Methanol

From Wikipedia, the free encyclopedia

Not to be confused with menthol or methanal.
Methanol

Names
Preferred IUPAC name
Methanol[1]
Other names
Carbinol
Columbian spirits
Hydroxymethane
Methyl alcohol
Methyl hydrate
Methyl hydroxide
Methylic alcohol
Methylol
Pyroligneous spirit
Wood alcohol
Wood naphtha
Wood spirit
Identifiers
 67-56-1
CAS Number
 Interactive image
3D model (JSmol)
3DMet B01170
Beilstein Reference 1098229
 CHEBI:17790
ChEBI
 864
ChemSpider
ECHA InfoCard 100.000.599
EC Number 200-659-6
Gmelin Reference 449
 D02309
KEGG
MeSH Methanol
 887
PubChem CID
RTECS number PC1400000
 Y4S76JWI15
UNII
UN number 1230
InChI[show]
SMILES[show]
Properties
CH
Chemical formula
3OH
Molar mass 32.04 g mol−1
Appearance Colorless liquid
Density 0.792 g·cm−3[2]
Melting point −97.6 °C (−143.7 °F; 175.6 K)
Boiling point 64.7 °C (148.5 °F; 337.8 K)
Solubility in water miscible
log P -0.69
Vapor pressure 13.02 kPa (at 20 °C)
Acidity (pKa) 15.5[3]
Magnetic
-21.40·10−6 cm3/mol
susceptibility (χ)
Refractive index (nD) 1.33141[4]
Viscosity 0.545 mPa×s (at 25 °C) [5]
Dipole moment 1.69 D
Hazards[10]
Safety data sheet See: data page

GHS pictograms
[6]

GHS signal word Danger [6]

GHS hazard H225, H301, H311, H331,
statements H370[6]
P210, P233, P240, P241, P242,
GHS precautionary P243, P260, P264, P270, P280,
statements P301+310, P303+361+353,
P304+340, P330[6]

NFPA 704
3
1
0
11 to 12 °C (52 to 54 °F; 284 to
Flash point
285 K)
Autoignition
470[7] °C (878 °F; 743 K)
temperature
Explosive limits 6%-36%[8]
Lethal dose or concentration (LD, LC):
5628 mg/kg (rat, oral)
LD50 (median 7300 mg/kg (mouse, oral)
dose) 12880 mg/kg (rat, oral)
14200 mg/kg (rabbit, oral)[9]
LC50 (median
64,000 ppm (rat, 4 hr)[9]
concentration)
LCLo (lowest 33,082 ppm (cat, 6 hr)
published) 37,594 ppm (mouse, 2 hr)[9]
US health exposure limits (NIOSH):
PEL (Permissible) TWA 200 ppm (260 mg/m3)[8]
 REL TWA 200 ppm (260 mg/m3) ST
(Recommended) 250 ppm (325 mg/m3) [skin][8]
IDLH (Immediate
6000 ppm[8]
danger)
Related compounds
Methanethiol
Related compounds
Silanol
Supplementary data page
Structure and Refractive index (n),
properties Dielectric constant (εr), etc.
Thermodynamic Phase behaviour
data solid–liquid–gas
Spectral data UV, IR, NMR, MS
Except where otherwise noted, data are given for
materials in their standard state (at 25 °C [77 °F],
100 kPa).
verify (what is ?)
Infobox references

Methanol (/ˈmɛθənɒl/), also known as methyl alcohol among others, is a chemical with
the formula CH3OH (often abbreviated MeOH). Methanol acquired the name "wood
alcohol" because it was once produced chiefly as a byproduct of the destructive distillation
of wood. Today, industrial methanol is produced in a catalytic process directly from carbon
monoxide, carbon dioxide, and hydrogen.

Methanol is the simplest alcohol, being only a methyl group linked to a hydroxyl group. It
is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to that of
ethanol (drinking alcohol).[11] However, unlike ethanol, methanol is highly toxic and unfit
for consumption. At room temperature, it is a polar liquid, and is used as an antifreeze,
solvent, fuel, and as a denaturant for ethanol. It is also used for producing biodiesel via
transesterification reaction.

Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria,

and is commonly present in small amounts in the environment. As a result, the atmosphere
contains a small amount of methanol vapor. But in only a few days, atmospheric methanol
is oxidized by sunlight to produce carbon dioxide and water.

Methanol is also found in abundant quantities in star-forming regions of space, and is used
in astronomy as a marker for such regions. It is detected through its spectral emission lines.
[12]

Methanol when drunk is metabolized first to formaldehyde and then to formic acid or
formate salts.[13] These are poisonous to the central nervous system and may result in
blindness, coma, and death. Because of these toxic properties, methanol is frequently used
as a denaturant additive for ethanol manufactured for industrial uses. This addition of
methanol exempts industrial ethanol (commonly known as "denatured alcohol" or
"methylated spirit") from liquor excise taxation in the US and some other countries.

Contents
 1 Occurrence
o 1.1 Human metabolite
 2 Toxicity
 3 Applications
o 3.1 Chemical industry
o 3.2 Fuel for vehicles
o 3.3 Production of synthesis gas
o 3.4 Energy carrier
o 3.5 Other applications
 4 Production
o 4.1 From synthesis gas
o 4.2 Other
 5 Quality specifications and analysis
o 5.1 Laboratory use
o 5.2 Commercial methanol
 6 History
 7 See also
 8 References
 9 Further reading
 10 External links

Occurrence
Human metabolite

Methanol is poisonous to the central nervous system and may cause blindness, coma, and
death. However, in small amounts, methanol is a natural endogenous compound found in
normal, healthy human individuals, concluded by one study which found a mean of
4.5 ppm in the exhaled breath of subjects.[14] The mean endogenous methanol in humans of
0.45 g/d may be metabolized from pectin found in fruit; one kilogram of apple produces up
to 1.4 g methanol.[15]

Toxicity
Main article: Methanol toxicity
See also: List of methanol poisoning incidents

Methanol has a high toxicity in humans. As little as 10 mL of pure methanol, ingested, is

metabolized into formic acid, which can cause permanent blindness by destruction of the
optic nerve. Thirty mL is potentially fatal,[16] although the median lethal dose is typically
100 mL (3.4 fl oz) (i.e. 1–2 mL/kg body weight of pure methanol[17]). The reference dose
for methanol is 2 mg/kg/day.[18] Toxic effects begin hours after ingestion, and antidotes can
often prevent permanent damage.[16] Because of its similarities in both appearance and odor
to ethanol (the alcohol in beverages), it is difficult to differentiate between the two (such is
also the case with denatured alcohol, adulterated liquors or very low quality alcoholic
beverages). However, there are cases of methanol resistance, such as that of Mike Malloy
who was the victim of a failed murder attempt by methanol in the early 1930s.[19]

Methanol is toxic by two mechanisms. First, methanol (whether it enters the body by
ingestion, inhalation, or absorption through the skin) can be fatal due to its CNS depressant
properties in the same manner as ethanol poisoning. Second, in a process of toxication, it is
metabolized to formic acid (which is present as the formate ion) via formaldehyde in a
process initiated by the enzyme alcohol dehydrogenase in the liver.[20] Methanol is
converted to formaldehyde via alcohol dehydrogenase (ADH) and formaldehyde is
converted to formic acid (formate) via aldehyde dehydrogenase (ALDH). The conversion to
formate via ALDH proceeds completely, with no detectable formaldehyde remaining. [21]
Formate is toxic because it inhibits mitochondrial cytochrome c oxidase, causing hypoxia at
the cellular level, and metabolic acidosis, among a variety of other metabolic disturbances.
[22]

Outbreaks of methanol poisoning have occurred due to contamination of drinking alcohol.

This is more common in the developing world.[23] In 2013 more than 1700 cases occurred in
the United States. Those affected are often adult males.[24] Outcomes may be good with
early treatment.[25] Toxicity to methanol was described as early as 1856.[26]

Applications
Methanol is used primarily as a feedstock for the manufacture of chemicals, and as a fuel
for specialized vehicles. As mentioned above, it is a common de-naturing agent. As a
common laboratory solvent, is especially useful for HPLC, UV/VIS spectroscopy, and
LCMS due to its low UV cutoff.

Chemical industry

Methanol is primarily used in making other chemicals. About 40% of methanol is

converted to formaldehyde, and from there into products as diverse as plastics, plywood,
paints, explosives, and permanent press textiles.

Condensation of methanol molecules to produce hydrocarbon chains and even aromatic

systems has been demonstrated with loss of water, carbon monoxide, and/or carbon dioxide
(loss of oxygen is prohibited on thermodynamic grounds). As early as 1880, an
aromatisation reaction which generated hexamethylbenzene as a minor product with a
mixture of mostly aliphatic hydrocarbons directly from methanol, using zinc chloride as
catalyst, had been demonstrated.[27][28] At 283 °C, the melting point of ZnCl2, the idealised
reaction for the production of hexamethylbenzene has a ΔG of −261 kcal mol−1.[27]
 15 CH
3OH → C
6(CH
3)
6 + 3 CH
4 + 15 H
2O

In the early 1970s, a process was developed by Mobil for producing gasoline fuel for
vehicles.[27] One such industrial facility was built at Motunui in New Zealand in the 1980s.
In the 1990s, large amounts of methanol were used in the United States to produce the
gasoline additive methyl tert-butyl ether (MTBE). While MTBE is no longer marketed in
the U.S., it is still widely used in other parts of the world. Methanol (or less commonly,
ethanol) is a component in the transesterification of triglycerides for production of
biodiesel.

Other chemical derivatives of methanol include acetic acid and dimethyl ether (DME), the
latter of which has replaced chlorofluorocarbons as an aerosol spray propellant. Dimethyl
ether can also be blended with liquified petroleum gas (LPG) for home heating and
cooking, and can be used as a replacement for transportation diesel fuel.

Of high interest to the petrochemical marketplace, methanol is an important ingredient in

new and lower-cost methods for producing propylene, which is much in demand. Such
methods include methanol-to-olefins (MTO), methanol-to-propylene (MTO/MTP),
metathesis, propane dehydrogenation (PDH), high severity FCC, and olefins cracking.

The market for proponyl became tight when the ethane prices fell in the US with the
exploration of shale gas reserves. The low priced ethylene produced from this raw material
has given chemical producers in North America a feedstock advantage. Such change has
put naphtha-fed steam crackers at a disadvantageous position, with many of them shutting
down or revamping to use ethane as feedstock. Nevertheless, the propylene output rates
from ethane-fed crackers are negligible.[29]

Fuel for vehicles

Main articles: Methanol fuel and methanol economy

Methanol is occasionally used to fuel internal combustion engines. Pure methanol is

required by rule to be used in Champcars, Monster Trucks, USAC sprint cars (as well as
midgets, modifieds, etc.), and other dirt track series, such as World of Outlaws, and
Motorcycle Speedway, mainly because, in the event of an accident, methanol does not
produce an opaque cloud of smoke. Since the late 1940s, Methanol is also used as the
primary fuel ingredient in the powerplants for radio control, control line, free flight
airplanes, cars and trucks; such engines use a platinum filament glow plug that ignites the
methanol vapor through a catalytic reaction. Drag racers, mud racers, and heavily modified
tractor pullers also use methanol as the primary fuel source. Methanol is required with a
supercharged engine in a Top Alcohol Dragster and, until the end of the 2006 season, all
vehicles in the Indianapolis 500 had to run on methanol. As a fuel for mud racers, methanol
mixed with gasoline and nitrous oxide produces more power than gasoline and nitrous
oxide alone.

Methanol burns in oxygen, including open air, forming carbon dioxide and water:

2 CH3OH + 3 O2 → 2 CO2 + 4 H2O

One problem with high concentrations of methanol in fuel is that alcohols corrode some
metals, particularly aluminium. An acid, albeit weak, methanol attacks the oxide coating
that normally protects the aluminium from corrosion:

6 CH3OH + Al2O3 → 2 Al(OCH3)3 + 3 H2O

The resulting methoxide salts are soluble in methanol, resulting in a clean aluminium
surface, which is readily oxidized by dissolved oxygen. Also, the methanol can act as an
oxidizer:

6 CH3OH + 2 Al → 2 Al(OCH3)3 + 3 H2

This reciprocal process effectively fuels corrosion until either the metal is eaten away or the
concentration of CH3OH is negligible. Methanol's corrosivity has been addressed with
methanol-compatible materials and fuel additives that serve as corrosion inhibitors.

Organic methanol, produced from wood or other organic materials (bioalcohol), has been
suggested as a renewable alternative to petroleum-based hydrocarbons. Low levels of
methanol can be used in existing vehicles with the addition of cosolvents and corrosion
inhibitors.

Methanol fuel has been proposed for ground transportation. The chief advantage of a
methanol economy is that it could be adapted to gasoline internal combustion engines with
minimum modification to the engines and to the infrastructure that delivers and stores
liquid fuel.

Safety in automotive fuels

Pure methanol has been used in open wheel auto racing since the mid-1960s. Unlike
petroleum fires, methanol fires can be extinguished with plain water. A methanol-based fire
burns invisibly, unlike gasoline, which burns with a visible flame. If a fire occurs on the
track, there is no flame or smoke to obstruct the view of fast approaching drivers, but this
can also delay visual detection of the fire and the initiation of fire suppression. The decision
to permanently switch to methanol in American IndyCar racing was a result of the
devastating crash and explosion at the 1964 Indianapolis 500, which killed drivers Eddie
Sachs and Dave MacDonald.[30] In 2007 IndyCars switched from methanol to ethanol.[31]
Government policy

The European Fuel Quality Directive allows up to 3% methanol with an equal amount of
cosolvent to be blended with gasoline sold in Europe. China uses more than one billion
gallons of methanol per year as a transportation fuel in low level blends for conventional
vehicles and high level blends in vehicles designed for methanol fuels.

In the US, the Open Fuel Standard Act of 2011 was introduced in the US Congress to
encourage car manufacturers to build cars capable of using methanol, gasoline, or ethanol
fuels. The bill is being championed by the Open Fuel Standard Coalition.

Production of synthesis gas

Stoichiometry for methanol production of syngas requires the ratio of H2 / CO to equal 2.

The partial oxidation process yields a ratio of 2, and the steam reforming process yields a
ratio of 3. The H2 / CO ratio can be lowered to some extent by the reverse water-gas shift
reaction,

CO2 + H2 → CO + H2O,

to provide the appropriate stoichiometry for methanol synthesis.

Energy carrier

Methanol is useful as an energy carrier because it is easier to store than hydrogen and burns
cleaner than fossil fuels.

Methanol is readily biodegradable in both aerobic (oxygen present) and anaerobic (oxygen
absent) environments. Methanol will not persist in the environment. The half-life for
methanol in groundwater is just one to seven days, while many common gasoline
components have half-lives in the hundreds of days (such as benzene at 10–730 days).
Since methanol is miscible with water and biodegradable, it is unlikely to accumulate in
groundwater, surface water, air or soil.[32]

Other applications

Methanol is a traditional denaturant for ethanol, the product being known as "denatured
alcohol" or "methylated spirit". This was commonly used during the Prohibition to
discourage consumption of bootlegged liquor, and ended up causing several deaths.[33]

Methanol is used as a solvent and as an antifreeze in pipelines and windshield washer fluid.

In some wastewater treatment plants, a small amount of methanol is added to wastewater to

provide a carbon food source for the denitrifying bacteria, which convert nitrates to
nitrogen gas and reduce the nitrification of sensitive aquifers.
During World War II, methanol was used as a fuel in several German military rocket
designs, under the name M-Stoff, and in a roughly 50/50 mixture with hydrazine, known as
C-Stoff.

Methanol was used as an automobile coolant antifreeze in the early 1900s.[34]

Methanol is used as a destaining agent in polyacrylamide gel electrophoresis.

Direct-methanol fuel cells are unique in their low temperature, atmospheric pressure
operation, allowing them to be miniaturized to an unprecedented degree.[35][36] This,
combined with the relatively easy and safe storage and handling of methanol, may open the
possibility of fuel cell-powered consumer electronics, such as laptop computers and mobile
phones.[37]

Methanol is also a widely used fuel in camping and boating stoves. Methanol burns well in
an unpressurized burner, so alcohol stoves are often very simple, sometimes little more than
a cup to hold fuel. This lack of complexity makes them a favorite of hikers who spend
extended time in the wilderness. Similarly, the alcohol can be gelled to reduce risk of
leaking or spilling, as with the brand "Sterno".

Methanol is mixed with water and injected into high performance diesel and gasoline
engines for an increase of power and a decrease in intake air temperature in a process
known as water methanol injection.

Production
From synthesis gas

Carbon monoxide and hydrogen react over a catalyst to produce methanol. Today, the most
widely used catalyst is a mixture of copper and zinc oxides, supported on alumina, as first
used by ICI in 1966. At 5–10 MPa (50–100 atm) and 250 °C (482 °F), the reaction is
characterized by high selectivity (>99.8%):

CO + 2 H2 → CH3OH

Since the production of synthesis gas from methane produces three moles of hydrogen for
every mole of carbon monoxide, whereas the synthesis consumes only two moles of
hydrogen gas per mole of carbon monoxide. One way of dealing with the excess hydrogen
is to inject carbon dioxide into the methanol synthesis reactor, where it, too, reacts to form
methanol according to the equation:

CO2 + 3 H2 → CH3OH + H2O

In terms of mechanism, the process occurs via initial conversion of CO into CO2, which is
then hydrogenated:[38]
 CO2 + 3 H2 → CH3OH + H2O

where the H2O byproduct is recycled via the water-gas shift reaction

CO + H2O → CO2 + H2,

This gives an overall reaction, which is the same as listed above.

CO + 2 H2 → CH3OH

Other

The catalytic conversion of methane to methanol has long been sought as a route to
methanol. This route is effected by enzymes such as methane monooxygenases but
commercial routes remain elusive because of the tendency for over-oxidation, i.e.,
methanol is more readily oxidized than methane.[39][40]

Quality specifications and analysis

Laboratory use

Methanol is available commercially in various purity grades for fine chemicals:

 "Synthesis" quality (corresponding to normal commercial methanol)

 Certified analytical quality
 Extremely pure qualities for semiconductor manufacture

Commercial methanol

In addition to laboratory grades, commercial methanol is generally classified according to

ASTM purity grades A and AA. Methanol for chemical use normally corresponds to Grade
AA. In addition to water, typical impurities include acetone and ethanol (which are very
difficult to separate by distillation). When methanol is delivered by ships or tankers used to
transport other substances, contamination by the previous cargo must be expected.
Comparative ultraviolet spectroscopy has proved a convenient, quick test method for
deciding whether a batch can be accepted and loaded. Traces of all chemicals derived from
aromatic parent substances, as well as a large number of other compounds, can be detected.
Further tests for establishing the quality of methanol include measurements of boiling point
range, density, permanganate number, turbidity, color index, and acid number. More
comprehensive tests include water determination according to the Karl Fischer method and
gas chromatographic determination of byproducts. However, the latter is relatively
expensive and time-consuming because several injections using different columns and
detectors must be made due to the variety of byproducts present.

History
In their embalming process, the ancient Egyptians used a mixture of substances, including
methanol, which they obtained from the pyrolysis of wood. Pure methanol, however, was
first isolated in 1661 by Robert Boyle, when he produced it via the distillation of buxus
(boxwood).[41] It later became known as "pyroxylic spirit". In 1834, the French chemists
Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition.[42]

They also introduced the word "methylène" to organic chemistry, forming it from Greek
methy = "alcoholic liquid" + hȳlē = "woodland, forest", with a Greek language error: xylon
= "wood as a material" would have been more suitable. "Methylène" designated a "radical"
that was about 14% hydrogen by weight and contained one carbon atom. This would be
CH2, but at the time carbon was thought to have an atomic weight only six times that of
hydrogen, so they gave the formula as CH.[42] They then called wood alcohol (l'esprit de
bois) "bihydrate de méthylène" (bihydrate because they thought the formula was C4H8O4 =
(CH)4(H2O)2!). The term "methyl" was derived in about 1840 by back-formation from
"methylene", and was then applied to describe "methyl alcohol". This was shortened to
"methanol" in 1892 by the International Conference on Chemical Nomenclature.[43] The
suffix -yl used in organic chemistry to form names of carbon groups, was extracted from
the word "methyl".

In 1923, the German chemists Alwin Mittasch and Mathias Pier, working for Badische-
Anilin & Soda-Fabrik (BASF), developed a means to convert synthesis gas (a mixture of
carbon monoxide, carbon dioxide, and hydrogen) into methanol. US patent 1,569,775 was
applied for on 4 Sep 1924 and issued on 12 January 1926; the process used a chromium and
manganese oxide catalyst with extremely vigorous conditions—pressures ranging from 50
to 220 atm, and temperatures up to 450 °C. Modern methanol production has been made
more efficient through use of catalysts (commonly copper) capable of operating at lower
pressures. The modern low pressure methanol (LPM) was developed by ICI in the late
1960s US 3326956 with the technology now owned by Johnson Matthey, which is a
leading licensor of methanol technology.

Methanol is one of the most heavily traded chemical commodities in the world, with an
estimated global demand of around 27 to 29 million metric tons. In recent years, production
capacity has expanded considerably, with new plants coming on-stream in South America,
China and the Middle East, the latter based on access to abundant supplies of methane gas.
Even though nameplate production capacity (coal-based) in China has grown significantly,
operating rates are estimated to be as low as 50 to 60%. No new production capacity is
scheduled to come on-stream until 2015.

The main applications for methanol are the production of formaldehyde (used in
construction and wooden boarding), acetic acid (basis for a.o. PET-bottles), MTBE (fuel
component and replacement for the very volatile diethyl ether) and more recently for the
formation of methyl esters in the production of bio-diesel. In China, demand is expected to
grow exponentially, not only caused by a growing internal market of the traditional
applications, but accelerated by new applications, such as direct blending (with gasoline),
Methanol-To-Olefins (e.g. propylene) and DME. Methanol can also be used to produce
gasoline.
Artist’s impression of the disc around the young star TW Hydrae.[44]

The use of methanol as a motor fuel received attention during the oil crises of the 1970s
due to its availability, low cost, and environmental benefits. By the mid-1990s, over 20,000
methanol "flexible fuel vehicles" capable of operating on methanol or gasoline were
introduced in the U.S. In addition, low levels of methanol were blended in gasoline fuels
sold in Europe during much of the 1980s and early-1990s. Automakers stopped building
methanol FFVs by the late-1990s, switching their attention to ethanol-fueled vehicles.
While the methanol FFV program was a technical success, rising methanol pricing in the
mid- to late-1990s during a period of slumping gasoline pump prices diminished the
interest in methanol fuels.[45]

In 2006, astronomers using the MERLIN array of radio telescopes at Jodrell Bank
Observatory discovered a large cloud of methanol in space, 288 billion miles across.[46][47] In
2016, astronomers detected methyl alcohol in a planet-forming disc around the young star
TW Hydrae using ALMA radio telescope.[4
Methanol
Published May 2014
Methanol is also known as methyl alcohol or wood alcohol. It was once produced chiefly as
a by-product of the destructive distillation of wood. Today, methanol is produced in a
catalytic industrial process directly from carbon dioxide, carbon monoxide and hydrogen.
Methanol is the simplest alcohol. At room temperature, it is a polar liquid, and is used as
antifreeze, a solvent, fuel, and as a denaturant for ethanol. It is also used to produce
biodiesel.
The following pie chart shows world consumption of methanol:
Worldwide, formaldehyde production is the largest consumer of methanol, accounting for
31% of world methanol demand in 2013. Demand is driven by the construction industry
since formaldehyde is used primarily to produce adhesives for the manufacture of various
construction board products. Historically, the major end product has been plywood, but in
developed countries, demand is also driven by the expanding use of engineering board
products such as OSB (oriented strandboard). These wood composite products require more
formaldehyde-based resin per square foot of board than plywood. Demand for
formaldehyde is highly dependent on general economic conditions, and, as an example, a
slowdown in construction can considerably reduce formaldehyde demand. Overall, global
methanol demand for formaldehyde production will grow at an average rate of just over 5%
per year from 2013 to 2018; it will remain the single-largest end use in 2018. Although it
will remain the largest end use, its share of total world methanol demand will decline to
28% in 2018 as a result of higher growth rates displayed by other end-use segments for
methanol.
Consumption of methanol in direct fuel applications is expected to show highly promising
growth trends in the next few years. These fuel uses of methanol include MTBE/TAME,
biodiesel, gasoline blending and dimethyl ether (DME). Gasoline blending applications for
methanol, mostly developed in China for the fuels segment, will increase at an average
annual rate of about 12.5% in the next five years, growing from a market share of 11% in
2013 to about 14% in 2018. All the other fuel end uses will also increase in the next five
years. This growth will be dependent largely upon the development of new applications as
well as general economic growth, since most of these applications (such as fuel cells) go
into durable goods uses (such as cars), which are directly linked to general economic
conditions. Additionally, growth will depend on the price trends for conventional energy
uses; with the considerable increase in (conventional) energy prices (since the trough in
early 2009), interest in developing methanol as an alternative fuel has once again increased.
MTBE/TAME accounted for 11% of world methanol demand in 2013. In the United States,
domestic consumption of MTBE increased substantially when the Clean Air Act
Amendments (CAAA) of 1990 mandated that oxygenated compounds be added to gasoline
as one aspect of a program to alleviate air pollution. The major effect of the CAAA was
realized in 1995, when RFG (reformulated gasoline) was required in about one-third of
U.S. motor fuels. In the United States, MTBE was the primary oxygenated compound for
use in RFG. In recent years, MTBE itself has come under attack, primarily because it was
found in groundwater as a result of leaking underground gasoline tanks. California—
formerly the leading consumer of MTBE—banned the use of MTBE at the end of 2003 and
several states followed suit. Methanol consumption for MTBE has been on the decline in
the United States since 1999, and since 2006, U.S. production of MTBE has only been for
the export markets or for the export-directed gasoline pool. In other regions of the world,
especially where lead compounds are currently used to maintain octane levels, some growth
for MTBE is still possible. MTBE/TAME is expected to grow at an average annual rate of
3% during 2013–2018, but its global market share will decrease to about 9% of methanol
consumption by 2018.
Acetic acid/anhydride accounted for 10% of the world methanol market in 2013 and is
expected to maintain the same market share in 2018. A major portion of acetic acid is
consumed for the production of vinyl acetate monomer (VAM) and, thus, demand for acetic
acid to some extent tracks the demand for VAM. Acetic acid is also used as a solvent for
terephthalic acid production. From 2013 to 2018, total global acetic acid demand will grow
at 5.7% per year, slower than the growth rate of 6.5% observed in the last five years. In the
United States, methanol consumption for acetic acid production will grow only at an
average annual rate of 1–1.5% in the next five years; the growth rate in China will be 9.5%
during the same period. Globally, methanol consumption for acetic acid production should
grow faster (5.7% per year growth) than total acetic acid production (5.4% per year growth)
since methanol-based production should grow faster than other (major) production routes.
Methanol-to-olefins and methanol-to-propylene (MTO/MTP) applications are gaining
momentum and are expected to grow at an average annual rate of 46.5% during 2013–2018.
This usage is driven solely by China and currently accounts for 2% of the total, eventually
accounting for 10% of world methanol consumption in 2018.