Methanol
| Methanol | |
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| IUPAC name | methanol |
| Other names | hydroxymethane methyl alcohol methyl hydrate wood alcohol carbinol |
| Identifiers | |
| CAS number | 67-56-1 |
| RTECS number | PC1400000 |
| SMILES |
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| ChemSpider ID | |
| Properties | |
| Molecular formula | CH3OH |
| Molar mass | 32.04 g/mol |
| Appearance | colorless liquid |
| Density | 0.7918 g/cm³, liquid |
| Melting point |
–97 °C, -142.9 °F (176 K) |
| Boiling point |
64.7 °C, 148.4 °F (337.8 K) |
| Solubility in water | Fully miscible |
| Acidity (pKa) | ~ 15.5 |
| Viscosity | 0.59 mPa·s at 20 °C |
| Dipole moment | 1.69 D (gas) |
| Hazards | |
| EU classification | Flammable (F) Toxic (T) |
| NFPA 704 |
 3
3
1
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| R-phrases | R11, R23/24/25, R39/23/24/25 |
| S-phrases | (S1/2), S7, S16, S36/37, S45 |
| Flash point | 11 °C |
| Related compounds | |
| Related alkanols | ethanol butanol |
| Related compounds | chloromethane methoxymethane |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox references |
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Methanol, also known as methyl alcohol, carbinol, wood alcohol, wood naphtha or wood spirits, is a chemical compound with chemical formula CH3OH (often abbreviated MeOH). It is the simplest alcohol, and is a light, volatile, colourless, flammable, toxic liquid with a distinctive odor that is somewhat milder and sweeter than ethanol. 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 ubiquitous in the environment. As a result, there is a small fraction of methanol vapor in the atmosphere. Over the course of several days, atmospheric methanol is oxidized by oxygen with the help of sunlight to carbon dioxide and water.
Methanol burns in air forming carbon dioxide and water:
- 2 CH3OH + 3 O2 → 2 CO2 + 4 H2O
A methanol flame is almost colorless in bright sunlight conditions, causing an additional safety hazard around open methanol flames.
Because of its toxic properties, methanol is frequently used as a denaturant additive for ethanol manufactured for industrial uses— this addition of methanol economically exempts industrial ethanol from the rather significant 'liquor' taxes that would otherwise be levied as it is the essence of all potable alcoholic beverages. Methanol is often called wood alcohol because it was once produced chiefly as a byproduct of the destructive distillation of wood. It is now produced synthetically by a multi-step process: natural gas or coal gas and steam are reformed in a furnace to produce hydrogen and carbon monoxide; then, hydrogen and carbon monoxide gases react under pressure in the presence of a catalyst. Methanol is also produced from the gasification of a range of renewable biomass materials, such as wood and black liquor from pulp and paper mills.
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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, who called it spirit of box, because he produced it via the distillation of boxwood. It later became known as pyroxylic spirit. In 1834, the French chemists Jean-Baptiste Dumas and Eugene Peligot determined its elemental composition. They also introduced the word methylene to organic chemistry, forming it from Greek methy = "wine" + hȳlē = wood (patch of trees). Its intended origin was "alcohol made from wood (substance)," but it has Greek language errors. 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. The suffix -yl used in organic chemistry to form names of carbon groups, was extracted from the word "methyl."
In 1923, the German chemists Matthias and Pier, working for BASF developed a means to convert synthesis gas (a mixture of carbon monoxide, carbon dioxide, and hydrogen) into methanol. A patent was filed Jan 12 1926 (reference no. 1,569,775). This process used a chromium and manganese oxide catalyst, and required 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 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 vehices" capable of operating on methanol or gasoline were introduced in the U.S. In addition, low levels of methanol were blending 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 deminished the interest in methanol fuels.
In 2006 astronomers using the MERLIN array of radio telescopes at Jodrell Bank Observatory discovered a large cloud of methanol in space, 300 billion miles across.
Production
Today, synthesis gas is most commonly produced from the methane component in natural gas rather than from coal. Three processes are commercially practiced. At moderate pressures of 1 to 2 MPa (10–20 atm) and high temperatures (around 850 °C), methane reacts with steam on a nickel catalyst to produce syngas according to the chemical equation:
This reaction, commonly called steam-methane reforming or SMR, is endothermic and the heat transfer limitations place limits on the size of and pressure in the catalytic reactors used. Methane can also undergo partial oxidation with molecular oxygen to produce syngas, as the following equation shows:
this reaction is exothermic and the heat given off can be used in-situ to drive the steam-methane reforming reaction. When the two processes are combined, it is referred to as autothermal reforming. The ratio of CO and H2 can be adjusted to some extent by the water-gas shift reaction,
to provide the appropriate stoichiometry for methanol synthesis.
The carbon monoxide and hydrogen then react on a second catalyst to produce methanol. Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina first used by ICI in 1966. At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze the production of methanol from carbon monoxide and hydrogen with high selectivity
It is worth noting that the production of synthesis gas from methane produces 3 moles of hydrogen for every mole of carbon monoxide, while the methanol synthesis consumes only 2 moles of hydrogen for every 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 chemical equation
Although natural gas is the most economical and widely used feedstock for methanol production, other feedstocks can be used. Coal is increasingly being used as a feedstock for methanol production, particularly in China. In addition, mature technologies available for biomass gasification are being utlized for methanol production.
Applications
Methanol is a common laboratory solvent. It is especially useful for HPLC and UV/VIS spectroscopy due to its low UV cutoff.
Feedstock
The largest use of methanol by far, is 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.
Also in the early 1970s, a Methanol to gasoline process was developed by Mobil for producing gasoline ready for use in vehicles. 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 not longer marketed in the U.S., it is still widely used in other parts of the world. In addition to direct use as a fuel, methanol (or less commonly, ethanol) is used as a component in the transesterification of triglycerides to yield a form of biodiesel.
Other chemical derivatives of methanol include dimethyl ether, which has replaced chlorofluorocarbons as an aerosol spray propellant, and acetic acid. Dimethyl ether, or "DME" also can be blended with liquified petroleum gas (LPG) for home heating and cooking, and can be used as a diesel replacement transportation fuel.
Automotive fuel
Methanol is used on a limited basis to fuel internal combustion engines, mainly by virtue of the fact that it is not nearly as flammable as gasoline. Methanol is harder to ignite than gasoline, and burns with just one-eight the heat. Pure methanol is required by rule to be used in Champcars, USAC sprint cars (as well as midgets, modifieds, etc.), and other dirt track series such as World of Outlaws. Methanol is also used in radio control, control line and free flight airplanes (required in the "glow-plug" engines that primarily power them), cars and trucks. Drag racers and mud racers also use methanol as their 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 methanol. Mud racers have mixed methanol with gasoline and nitrous oxide to produce more power than gasoline and nitrous oxide alone.
One of the drawbacks of methanol as a fuel is its corrosivity to some metals, including aluminum. Methanol, although a weak acid, 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 clean aluminum surface, which is readily oxidized by some 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. Concerns with methanol's corrosivity have been addressed by using methanol compatible materials, and fuel additives that serve as corrosion inhibitors.
When produced from wood or other organic materials, the resulting organic methanol (bioalcohol) has been suggested as renewable alternative to petroleum-based hydrocarbons. Low levels of methanol can be used in existing vehicles, with the use of proper cosolvents and corrosion inhibitors. The European Fuel Quality Directive allows up to 3% methanol with an equal amount of cosolvent to be blending in gasoline sold in Europe. Today, China uses more than one billion gallons of methanol per year as a transportation fuel in both low level blends used in existing vehicles, and as high level blends in vehicles designed to accommodate the use of methanol fuels.
Other applications
Methanol is a traditional denaturant for ethanol, thus giving the term methylated spirit.
Methanol is also 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 food source of carbon for the denitrifying bacteria, which convert nitrates to nitrogen to reduce the denitrification of sensitive aquifers.
During World War II, methanol was used as a fuel in several German military rocket designs, under name M-Stoff, and in a mixture as C-Stoff.
Methanol is used as a denaturing 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. 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 for laptop computers and mobile phones.[1]
Methanol is also a widely used fuel in camping and boating stoves. The Swedish made Trangia stoves are among the best known alcohol burning 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. In Roland Mueser's book Long-Distance Hiking: Lessons from the Appalachian Trail, Mueser did a survey of stoves used by thru-hikers and found that alcohol was the only stove type with a zero percent failure rate.
Health and safety
Toxicity
Methanol is toxic by two mechanisms. Firstly, 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. Secondly, in a process of toxication, it is metabolised to formic acid (which is present as the formate ion) via formaldehyde in a process initiated by the enzyme alcohol dehydrogenase in the liver. The reaction to formate proceeds completely, with no detectable formaldehyde remaining.[2]. Formate is toxic because it inhibits mitochondrial cytochrome c oxidase, causing the symptoms of hypoxia at cellular level, and also causing metabolic acidosis among a variety of other metabolic disturbances[3]. One of the common symptoms seen in methanol poisoning is permanent blindness by destruction of the optic nerve.[4] Fetal tissue will not tolerate methanol. If methanol has been ingested, a doctor should be contacted immediately. The usual fatal dose is 100–125 mL (4 fl oz). Toxic effects take hours to start, and effective antidotes can often prevent permanent damage. This is treated using ethanol or fomepizole.[5] Either of these drugs acts to slow down the action of alcohol dehydrogenase on methanol by means of competitive inhibition, so that it is excreted by the kidneys rather than being transformed into toxic metabolites.
The initial symptoms of methanol intoxication are those of central nervous system depression: headache, dizziness, nausea, lack of coordination, confusion, drowsiness, and with sufficiently large doses, unconsciousness and death. The initial symptoms of methanol exposure are usually less severe than the symptoms resulting from the ingestion of a similar quantity of ethanol.
Once the initial symptoms have passed, a second set of symptoms arises, 10 to as much as 30 hours after the initial exposure to methanol, including blurring or complete loss of vision and acidosis. These symptoms result from the accumulation of toxic levels of formate in the bloodstream, and may progress to death by respiratory failure. The ester derivatives of methanol do not share this toxicity.
Ethanol is sometimes denatured (adulterated), and thus made undrinkable, by the addition of methanol. The result is known as methylated spirit or "meths" (UK use). (The latter should not be confused with meth, a common U.S. abbreviation for methamphetamine.)
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 visible smoke. If a fire occurs on the track, there is no 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 actions. 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.[6]
- Note: In 2007 IndyCars switched from methanol to ethanol.[1]
One concern with the addition of methanol to automotive fuels is highlighted by recent groundwater impacts from the fuel additive methyl tert-butyl ether (MTBE). Leaking underground gasoline storage tanks created MTBE plumes in groundwater that eventually contaminated well water. However, since 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 infinitely soluble in water and biodegradable, methanol is unlikely to accumulate in groundwater, surface water, air or soil. (Reference: Evaluation of the Fate and Transport of Methanol in the Environment, Malcolm Pirnie, January 1999).
See also
- Liquid fuels
- Methanol fuel
- List of Stoffs
- Methanol (data page)
- Methanol economy
- Aspartame
Notes
- ↑ Sandy Berger (September 30, 2006). "Methanol Laptop Fuel". Compu·Kiss. Retrieved on 2007-05-22.
- ↑ McMartin KE, Martin-Amat G, Noker PE, Tephly TR (March 1979). "Lack of a role for formaldehyde in methanol poisoning in the monkey". Biochem. Pharmacol. 28 (5): 645–9. PMID 109089. http://linkinghub.elsevier.com/retrieve/pii/0006-2952(79)90149-7.
- ↑ Liesivuori J, Savolainen H (September 1991). "Methanol and formic acid toxicity: biochemical mechanisms". Pharmacol. Toxicol. 69 (3): 157–63. PMID 1665561.
- ↑ "Methanol and Blindness". Ask A Scientist, Chemistry Archive. Retrieved on 22 May 2007.
- ↑ (January 2001)"Fomepizole in the Treatment of Poisoning" in Pediatrics Volume 107 (No. 1). Retrieved on 22 May 2007.
- ↑ McDonald, Norris, "Green no longer bad luck at Indy", Toronto Star, http://www.thestar.com/comment/columnists/article/205088
References
- Robert Boyle, The Sceptical Chymist (1661) – contains account of distillation of wood alcohol.
- Gallucci, F., Basile, A., Drioli, E., Methanol as an energy source and/or energy carrier in membrane processes Separation and Purification Reviews 36 (2), pp. 175-202
External links
- Race Car Book RaceCarBook.com, includes technical articles and methanol racing book information.
- The Methanol Institute Industry trade group, lots of information on methanol's use in fuel cells and as an alternative fuel.
- The methanol story: a sustainable fuel for the future article by Ford Motor's Roberta Nichols, the mother of the flexible fuel vehicle, discussing Gasoline-Ethanol-Methanol flexibility in the Journal of Scientific & Industrial Research
- National Pollutant Inventory - Methanol Fact Sheet
- Methanol Discovered in Space
- Vapor pressure and liquid density calculation
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