Methanol

Methanol
Names
Pronunciation /ˈmɛθənɒl/
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
3D model (JSmol)
3DMet B01170
1098229
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.599
EC Number 200-659-6
449
KEGG
MeSH Methanol
RTECS number PC1400000
UNII
UN number 1230
Properties
CH
3OH or CH
4O
Molar mass 32.04 g mol−1
Appearance Colorless liquid
Density 0.792 g/cm3[2]
Melting point −97.6 °C (−143.7 °F; 175.6 K)
Boiling point 64.7 °C (148.5 °F; 337.8 K)
miscible
log P −0.69
Vapor pressure 13.02 kPa (at 20 °C)
Acidity (pKa) 15.5[3]
−21.40·10−6 cm3/mol
1.33141[4]
Viscosity 0.545 mPa·s (at 25 °C) [5]
1.69 D
Hazards[6] [7]
Main hazards Moderately Toxic for small animals – Highly Toxic to large animals and humans — May be fatal/lethal or cause blindness and damage to the liver, kidneys, and heart if swallowed – Toxic effects from repeated over exposure have an accumulative effect on the central nervous system, especially the optic nerve – Symptoms may be delayed, become severe after 12 to 18 hours, and linger for several days after exposure [8]
Safety data sheet See: data page
GHS pictograms [9]
GHS signal word Danger [9]
H225, H301, H311, H331, H370[9]
P210, P233, P240, P241, P242, P243, P260, P264, P270, P271, P280, P301+330+331, P310, P302+352, P312, P303+361+353, P304+340, P311, P305+351+338, P307+311, P337+313, P361, P363, P370+378, P403+233[9]
NFPA 704
Flash point 11 to 12 °C (52 to 54 °F; 284 to 285 K)
470 °C (878 °F; 743 K)[11]

385 °C (725 °F; 658 K)[12]

Explosive limits 6–36%[13]
Lethal dose or concentration (LD, LC):
5628 mg/kg (rat, oral)
7300 mg/kg (mouse, oral)
12880 mg/kg (rat, oral)
14200 mg/kg (rabbit, oral)[14]
64,000 ppm (rat, 4 h)[14]
33,082 ppm (cat, 6 h)
37,594 ppm (mouse, 2 h)[14]
US health exposure limits (NIOSH):
PEL (Permissible)
 TWA 200 ppm (260 mg/m3)[13]
REL (Recommended)
 TWA 200 ppm (260 mg/m3) ST 250 ppm (325 mg/m3) [skin][13]
IDLH (Immediate danger)
 6000 ppm[13]
Related compounds
Related compounds
 Methanethiol
Silanol
Supplementary data page
Refractive index (n),
Dielectric constant (εr), etc.
Thermodynamic
data
 Phase behaviour
solid–liquid–gas
UV, IR, NMR, MS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is ☑Y☒N ?)
Infobox references

Methanol, also known as methyl alcohol among others, is a chemical with the formula CH3OH (a methyl group linked to a hydroxyl group, often abbreviated MeOH). Methanol acquired the name wood alcohol because it was once produced chiefly by the destructive distillation of wood. Today, methanol is mainly produced industrially by hydrogenation of carbon monoxide.[15]

Methanol is the simplest alcohol, consisting of a methyl group linked to a hydroxyl group. It is a light, volatile, colorless, flammable liquid with a distinctive odor similar to that of ethanol (drinking alcohol).[16] Methanol is however far more toxic than ethanol. At room temperature, it is a polar liquid. With more than 20 million tons produced annually, it is used as a precursor to other commodity chemicals, including formaldehyde, acetic acid, methyl tert-butyl ether, as well as a host of more specialized chemicals.[15]

Occurrence

Small amounts of methanol are found in normal, healthy human individuals, concluded by one study which found a mean of 4.5 ppm in the exhaled breath of subjects.[17] 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.[18]

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. Atmospheric methanol is oxidized by air in sunlight to carbon dioxide and water over the course of days.

Interstellar medium

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.[19]

In 2006, astronomers using the MERLIN array of radio telescopes at Jodrell Bank Observatory discovered a large cloud of methanol in space, 288 million miles (463 million km) across.[20][21] In 2016, astronomers detected methyl alcohol in a planet-forming disc around the young star TW Hydrae using ALMA radio telescope.[22]

Toxicity

Methanol has low acute toxicity in humans but is dangerous because, together with ethanol, it is occasionally ingested in large volumes. As little as 10 mL (0.34 US fl oz) of pure methanol can cause permanent blindness by destruction of the optic nerve. 30 mL (1.0 US fl oz) is potentially fatal.[23] The median lethal dose is 100 mL (3.4 US fl oz) (i.e. 1–2 mL/kg body weight of pure methanol[24]). The reference dose for methanol is 2 mg/kg in a day.[25][26] Toxic effects begin hours after ingestion, and antidotes can often prevent permanent damage.[23] 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, cases exist of methanol resistance, such as that of Mike Malloy who was the victim of a failed murder attempt by methanol in the early 1930s.[27]

Methanol is toxic by two mechanisms. First, methanol 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.[28] 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.[29] 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.[30]

Outbreaks of methanol poisoning have occurred due to contamination of drinking alcohol. This is more common in the developing world.[31] In 2013 more than 1700 cases occurred in the United States. Those affected are often adult men.[32] Outcomes may be good with early treatment.[33] Toxicity to methanol was described as early as 1856.[34]

Because of its 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.

Applications

Heavy chemicals: formaldehyde, acetic acid, methyl tert-butylether

Methanol is primarily converted to formaldehyde, which is widely used in many areas, especially polymers. The conversion entails oxidation:

2 CH3OH + O2 → 2 CH2O + 2 H2O

Acetic acid can be produced from methanol.

The Cativa process converts methanol into acetic acid.[35]

Methanol and isobutene are combined to give methyl tert-butyl ether (MTBE). MTBE is a major octane booster in gasoline.

Methanol to hydrocarbons, olefins, gasoline

Condensation of methanol to produce hydrocarbons and even aromatic systems is the basis of several technologies related to gas to liquids. These include methanol-to-hydrocarbons (MTH), methanol to gasoline (MTG), and methanol to olefins (MTO), and methanol to propylene (MTP). These conversions are catalyzed by zeolites as heterogeneous catalysts. The MTG process was once commercialized at Motunui in New Zealand.[36][37]

Gasoline additive

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.

Other chemicals

Methanol is the precursor to most simple methylamines, methyl halides, methyl ethers.[15] Methyl esters are produced from methanol, including the transesterification of fats and production of biodiesel via transesterification.[38][39]

Niche and potential uses

Energy carrier

Methanol is a promising energy carrier because, as a liquid, it is easier to store than hydrogen and natural gas. Its energy density is however low reflecting the fact that it represents partially combusted methane. Its energy density is 15.6 MJ/L, whereas ethanol's is 24 and gasoline's is 33 MJ/L.

Further advantages for methanol is its ready biodegradability and low toxicity. It does not persist in either aerobic (oxygen-present) or anaerobic (oxygen-absent) environments. 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.[40]

Fuel for vehicles

Methanol is occasionally used to fuel internal combustion engines. It burns 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. 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. Its energy density is however only half that of gasoline, meaning that twice the volume of methanol would be required.

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.[41]

Methanol is used as a solvent and as an antifreeze in pipelines and windshield washer fluid. Methanol was used as an automobile coolant antifreeze in the early 1900s.[42]

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.

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.[43][44] 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.[45]

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

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:[46]

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

Biosynthesis

The catalytic conversion of methane to methanol is effected by enzymes including methane monooxygenases. These enzymes are mixed-function oxygenases, i.e. oxygenation is coupled with production of water:[47]

CH4 + O2 + NADPH + H+ → CH3OH + H2O + NAD+

Both Fe- and Cu-dependent enzymes have been characterized.[48] Intense but largely fruitless efforts have been undertaken to emulate this reactivity.[49][50] Methanol is more easily oxidized than is the feedstock methane, so the reactions tend not to be selective. Some strategies exist to circumvent this problem. Examples include Shilov systems and Fe- and Cu containing zeolites.[51] These systems do not necessarily mimick the mechanisms employed by metalloenzymes, but draw some inspiration from them. Active sites can vary substantially from those known in the enzymes. For example, a dinuclear active site is proposed in the sMMO enzyme, whereas a mononuclear iron (alpha-Oxygen) is proposed in the Fe-zeolite.[52]

Quality specifications and analysis

Methanol is available commercially in various purity 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). UV-vis spectroscopy is a convenient method for detecting aromatic impurities. Water content can be determined by the Karl-Fischer titration.

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).[53] It later became known as "pyroxylic spirit". In 1834, the French chemists Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition.[54] 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.[54] 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.[55] 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 (US 1569775 ) 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) process 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.

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.

The use of methanol as a motor fuel received attention during the oil crises of the 1970s. 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 interest in methanol fuels.[56]

In the early 1970s, a process was developed by Mobil for producing gasoline fuel from methanol.

Between the 1960s and 1980s methanol emerged as a precursor to the feedstock chemicals acetic acid and acetic anhydride. These processes include the Monsanto acetic acid synthesis, Cativa process, and Tennessee Eastman acetic anhydride process.

See also

References

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  2. ↑ Lide, D. R., ed. (2005). CRC Handbook of Chemistry and Physics (86th ed.). Boca Raton (FL): CRC Press. ISBN 0-8493-0486-5.
  3. ↑ Ballinger, P.; Long, F. A. (1960). "Acid Ionization Constants of Alcohols. II. Acidities of Some Substituted Methanols and Related Compounds". J. Am. Chem. Soc. 82 (4): 795–798. doi:10.1021/ja01489a008.
  4. ↑ "RefractiveIndex.INFO - Refractive index database".
  5. ↑ González, Begoña (2007). "Density, dynamic viscosity, and derived properties of binary mixtures of methanol or ethanol with water, ethyl acetate, and methyl acetate at T = (293.15, 298.15, and 303.15) K". The Journal of Chemical Thermodynamics. 39 (12): 1578–1588. doi:10.1016/j.jct.2007.05.004.
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  12. ↑ "Methanol Safe Handling Manual" (PDF). Methanol Institute. 2017. p. 243. Retrieved 3 August 2018.
  13. 1 2 3 4 "NIOSH Pocket Guide to Chemical Hazards #0397". National Institute for Occupational Safety and Health (NIOSH).
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  19. ↑ Brooks Hays (17 April 2015). "Why astronomers hate the lawn-mowing Roomba". Space Daily.
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  22. ↑ "First Detection of Methyl Alcohol in a Planet-forming Disc". Retrieved 22 June 2016.
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  27. ↑ Blum, Deborah (January 2011). The Poisoner's Handbook: Murder and the Birth of Forensic Medicine in Jazz Age New York. Penguin Books. p. 231. ISBN 978-0-14-311882-4.
  28. ↑ Schep LJ, Slaughter RJ, Vale JA, Beasley DM (2009). "A seaman with blindness and confusion". BMJ. 339: b3929. doi:10.1136/bmj.b3929. PMID 19793790.
  29. ↑ McMartin KE, Martin-Amat G, Noker PE, Tephly TR (1979). "Lack of a role for formaldehyde in methanol poisoning in the monkey". Biochem. Pharmacol. 28 (5): 645–9. doi:10.1016/0006-2952(79)90149-7. PMID 109089.
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  50. ↑ Hammond, C.; Jenkins, R. L.; Dimitratos, N.; Lopez-Sanchez, J. A.; Ab Rahim, M. H.; Forde, M. M.; Thetford, A.; Murphy, D. M.; Hagen, H.; Stangland, E. E.; Moulijn, J. M.; Taylor, S. H.; Willock, D. J.; Hutchings, G. J. (2012). "Catalytic and Mechanistic Insights of the Low-Temperature Selective Oxidation of Methane over Cu-Promoted Fe-ZSM-5". Chemistry: A European Journal. 18 (49): 15735–45. doi:10.1002/chem.201202802. PMID 23150452.
  51. ↑ Snyder, Benjamin E. R.; Bols, Max L.; Schoonheydt, Robert A.; Sels, Bert F.; Solomon, Edward I. (2017-12-19). "Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes". Chemical Reviews. 118 (5): 2718–2768. doi:10.1021/acs.chemrev.7b00344. ISSN 0009-2665. PMID 29256242.
  52. ↑ Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.; Hallaert, Simon D.; Böttger, Lars H.; Ungur, Liviu; Pierloot, Kristine; Schoonheydt, Robert A.; Sels, Bert F. (2016). "The active site of low-temperature methane hydroxylation in iron-containing zeolites". Nature. 536 (7616): 317–321. Bibcode:2016Natur.536..317S. doi:10.1038/nature19059. ISSN 0028-0836. PMID 27535535.
  53. ↑ Boyle discusses the distillation of liquids from the wood of the box shrub in: Robert Boyle, The Sceptical Chymist (London, England: J. Cadwell, 1661), pp. 192–195.
  54. 1 2 A report on methanol to the French Academy of Sciences by J. Dumas and E. Péligot began during the Academy's meeting of 27 October 1834 and finished during the meeting of 3 November 1834. See: Procès-verbaux des séances de l'Académie, 10 : 600–601. Available on: Gallica. The complete report appears in: J. Dumas and E. Péligot (1835) "Mémoire sur l'espirit de bois et sur les divers composés ethérés qui en proviennent" (Memoir on spirit of wood and on the various ethereal compounds that derive therefrom), Annales de chimie et de physique, 58 : 5–74; from page 9: Nous donnerons le nom de méthylène (1) à un radical … (1) Μεθυ, vin, et υλη, bois; c'est-à-dire vin ou liqueur spiritueuse du bois. (We will give the name methylene (1) to a radical … (1) methy, wine, and hulē, wood; that is, wine or spirit of wood.)
  55. ↑ For a report on the International Conference on Chemical Nomenclature that was held in April 1892 in Geneva, Switzerland, see:
    • Armstrong, Henry E (1892). "The International Conference on Chemical Nomenclature". Nature. 46 (1177): 56–9. Bibcode:1892Natur..46...56A. doi:10.1038/046056c0.
    • Armstrong's report is reprinted with the resolutions in English in: Armstrong, Henry (1892). "The International Conference on Chemical Nomenclature". The Journal of Analytical and Applied Chemistry. 6 (1177): 390–400. Bibcode:1892Natur..46...56A. doi:10.1038/046056c0. p. 398: 15. The alcohols and the phenols will be called after the name of the hydrocarbon from which they are derived, terminated with the suffix ol (ex. pentanol, pentenol, etc.).
  56. ↑ Halderman, James D.; Martin, Tony (2009). Hybrid and alternative fuel vehicles. Pearson/Prentice Hall. ISBN 978-0-13-504414-8.

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