production facility composed of a group of chemical engineering unit processes and unit operations refining certain materials or converting raw material into products of value. Types of refineries Different types of refineries a ...
, in the production of chemicals and in food processing. Very large quantities of hydrogen are used in the industrial synthesis of ammonia. At high temperatures (700–1100 °C) and in the presence of a
metal A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, electricity and thermal conductivity, heat relatively well. These properties are all associated wit ...
-based
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
(
nickel Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...
), steam reacts with methane to yield a mixture of CO and , known as "water gas" or "
syngas Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide in various ratios. The gas often contains some carbon dioxide and methane. It is principally used for producing ammonia or methanol. Syngas is combustible and can be used as ...
": : This reaction is strongly
endothermic An endothermic process is a chemical or physical process that absorbs heat from its surroundings. In terms of thermodynamics, it is a thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, ...
(consumes heat, 206 kJ/mol). Additional hydrogen is obtained by the reaction of CO with water via the
water-gas shift reaction Water gas is a kind of fuel gas, a mixture of carbon monoxide and hydrogen. It is produced by "alternately hot blowing a fuel layer okewith air and gasifying it with steam". The caloric yield of the fuel produced by this method is about 10% o ...
: : This reaction is mildly
exothermic In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity (e ...
(produces heat, −41 kJ/mol). Methane is also subjected to free-radical chlorination in the production of chloromethanes, although
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical compound and the simplest aliphatic Alcohol (chemistry), alcohol, with the chemical formula (a methyl group linked to a hydroxyl group, often ab ...
is a more typical precursor.Rossberg, M. ''et al.'' (2006) "Chlorinated Hydrocarbons" in ''Ullmann's Encyclopedia of Industrial Chemistry'', Wiley-VCH, Weinheim. . Hydrogen can also be produced via the direct decomposition of methane, also known as methane
pyrolysis Pyrolysis is a process involving the Bond cleavage, separation of covalent bonds in organic matter by thermal decomposition within an Chemically inert, inert environment without oxygen. Etymology The word ''pyrolysis'' is coined from the Gree ...
, which, unlike steam reforming, produces no
greenhouse gas Greenhouse gases (GHGs) are the gases in the atmosphere that raise the surface temperature of planets such as the Earth. Unlike other gases, greenhouse gases absorb the radiations that a planet emits, resulting in the greenhouse effect. T ...
es (GHG). The heat needed for the reaction can also be GHG emission free, e.g. from concentrated sunlight, renewable electricity, or burning some of the produced hydrogen. If the methane is from
biogas Biogas is a gaseous renewable energy source produced from raw materials such as agricultural waste, manure, municipal waste, plant material, sewage, green waste, Wastewater treatment, wastewater, and food waste. Biogas is produced by anaerobic ...
then the process can be a
carbon sink A carbon sink is a natural or artificial carbon sequestration process that "removes a  greenhouse gas, an aerosol or a precursor of a greenhouse gas from the atmosphere". These sinks form an important part of the natural carbon cycle. An overar ...
. Temperatures in excess of 1200 °C are required to break the bonds of methane to produce hydrogen gas and solid carbon. However, through the use of a suitable catalyst the reaction temperature can be reduced to between 550 and 900 °C depending on the chosen catalyst. Dozens of catalysts have been tested, including unsupported and supported metal catalysts, carbonaceous and metal-carbon catalysts. The reaction is moderately endothermic as shown in the reaction equation below. : :( 74.8
kJ/mol The joule per mole (symbol: J·mol−1 or J/mol) is the unit of energy per amount of substance in the International System of Units (SI), such that energy is measured in joules, and the amount of substance is measured in moles. It is also an SI ...
)


Refrigerant

As a
refrigerant A refrigerant is a working fluid used in the cooling, heating, or reverse cooling/heating cycles of air conditioning systems and heat pumps, where they undergo a repeated phase transition from a liquid to a gas and back again. Refrigerants are ...
, methane has the
ASHRAE The American Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE ) is an American professional association seeking to advance heating, ventilation, air conditioning and refrigeration (HVAC&R) systems design and constructio ...
designation R-50.


Generation

Methane can be generated through geological, biological or industrial routes.


Geological routes

The two main routes for geological methane generation are (i) organic (thermally generated, or thermogenic) and (ii) inorganic (
abiotic In biology and ecology, abiotic components or abiotic factors are non-living chemical and physical parts of the environment that affect living organisms and the functioning of ecosystems. Abiotic factors and the phenomena associated with them und ...
). Thermogenic methane occurs due to the breakup of organic matter at elevated temperatures and pressures in deep sedimentary
strata In geology and related fields, a stratum (: strata) is a layer of Rock (geology), rock or sediment characterized by certain Lithology, lithologic properties or attributes that distinguish it from adjacent layers from which it is separated by v ...
. Most methane in sedimentary basins is thermogenic; therefore, thermogenic methane is the most important source of natural gas. Thermogenic methane components are typically considered to be relic (from an earlier time). Generally, formation of thermogenic methane (at depth) can occur through organic matter breakup, or organic synthesis. Both ways can involve microorganisms (
methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. It is the fourth and final stage of anaerobic digestion. Organisms capable of producing methane for energy conservation h ...
), but may also occur inorganically. The processes involved can also consume methane, with and without microorganisms. The more important source of methane at depth (crystalline bedrock) is abiotic. Abiotic means that methane is created from inorganic compounds, without biological activity, either through magmatic processes or via water-rock reactions that occur at low temperatures and pressures, like
serpentinization Serpentinization is a hydration and Metamorphic rock, metamorphic transformation of ferromagnesian minerals, such as olivine and pyroxene, in mafic and ultramafic rock to produce serpentinite. Minerals formed by serpentinization include the Serp ...
.


Biological routes

Most of Earth's methane is
biogenic A biogenic substance is a product made by or of life forms. While the term originally was specific to metabolite compounds that had toxic effects on other organisms, it has developed to encompass any constituents, secretions, and metabolites of p ...
and is produced by
methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. It is the fourth and final stage of anaerobic digestion. Organisms capable of producing methane for energy conservation h ...
,Lessner, Daniel J. (Dec 2009) Methanogenesis Biochemistry. In: eLS. John Wiley & Sons Ltd, Chichester. http://www.els.net a form of anaerobic respiration only known to be conducted by some members of the domain
Archaea Archaea ( ) is a Domain (biology), domain of organisms. Traditionally, Archaea only included its Prokaryote, prokaryotic members, but this has since been found to be paraphyletic, as eukaryotes are known to have evolved from archaea. Even thou ...
. Methanogens occur in
landfill A landfill is a site for the disposal of waste materials. It is the oldest and most common form of waste disposal, although the systematic burial of waste with daily, intermediate and final covers only began in the 1940s. In the past, waste was ...
s and
soils Soil, also commonly referred to as earth, is a mixture of organic matter, minerals, gases, water, and organisms that together support the life of plants and soil organisms. Some scientific definitions distinguish dirt from ''soil'' by restri ...
,
ruminants Ruminants are herbivorous grazing or browsing artiodactyls belonging to the suborder Ruminantia that are able to acquire nutrients from plant-based food by Enteric fermentation, fermenting it in a specialized stomach prior to digestion, principa ...
(for example,
cattle Cattle (''Bos taurus'') are large, domesticated, bovid ungulates widely kept as livestock. They are prominent modern members of the subfamily Bovinae and the most widespread species of the genus '' Bos''. Mature female cattle are calle ...
), the guts of termites, and the
anoxic Anoxia means a total depletion in the level of oxygen, an extreme form of hypoxia or "low oxygen". The terms anoxia and hypoxia are used in various contexts: * Anoxic waters, sea water, fresh water or groundwater that are depleted of dissolved ox ...
sediments below the seafloor and the bottom of lakes. This multistep process is used by these microorganisms for energy. The net reaction of methanogenesis is: : The final step in the process is catalyzed by the enzyme
methyl coenzyme M reductase In enzymology, coenzyme-B sulfoethylthiotransferase, also known as methyl-coenzyme M reductase (MCR) or most systematically as 2-(methylthio)ethanesulfonate:N-(7-thioheptanoyl)-3-O-phosphothreonine S-(2-sulfoethyl)thiotransferase is an enzyme that ...
(MCR).


Wetlands

Wetlands are the largest natural sources of methane to the atmosphere, accounting for approximately 20 – 30% of atmospheric methane. Climate change is increasing the amount of methane released from wetlands due to increased temperatures and altered rainfall patterns. This phenomenon is called ''wetland methane feedback''.
Rice Rice is a cereal grain and in its Domestication, domesticated form is the staple food of over half of the world's population, particularly in Asia and Africa. Rice is the seed of the grass species ''Oryza sativa'' (Asian rice)—or, much l ...
cultivation generates as much as 12% of total global methane emissions due to the long-term flooding of rice fields.


Ruminants

Ruminants such as cattle belch out methane, accounting for about 22% of the U.S. annual methane emissions to the atmosphere. One study reported that the livestock sector in general (primarily cattle, chickens, and pigs) produces 37% of all human-induced methane. A 2013 study estimated that livestock accounted for 44% of human-induced methane and about 15% of human-induced greenhouse gas emissions. Many efforts are underway to reduce livestock methane production, such as medical treatments and dietary adjustments, and to trap the gas to use its combustion energy.


Seafloor sediments

Most of the subseafloor is
anoxic Anoxia means a total depletion in the level of oxygen, an extreme form of hypoxia or "low oxygen". The terms anoxia and hypoxia are used in various contexts: * Anoxic waters, sea water, fresh water or groundwater that are depleted of dissolved ox ...
because oxygen is removed by
aerobic Aerobic means "requiring air," in which "air" usually means oxygen. Aerobic may also refer to * Aerobic exercise, prolonged exercise of moderate intensity * Aerobics, a form of aerobic exercise * Aerobic respiration, the aerobic process of cellu ...
microorganisms within the first few centimeters of the
sediment Sediment is a solid material that is transported to a new location where it is deposited. It occurs naturally and, through the processes of weathering and erosion, is broken down and subsequently sediment transport, transported by the action of ...
. Below the oxygen-replete seafloor, methanogens produce methane that is either used by other organisms or becomes trapped in Clathrate hydrate, gas hydrates. These other organisms that utilize methane for energy are known as methanotrophs ('methane-eating'), and are the main reason why little methane generated at depth reaches the sea surface. Consortia of Archaea and Bacteria have been found to oxidize methane via
anaerobic oxidation of methane Anaerobic oxidation of methane (AOM) is a methane-consuming microbial process occurring in anoxic marine and freshwater sediments. AOM is known to occur among mesophiles, but also in psychrophiles, thermophiles, halophiles, acidophiles, and al ...
(AOM); the organisms responsible for this are anaerobic methanotrophic Archaea (ANME) and Sulfate-reducing microorganism, sulfate-reducing bacteria (SRB).


Industrial routes

Given its cheap abundance in natural gas, there is little incentive to produce methane industrially. Methane can be produced by hydrogenation, hydrogenating carbon dioxide through the Sabatier process. Methane is also a side product of the hydrogenation of carbon monoxide in the Fischer–Tropsch process, which is practiced on a large scale to produce longer-chain molecules than methane. An example of large-scale coal-to-methane gasification is the Great Plains Synfuels plant, started in 1984 in Beulah, North Dakota as a way to develop abundant local resources of low-grade lignite, a resource that is otherwise difficult to transport for its weight, Coal assay#Ash, ash content, low calorific value and propensity to spontaneous combustion during storage and transport. A number of similar plants exist around the world, although mostly these plants are targeted towards the production of long chain alkanes for use as gasoline, Diesel fuel, diesel, or feedstock to other processes. Power to gas#Power to methane, Power to methane is a technology that uses electricity, electrical power to produce hydrogen from water by electrolysis and uses the Sabatier reaction to combine hydrogen with
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
to produce methane.


Laboratory synthesis

Methane can be produced by protonation of methyl lithium or a methyl Grignard reagent such as methylmagnesium chloride. It can also be made from anhydrous sodium acetate and dry sodium hydroxide, mixed and heated above 300 °C (with sodium carbonate as byproduct). In practice, a requirement for pure methane can easily be fulfilled by steel gas bottle from standard gas suppliers.


Occurrence

Methane is the major component of natural gas, about 87% by volume. The major source of methane is extraction from geological deposits known as natural gas fields, with coal seam gas extraction becoming a major source (see coal bed methane extraction, a method for extracting methane from a coal deposit, while enhanced coal bed methane recovery is a method of recovering methane from non-mineable coal seams). It is associated with other
hydrocarbon 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 Hydrophobe, hydrophobic; their odor is usually fain ...
fuels, and sometimes accompanied by helium and nitrogen. Methane is produced at shallow levels (low pressure) by anaerobic organism, anaerobic Decomposition, decay of organic matter and reworked methane from deep under the Earth's surface. In general, the sediments that generate natural gas are buried deeper and at higher temperatures than those that contain Petroleum, oil. Methane is generally transported in bulk by Pipeline transport, pipeline in its natural gas form, or by LNG carriers in its liquefied form; few countries transport it by truck.


Atmospheric methane and climate change

Methane is an important
greenhouse gas Greenhouse gases (GHGs) are the gases in the atmosphere that raise the surface temperature of planets such as the Earth. Unlike other gases, greenhouse gases absorb the radiations that a planet emits, resulting in the greenhouse effect. T ...
, responsible for around 30% of the rise in global temperatures since the industrial revolution. Methane has a global warming potential (GWP) of 29.8 ± 11 compared to (potential of 1) over a 100-year period, and 82.5 ± 25.8 over a 20-year period. This means that, for example, a Fugitive gas emissions, leak of one tonne of methane is equivalent to emitting 82.5 tonnes of carbon dioxide. Burning methane and producing carbon dioxide also reduces the greenhouse gas impact compared to simply venting methane to the atmosphere. As methane is gradually converted into carbon dioxide (and water) in the atmosphere, these values include the climate forcing from the carbon dioxide produced from methane over these timescales. Annual global methane emissions are currently approximately 580 Mt, 40% of which is from natural sources and the remaining 60% originating from human activity, known as anthropogenic emissions. The largest anthropogenic source is agriculture, responsible for around one quarter of emissions, closely followed by the Energy industry, energy sector, which includes emissions from coal, oil, natural gas and biofuels. Keeling Curve, Historic methane concentrations in the world's atmosphere have ranged between 300 and 400 nmol/mol during glacial periods commonly known as ice ages, and between 600 and 700 nmol/mol during the warm interglacial periods. A 2012 NASA website said the oceans were a potential important source of Arctic methane, but more recent studies associate increasing methane levels as caused by human activity. Global monitoring of atmospheric methane concentrations began in the 1980s. The Earth's atmospheric methane concentration has increased 160% since preindustrial levels in the mid-18th century. In 2013, atmospheric methane accounted for 20% of the total
radiative forcing Radiative forcing (or climate forcing) is a concept used to quantify a change to the balance of energy flowing through a planetary atmosphere. Various factors contribute to this change in energy balance, such as concentrations of greenhouse gases ...
from all of the long-lived and globally mixed greenhouse gases. Between 2011 and 2019 the annual average increase of methane in the atmosphere was 1866 ppb. From 2015 to 2019 sharp rises in levels of atmospheric methane were recorded. In 2019, the atmospheric methane concentration was higher than at any time in the last 800,000 years. As stated in the IPCC Sixth Assessment Report, AR6 of the Intergovernmental Panel on Climate Change, IPCC, "Since 1750, increases in (47%) and (156%) concentrations far exceed, and increases in (23%) are similar to, the natural multi-millennial changes between glacial and interglacial periods over at least the past 800,000 years (very high confidence)". In February 2020, it was reported that fugitive emissions and gas venting from the fossil fuel industry may have been significantly underestimated. The largest annual increase occurred in 2021 with the overwhelming percentage caused by human activity. Climate change can increase atmospheric methane levels by increasing methane production in natural ecosystems, forming a climate change feedback. Another explanation for the rise in methane emissions could be a slowdown of the chemical reaction that removes methane from the atmosphere. Over 100 countries have signed th
Global Methane Pledge
launched in 2021, promising to cut their methane emissions by 30% by 2030. This could avoid 0.2 °C of warming globally by 2050, although there have been calls for higher commitments in order to reach this target. The International Energy Agency's 2022 report states "the most cost-effective opportunities for methane abatement are in the energy sector, especially in oil and gas operations".


Clathrates

Methane clathrates (also known as methane hydrates) are solid cages of water molecules that trap single molecules of methane. Significant reservoirs of methane clathrates have been found in arctic permafrost and along continental margins beneath the Seabed, ocean floor within the Gas hydrate stability zone, gas clathrate stability zone, located at high pressures (1 to 100 MPa; lower end requires lower temperature) and low temperatures (< 15 °C; upper end requires higher pressure). Methane clathrates can form from biogenic methane, thermogenic methane, or a mix of the two. These deposits are both a potential source of methane fuel as well as a potential contributor to global warming.Miller, G. Tyler (2007). ''Sustaining the Earth: An Integrated Approach''. U.S.: Thomson Advantage Books, p. 160. The global mass of carbon stored in gas clathrates is still uncertain and has been estimated as high as 12,500 Gigaton, Gt carbon and as low as 500 Gt carbon. The estimate has declined over time with a most recent estimate of ≈1800 Gt carbon. A large part of this uncertainty is due to our knowledge gap in sources and sinks of methane and the distribution of methane clathrates at the global scale. For example, a source of methane was discovered relatively recently in an Mid-ocean ridge, ultraslow spreading ridge in the Arctic. Some climate models suggest that today's methane emission regime from the ocean floor is potentially similar to that during the period of the Paleocene–Eocene Thermal Maximum (PETM) around 55.5 million years ago, although there are no data indicating that methane from clathrate dissociation currently reaches the atmosphere. Arctic methane release from permafrost and seafloor methane clathrates is a potential consequence and further cause of global warming; this is known as the clathrate gun hypothesis. Data from 2016 indicate that Arctic permafrost thaws faster than predicted.


Public safety and the environment

Methane "degrades air quality and adversely impacts human health, agricultural yields, and ecosystem productivity". Methane is extremely flammable and may form explosive mixtures with air. Methane gas explosions are responsible for many deadly mining disasters. A methane gas explosion was the cause of the Upper Big Branch Mine disaster, Upper Big Branch coal mine disaster in West Virginia on April 5, 2010, killing 29. Natural gas accidental release has also been a major focus in the field of safety engineering, due to past accidental releases that concluded in the formation of jet fire disasters. The 2015–2016 Aliso Canyon gas leak, methane gas leak in Aliso Canyon, California was considered to be the worst in terms of its environmental effect in American history. It was also described as more damaging to the environment than Deepwater Horizon oil spill, Deepwater Horizon's leak in the Gulf of Mexico. In May 2023 ''The Guardian'' published a report blaming Turkmenistan as the worst in the world for methane ''super emitting''. The data collected by Kayrros researchers indicate that two large Turkmen fossil fuel fields Methane leak, leaked 2.6 million and 1.8 million metric tonnes of methane in 2022 alone, pumping the Carbon dioxide, equivalent of 366 million tonnes into the atmosphere, surpassing the annual emissions of the United Kingdom. Methane is also an asphyxiant gas, asphyxiant if the oxygen concentration is reduced to below about 16% by displacement, as most people can Cabin pressurization#Need for cabin pressurization, tolerate a reduction from 21% to 16% without ill effects. The concentration of methane at which asphyxiation risk becomes significant is much higher than the 5–15% concentration in a flammable or explosive mixture. Methane off-gas can penetrate the interiors of buildings near landfills and expose occupants to significant levels of methane. Some buildings have specially engineered recovery systems below their basements to actively capture this gas and vent it away from the building.


Extraterrestrial methane


Interstellar medium

Methane is abundant in many parts of the Solar System and potentially could be harvested on the surface of another Solar System body (in particular, using In situ resource utilization, methane production from local materials found on
Mars Mars is the fourth planet from the Sun. It is also known as the "Red Planet", because of its orange-red appearance. Mars is a desert-like rocky planet with a tenuous carbon dioxide () atmosphere. At the average surface level the atmosph ...
or Titan (moon), Titan), providing fuel for a return journey. Negative methane, the Ion, negative ion of methane, is also known to exist in interstellar space. Its mechanism of formation is not fully understood.


Mars

Methane has been detected on all planets of the Solar System and most of the larger moons. With the possible exception of Life on Mars, Mars, it is believed to have come from Abiogenic petroleum origin, abiotic processes. The Curiosity (rover), ''Curiosity'' rover has documented seasonal fluctuations of Atmosphere of Mars, atmospheric methane levels on Mars. These fluctuations peaked at the end of the Martian summer at 0.6 parts per billion. Methane has been proposed as a possible rocket propellant on future Human mission to Mars, Mars missions due in part to the possibility of synthesizing it on the planet by In situ resource utilization#Mars, in situ resource utilization. An adaptation of the Sabatier reaction, Sabatier methanation reaction may be used with a mixed catalyst bed and a Water-gas shift reaction#Reverse water-gas shift, reverse water-gas shift in a single reactor to produce methane and
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
from the raw materials available on Mars, utilizing water from the Martian soil, Martian subsoil and
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
in the Atmosphere of Mars, Martian atmosphere. Methane could be produced by a non-biological process called serpentinite, serpentinization involving water, carbon dioxide, and the mineral olivine, which is known to be common on Mars.


Titan

Methane has been detected in vast abundance on Titan (moon), Titan, the largest moon of Saturn. It comprises a significant portion of Atmosphere of Titan, its atmosphere and also exists in a liquid form on its surface, where it comprises the majority of the liquid in Titan's Lakes of Titan, vast lakes of hydrocarbons, the Ligeia Mare, second largest of which is believed to be almost pure methane in composition. The presence of stable lakes of liquid methane on Titan, as well as the surface of Titan being highly chemically active and rich in organic compounds, has led scientists to consider the Life on Titan#Hydrocarbons as solvents, possibility of life existing within Titan's lakes, using methane as a solvent in the place of water for Earth-based life and using hydrogen in the atmosphere to derive energy with acetylene.


History

The discovery of methane is credited to Italian people, Italian physicist Alessandro Volta, who characterized numerous properties including its flammability limit and origin from decaying organic matter.Volta, Alessandro (1777
''Lettere del Signor Don Alessandro Volta ... Sull' Aria Inflammable Nativa Delle Paludi''
[Letters of Signor Don Alessandro Volta ... on the flammable native air of the marshes], Milan, Italy: Giuseppe Marelli.
Volta was initially motivated by reports of inflammable air present in marshes by his friend Father Carlo Guiseppe Campi. While on a fishing trip to Lake Maggiore straddling Italy and Switzerland in November 1776, he noticed the presence of bubbles in the nearby marshes and decided to investigate. Volta collected the gas rising from the marsh and demonstrated that the gas was inflammable. Volta notes similar observations of inflammable air were present previously in scientific literature, including a letter written by Benjamin Franklin. Following the Felling mine disasters#1812 disaster, Felling mine disaster of 1812 in which 92 men perished, Sir Humphry Davy established that the feared firedamp was in fact largely methane. The name "methane" was coined in 1866 by the German chemist August Wilhelm von Hofmann. The name was derived from Methanol#History, methanol.


Etymology

Etymologically, the word ''methane'' is coined from the chemical suffix "''-ane''", which denotes substances belonging to the alkane family; and the word ''methyl'', which is derived from the German (1840) or directly from the French , which is a back-formation from the French (corresponding to English "methylene"), the root of which was coined by Jean-Baptiste Dumas and Eugène Péligot in 1834 from the Greek (wine) (related to English "mead") and (meaning "wood"). The radical is named after this because it was first detected in
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical compound and the simplest aliphatic Alcohol (chemistry), alcohol, with the chemical formula (a methyl group linked to a hydroxyl group, often ab ...
, an alcohol first isolated by distillation of wood. The chemical suffix ''-ane'' is from the coordinating chemical suffix ''-ine'' which is from Latin feminine suffix ''-ina'' which is applied to represent abstracts. The coordination of "-ane", "-ene", "-one", etc. was proposed in 1866 by German chemist August Wilhelm von Hofmann.


Abbreviations

The abbreviation -C can mean the mass of carbon contained in a mass of methane, and the mass of methane is always 1.33 times the mass of -C. -C can also mean the methane-carbon ratio, which is 1.33 by mass. Methane at scales of the atmosphere is commonly measured in teragrams (Tg ) or millions of metric tons (MMT ), which mean the same thing. Other standard units are also used, such as nanomole (nmol, one billionth of a mole), Mole (unit), mole (mol), kilogram, and gram.


See also


Explanatory notes


Citations


Cited sources

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External links


Methane
at ''The Periodic Table of Videos'' (University of Nottingham)
International Chemical Safety Card 0291


– United States Geological Survey (archived 6 February 2004) *
CDC – Handbook for Methane Control in Mining
(PDF) {{Authority control Methane, Anaerobic digestion Fuel gas Fuels Gaseous signaling molecules Greenhouse gases Industrial gases Organic compounds with 1 carbon atom