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Methyl tert-butyl ether

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Methyl tert-butyl ether
MTBE
MTBE
MTBE
MTBE
Names
IUPAC name
2-Methoxy-2-methylpropane
Other names
Methyl tertiary-butyl ether
Methyl tert-butyl ether
Methyl t-butyl ether
MTBE
tert-Butyl methyl ether
tBME
Identifiers
3D model (JSmol)
ECHA InfoCard 100.015.140 Edit this at Wikidata
  • CC(C)(C)OC
Properties
C5H12O
Molar mass 88.15 g/mol
Density 0.7404 g/cm³
Melting point −109 °C (−164 °F; 164 K)
Boiling point 55.2 °C (131.4 °F; 328.3 K)
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability (yellow): no hazard codeSpecial hazards (white): no code
1
3
Flash point -10 °C
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Methyl tert-butyl ether, also known as methyl tertiary butyl ether and MTBE, is a chemical compound with molecular formula C5H12O. MTBE is a volatile, flammable and colorless liquid that is immiscible with water. MTBE has a minty odor vaguely reminiscent of diethyl ether, leading to unpleasant taste and odor in water. MTBE is a gasoline additive, used as an oxygenate and to raise the octane number, although its use has declined in the United States in response to environmental and health concerns. It has been found to easily pollute large quantities of groundwater when gasoline with MTBE is spilled or leaked at gas stations. MTBE is also used in organic chemistry as a relatively inexpensive solvent with properties comparable to diethyl ether but with a higher boiling point and lower solubility in water. It is also used medically to dissolve gallstones.

Production

MTBE is manufactured via the chemical reaction of methanol and isobutylene. Methanol is derived from natural gas, and isobutylene is derived from butane obtained from crude oil or natural gas, thus MTBE is a fossil fuel. In the United States, it was produced in very large quantities (more than 200,000 barrels per day in 1999) during its use as a fuel additive. Due to widespread releases of MTBE-containing gasoline from underground storage tanks all over the US, various jurisdictions banned the use of MTBE and production was reduced. MTBE contamination in drinking water aquifers is a serious concern in many states (the most famous cases are Lake Tahoe and Santa Monica). Most American gasoline retailers have ceased using MTBE as an oxygenate and US production has declined. Similarly, lack of growth or even decline of MTBE production has been seen in Western Europe. This is due to the alternative ethanol-derived ether ETBE being given more favorable tax treatment. In other parts of the world, which account for about a half of 2004 production, the use of MTBE will continue and even grow.[1]

Physical properties

MTBE forms azeotropes with water (52.6 °C) and methanol (51.3 °C).

Uses

MTBE is almost exclusively used as a fuel component in engine gasoline. It is one of a group of chemicals commonly known as oxygenates because they raise the oxygen content of gasoline.

As anti-knocking agent

In the US it has been used in gasoline at low levels since 1979 to replace tetra-ethyl lead and to increase its octane rating helping prevent engine knocking. Oxygen helps gasoline burn more completely, reducing tailpipe emissions from pre-1984 motor vehicles; dilutes or displaces gasoline components such as aromatics (e.g., benzene) and sulfur; and optimizes the oxidation during combustion. Most refiners chose MTBE over other oxygenates primarily for its blending characteristics and for economic reasons.

Since 1992, MTBE has been used at higher concentrations in some gasoline to fulfill the oxygenate requirements set by the United States Congress in Clean Air Act amendments; however, since 1999, in California and other locations MTBE has begun to be phased out because of groundwater contamination.[2] Due to its higher solubility in water MTBE moves more quickly than other fuel components.[2] The Energy Policy Act of 2005 reduces the federal requirement for oxygen content in reformulated gasoline.[3]

In 1995 high levels of MTBE were unexpectedly discovered in the water wells of Santa Monica, California, and the U.S. Geological Survey reported detections.[4] Subsequent U.S. findings indicate tens of thousands of contaminated sites in water wells distributed across the country. As per toxicity alone, MTBE is not classified as a hazard for the environment, but it imparts an unpleasant taste to water already at very low concentrations. The maximum contaminant level of MTBE in drinking water has not yet been established by the EPA. The leakage problem is partially attributed to the lack of effective regulations for underground storage tanks, but spillage from overfilling is also a contributor. As an ingredient in unleaded gasoline, MTBE is the most water soluble component. When dissolved in groundwater, MTBE will lead the contaminant plume with the remaining components such as benzene and toluene following. Thus the discovery of MTBE in public groundwater wells indicates that the contaminant source was a gasoline release. Its criticism and subsequent decreased usage, some claim, is more a product of its easy detectability (taste) in extremely low concentrations (ppb) than its toxicity. The MTBE concentrations used in the EU (usually 1.0–1.6%) and allowed (maximum 5%) in Europe are lower than in California.[5]

Alternatives

Other compounds are available as oxygenate additives for gasoline including ethanol and related ethers, e.g. tert-amyl methyl ether (TAME). Reasons for using MTBE include economic considerations, as some of the production is obtained by adding methanol to isobutylene produced as a by-product of other processes. However, most MTBE facilities have to manufacture the methanol and isobutylene required to produce MTBE.

Ethanol has been advertised as a safe alternative by the agricultural interest groups in the USA and Europe. Its lack of toxicity is not different from MTBE, but as a polar solvent, it drives off nonpolar hydrocarbons from the gasoline, a problem that MTBE does not cause. Volatile hydrocarbons in gasoline vapors are known carcinogens and produce photochemical smog. Ethanol's higher cost requires government intervention in the form of subsidies or mandated usage to be competitive. In 2003, California was the first U.S. state to start replacing MTBE with ethanol. Several other states started switching soon thereafter.

Advocates of both sides of the debate in the United States sometimes claim that gasoline manufacturers have been forced to add MTBE to gasoline by law. It might be more correct to say they have been induced to do so, although any oxygenate would fulfill the law.

An alternative to straight ethanol is the related ether ETBE, which is manufactured from ethanol and isobutene. Its performance as an additive is similar to MTBE, but due to the higher price of ethanol compared to methanol, it is more expensive.

Higher quality gasoline is also an alternative, i.e., so that additives such as MTBE are unnecessary. Iso-octane itself is used. MTBE plants can be retrofitted to produce iso-octane from isobutylene.[6],[7]

In the long run, diesel fuel is also an alternative, although it requires a major switchover to diesel-run cars. There are several varieties of biodiesel; both oxygen-containing esters and oxygen-free alkane biodiesels are available.

As a solvent

As a solvent, MTBE possesses one distinct advantage over most ethers - it has a much lower tendency to form explosive organic peroxides. Opened bottles of diethyl ether or THF can build up dangerous levels of these peroxides in months, whereas samples of MTBE are usually safe for years (but they should still be tested periodically). For this reason (as well as its higher boiling point), it is used as a solvent extensively in industry, where safety concerns and regulations make working with diethyl ether, THF, or other ethers much more difficult and expensive. However, despite the popularity of MTBE in industrial settings, it is rarely used as a solvent in academia. Research volumes are much smaller, leading to lower risks from other ethers, and in addition the use of MTBE as a solvent is very rare in literature synthetic procedures.

As a chemical reagent

Being an ether, MTBE is a Lewis base. However, unlike other ethers such as diethyl ether or THF, it does not coordinate well enough with magnesium to be used for making Grignard reagents. The tert-butyl group is easily cleaved off under strongly acidic conditions (forming a moderately stable carbocation), particularly if heated (isobutylene is lost), something which can limit the use of MTBE as a solvent.

Persistence and pervasiveness in the environment

MTBE gives water an unpleasant taste at very low concentrations, and thus can render large quantities of groundwater non-potable. MTBE is often introduced into water-supply aquifers by leaking underground storage tanks (USTs) at gasoline stations or by gasoline containing MTBE spilled onto the ground. Although USTs are much better constructed now than in the 1980s, accidental releases still take place because of the very large number of USTs. The high solubility and persistence of MTBE cause it to travel faster and farther than many other components of gasoline when released into an aquifer. Because it is water soluble, it easily moves through soil, polluting both surface and groundwater.[8]

MTBE has widespread occurrences in the aquifers of North America, where the majority of groundwater chemistry data has been acquired. As one regional example, the San Francisco Bay Area Regional Water Quality Control Board has indicated MTBE is one of the groundwater pollutants of most widespread concern in this metropolitan region.[9]

MTBE is biodegradable to CO2 and water under aerobic conditions with the correct bacteria. However, the natural occurrence of these bacteria with the ability to break ether bonds is not high, and it appears that most strains of MTBE-oxidizing bacteria are slow-growing bacteria with low biomass production per unit MTBE oxidized. In the proper type of bioreactor, such as a fluidized bed bioreactor, MTBE can be rapidly and economically removed from water to undetectable levels. Activated carbon produced from coconut shells and optimized for MTBE adsorption can also reduce MTBE to undetectable levels.[10]

Health risks

The IARC, a cancer research agency of the World Health Organization, maintains MTBE is not classifiable as a human carcinogen. MTBE can be tasted in water at concentrations of 5 – 15 µg/l[11].

MTBE is not classified as a human carcinogen at low exposure levels by the International Agency for Research on Cancer (IARC).[12] However, exposure to large doses of MTBE carries significant non-cancer-related health risks. The effects of the prolonged presence of this alcohol derivative are not fully understood.

As of 2007, researchers have limited data about the health effects of ingestion of MTBE. The United States Environmental Protection Agency (EPA) has concluded that available data are not adequate to quantify health risks of MTBE at low exposure levels in drinking water, but that the data support the conclusion that MTBE is a potential human carcinogen at high doses.[13]

Legislation and litigation

Main article: Methyl tert-butyl ether controversy

United States

MTBE removal from groundwater and soil contamination in the U.S. is estimated to cost from $1[14] to $30[15]billion, including removing the compound from aquifers and municipal water supplies and replacing leaky underground oil tanks. There is some controversy centered around the question of who will pay the costs of this remediation. In one case, the cost to oil companies to clean up the MTBE in wells belonging to Santa Monica is estimated to exceed $200 million.[16] In another case, the CIty of New York estimated a $250 million cost for cleanup of a single wellfield in Queens, NY. [17]

Recent state laws have been passed to ban MTBE in certain areas. California and New York, which together accounted for 40% of U.S. MTBE consumption, banned the chemical starting January 1, 2004, and as of September 2005, twenty-five states had signed legislation banning MTBE. (A table of state by state information, as of 2002, is available at the United States Department of Energy website.[18]

In 2000, the EPA drafted plans to phase out the use of MTBE nationwide over four years. As of fall 2006, hundreds of lawsuits are still pending regarding MTBE contamination of public and private drinking water supplies.

The Energy Policy Act of 2005, passed in the House on April 21, 2005, did not include a provision for shielding MTBE manufacturers from water contamination lawsuits. This provision was first proposed in 2003 and had been thought by some to be a priority of Tom DeLay and Rep. Joe Barton, then chairman of the Energy and Commerce Committee.[19] This bill did include a provision that gives MTBE makers, including some major oil companies, $2 billion in transition assistance as MTBE is phased out over the next nine years.[20] Due to opposition in the Senate,[21] the conference report dropped all MTBE provisions. The final bill was passed by both houses and signed into law by President Bush.[22] The lack of MTBE liability protection is resulting in a switchover to the use of ethanol as a gasoline additive. Some traders and consumer advocates are blaming this for an increase in gasoline prices.[23]

Certain patents important in the manufacture of MTBE are not held by American companies; for example, United States patent 5536886, Process for preparing alkyl ethers,[24] is owned by the Finnish company Neste. The same corporation also went on to patent the replacement of the MTBE process, an octane production process trademarked NExOCTANE.

The EPA currently lists methyl tertiary butyl ether (MTBE) as a candidate for a maximum contaminant level (MCL) in drinking water[25]. MCLs are determined by the EPA using toxicity data.

References

  1. ^ Michael Malveda, Hossein Janshekar, Masahiro Yoneyama. Gasoline Octane Improvers/Oxygenates. SRI Consulting. http://www.sriconsulting.com/CEH/Public/Reports/543.7500/
  2. ^ a b (California Air Resources Board, 2004)
  3. ^ http://www.epa.gov/otaq/rfg regs.htm#usage
  4. ^ U.S. Geological Survay detections
  5. ^ European Commission. MTBE and the Requirements for Underground Storage Tank Construction and Operation in Member States.
  6. ^ http://www.nesteengineering.com/default.asp?path=111,360,362,477
  7. ^ http://www.halliburton.com/kbr/hydroChem/petroChem/nexoctane.jsp
  8. ^ http://www.handpmg.com/lustline31-mtbe-or-benzene.htm
  9. ^ San Francisco Bay Area Regional Water Quality Control Board Integrated Basin Management Plan (2004)
  10. ^ link text
  11. ^ Fischer A, Oehm C, Selle M, Werner P. (2005). "Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)". Environ Sci Pollut Res Int. 12 (6): 381–6. doi:10.1065/espr2005.08.277. PMID 16305145.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  12. ^ http://monographs.iarc.fr/ENG/Monographs/vol73/volume73.pdf
  13. ^ http://www.epa.gov/mtbe/faq.htm#concerns
  14. ^ SIGMA - Weekly Report
  15. ^ Long Island Utility Fighting to Defeat MTBE Safe Harbor - Napoli Bern - Attorneys
  16. ^ AmeriScan: February 17, 2005
  17. ^ [http://www.nytimes.com/2009/10/20/science/earth/20exxon.html
  18. ^ Website U.S. Department of Energy
  19. ^ http://www.cnn.com/2005/POLITICS/04/21/energy.bill.mtbe.ap/
  20. ^ http://www.msnbc.msn.com/id/7574562/+MTBE&hl=en
  21. ^ Charles Babington, House Again Passes GOP Energy Measures, Washington Post, June 16, 2004, at A4 (House passes Energy Bill, but Senate opponents of MTBE provision in House Bill have the votes to prevent its enactment).
  22. ^ http://thomas.loc.gov/cgi-bin/bdquery/z?d109:h.r.00006:
  23. ^ prices ethanol/index.htm?cnn=yes http://money.cnn.com/2006/04/18/news/economy/gas prices ethanol/index.htm?cnn=yes
  24. ^ http://www.freepatentsonline.com/5536886.html
  25. ^ CCL 2 List

See also

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