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Methyl tert-butyl ether

From Wikipedia, the free encyclopedia
Methyl tert-butyl ether
Skeletal formula of MTBE
Ball-and-stick model of the MTBE molecule
Names
Preferred IUPAC name
2-Methoxy-2-methylpropane
Other names
  • Methyl tertiary-butyl ether
  • Methyl t-butyl ether
  • MTBE
  • tert-Butyl methyl ether
  • tBME
  • tert-BuOMe
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.015.140 Edit this at Wikidata
KEGG
UNII
  • InChI=1S/C5H12O/c1-5(2,3)6-4/h1-4H3 checkY
    Key: BZLVMXJERCGZMT-UHFFFAOYSA-N checkY
  • InChI=1/C5H12O/c1-5(2,3)6-4/h1-4H3
    Key: BZLVMXJERCGZMT-UHFFFAOYAA
  • O(C(C)(C)C)C
Properties
C5H12O
Molar mass 88.150 g·mol−1
Appearance colourless liquid
Density 0.7404 g/cm3
Melting point −108.6 °C (−163.5 °F; 164.6 K)
Boiling point 55.5 °C (131.9 °F; 328.6 K)
26 g/L (20 °C)[1]
Vapor pressure 27kPa (20ºC)
Viscosity 3.4·10-4 Pa·s (at 25ºC)
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 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 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
3
0
Flash point −32.78 °C (−27.00 °F; 240.37 K)
435 °C (815 °F; 708 K)
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 (MTBE), also known as tert-butyl methyl ether, is an organic compound with a structural formula (CH3)3COCH3. MTBE is a volatile, flammable, and colorless liquid that is sparingly soluble in water.[1] Primarily used as a fuel additive, MTBE is blended into gasoline to increase its octane rating and knock resistance, and reduce unwanted emissions.[2][3]

Production and properties

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MTBE is manufactured via the chemical reaction of methanol and isobutylene. Methanol is primarily derived from natural gas,[4] where steam reforming converts the various light hydrocarbons in natural gas (primarily methane) into carbon monoxide and hydrogen.[5] The resulting gases then further react in the presence of a catalyst to form methanol.[6] Isobutylene can be produced through a variety of methods. n-butane can be isomerized into isobutane which can be dehydrogenated to isobutylene.[7] In the Halcon process, t-Butyl hydroperoxide derived from isobutane oxygenation is treated with propylene to produce propylene oxide and t-butanol. The t-butanol can be dehydrated to isobutylene.

MTBE production across the globe has been steady because of its positive impact on engine performance.[8]

US perspective

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Under pressure from the bioethanol lobby,[8] production of MTBE in the U.S. peaked in 1999 at 260,000 barrels per day[9] before dropping down due to environmental and health concerrns to about 50,000 barrels per day and holding steady,[10] mostly for the export market. After the purchase of SABIC,[11][12] oil giant Saudi Aramco is now considered to be the world's largest producer[13] with an estimated production capacity of 2.37 million metric tons per year (mt/yr).[14] Worldwide production capacity of MTBE in 2018 was estimated to be 35 million metric tons.[15]

Uses

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

As anti-knocking agent

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In the U.S. MTBE has been used in gasoline at low levels since 1979, replacing tetraethyllead (TEL) as an antiknock (octane rating) additive to prevent engine knocking.[16] Oxygenates also help gasoline burn more completely, reducing tailpipe emissions. Oxygenates also dilute or displace gasoline components such as aromatics (e.g., benzene). Before the introduction of other oxygenates and octane enhancers, refiners chose MTBE for its blending characteristics and low cost.

Alternatives to MTBE as an anti-knock agent

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Other oxygenates are available as additives for gasoline including ethanol and other ethers such as ETBE.

Ethanol has been advertised as a safe alternative by agricultural and other interest groups in the U.S. and Europe. In 2003, California was the first U.S. state to start replacing MTBE with ethanol.

An alternative to ethanol is 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, so that additives such as MTBE are unnecessary. Iso-octane itself is used. MTBE plants can be retrofitted to produce iso-octane from isobutylene.[17][18]

As a solvent

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MTBE is sometimes used as a solvent,[19][20][21] although it is used less commonly than diethyl ether. Although an ether, MTBE is a poor Lewis base and does not support formation of Grignard reagents. It is also unstable toward strong acids. It reacts dangerously with bromine.[22]

MTBE forms azeotropes with water (52.6 °C; 96.5% MTBE)[23] and methanol (51.3 °C; 68.6% MTBE).[24] The solubility of water in MTBE is reported to be 1.5 g/100g at 23 °C.[23]

In an investigational medical procedure called contact dissolution therapy, MTBE is injected directly into the gallbladder to dissolve cholesterol gallstones. Due to concerns of MTBE toxicity and potentially serious side effects in the event of solvent draining into the duodenum, and the advent of laparoscopic surgery techniques, this procedure is considered obsolete. [25][26][27]

MTBE is used in organic chemistry as a relatively inexpensive solvent with properties comparable to diethyl ether, but with a higher boiling point and less solubility in water. As a solvent, MTBE has one distinct advantage over most ethers - it has a much lower tendency to form explosive organic peroxides. It is widely used as a solvent in industry where, for safety and regulatory reasons, handling diethyl ether or other ethers is much more difficult and expensive. MTBE as a solvent is used in the oil refining industry as a method for dewaxing waxy petroleum fractions.

Persistence and pervasiveness in the environment

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MTBE gives water an unpleasant taste at very low concentrations. MTBE often is introduced into water-supply aquifers by leaking underground storage tanks (USTs) at gasoline stations or spills of gasoline. The higher water solubility and persistence of MTBE cause it to travel faster and farther than many other components of gasoline when released into an aquifer.[28]

MTBE is biodegraded by the action of bacteria. In the proper type of bioreactor, such as a fluidized bed bioreactor, MTBE may be removed rapidly and economically from water to undetectable levels. Activated carbon produced from coconut shells and optimized for MTBE adsorption may reduce MTBE to undetectable levels,[29] although this level of reduction is likely to occur only in the most ideal circumstances. There are currently no known published cases of any in-situ treatment method that has been capable of reducing contaminant concentrations to baseline (pre-development) conditions within the aquifer soil matrix.

According to the International Agency for Research on Cancer (IARC), a branch of the World Health Organization, MTBE is not classified as a human carcinogen. MTBE may be tasted in water at concentrations of 5–15 μg/L (5-15ppb).[30]

Regulation and litigation in the U.S.

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Main article: MTBE controversy

Restrictions on MTBE manufacturing and use

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The Energy Policy Act of 2005, as approved by the U.S. House of Representatives, 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.[31] This bill did include a provision that gave MTBE makers, including some major oil companies, $2 billion in transition assistance while MTBE was phased out over the following nine years.[32] Due to opposition in the Senate,[33] the conference report dropped all MTBE provisions. The final bill was signed into law by President George W. Bush.[34] The lack of MTBE liability protection is resulting in a switchover to the use of ethanol as a gasoline additive.

Cleanup costs and litigation

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MTBE removal from groundwater and soil contamination in the U.S. was estimated to cost from $1 billion[35] to US$30 billion,[36] including removing the compound from aquifers and municipal water supplies and replacing leaky underground oil tanks. In one case, the cost to oil companies to clean up the MTBE in wells belonging to the city of Santa Monica, California was estimated to exceed $200 million.[37] In another case, New York City estimated a $250 million cost for cleanup of a single wellfield in the borough of Queens in 2009.[38] In 2013 a jury awarded the State of New Hampshire $236 million in damages in order to treat groundwater contaminated by MTBE.[39]

Many lawsuits are still pending regarding MTBE contamination of public and private drinking water supplies.

Drinking water regulations

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EPA first listed MTBE in 1998 as a candidate for development of a national Maximum Contaminant Level (MCL) standard in drinking water.[40] The agency listed MTBE on its Contaminant Candidate List in 2022 but has not announced whether it will develop an MCL.[41] EPA uses toxicity data in developing MCLs for public water systems.[42]

California established a state-level MCL for MTBE, 13 micrograms per liter, in 2000.[43]

See also

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References

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  1. ^ a b Record of Methyl tert-butyl ether in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  2. ^ "Methyl tertiary butyl ether prices, markets & analysis". ICIS Explore. Retrieved 2020-06-28.
  3. ^ "Oxygenates". www.api.org. Retrieved 2020-06-28.
  4. ^ "How is Methanol Produced". METHANOL INSTITUTE. Retrieved 2020-06-29.
  5. ^ Anzelmo, Bryce; Wilcox, Jennifer; Liguori, Simona. "Hydrogen production via natural gas steam reforming in a Pd-Au membrane reactor. Investigation of reaction temperature and GHSV effects and long-term stability" (PDF). Journal of Membrane Science: 25–32.[permanent dead link‍]
  6. ^ "methanol | Properties, Production, Uses, & Poisoning". Encyclopedia Britannica. Retrieved 2020-06-29.
  7. ^ "Methyl Tertiary Butyl Ether (MTBE) Production and Manufacturing Process". ICIS Explore. Retrieved 2020-06-29.
  8. ^ a b Werner Dabelstein, Arno Reglitzky, Andrea Schütze and Klaus Reders "Automotive Fuels" in Ullmann's Encyclopedia of Industrial Chemistry 2007, Wiley-VCH, Weinheim. doi:10.1002/14356007.a16_719.pub2
  9. ^ "The United States continues to export MTBE, mainly to Mexico, Chile, and Venezuela - Today in Energy - U.S. Energy Information Administration (EIA)". www.eia.gov. Retrieved 2020-06-28.
  10. ^ "United States | Methyl Tertiary Butyl Ether (MTBE): Production | Economic Indicators". www.ceicdata.com. Retrieved 2020-06-28.
  11. ^ "Aramco completes its acquisition of a 70% stake in SABIC from the Public Investment Fund (PIF)". www.saudiaramco.com. 17 June 2020. Retrieved 2020-06-29.
  12. ^ "Saudi Aramco buys SABIC shares on market as it completes acquisition". Reuters. 2020-06-14. Retrieved 2020-06-29.
  13. ^ "Saudi Aramco to have largest MTBE capacity in Middle East and Asia". Retrieved 2020-06-29.
  14. ^ "Saudi Aramco's MTBE trading volume likely to rise after Sabic purchase | S&P Global Platts". www.spglobal.com. 2019-04-09. Retrieved 2020-06-29.
  15. ^ "MTBE annual production capacity globally 2023". Statista. Retrieved 2020-06-28.
  16. ^ "Overview | Methyl Tertiary Butyl Ether (MTBE) | US EPA". archive.epa.gov. Retrieved 2021-04-07.
  17. ^ "NExOCTANE™ - Neste Jacobs". www.nesteengineering.com. Archived from the original on January 6, 2006.
  18. ^ "KBR - NExOCTANE™". Archived from the original on 2006-01-06. Retrieved 2006-01-31.
  19. ^ Matyash, V.; Liebisch, G.; Kurzchalia, T. V.; Shevchenko, A.; Schwudke, D. (2008). "Lipid extraction by methyl-tert-butyl ether for high-throughput lipidomics". The Journal of Lipid Research. 49 (5): 1137–1146. doi:10.1194/jlr.D700041-JLR200. PMC 2311442. PMID 18281723.
  20. ^ Vopička, Ondřej; Pilnáček, Kryštof; Číhal, Petr; Friess, Karel (2016-03-01). "Sorption of methanol, dimethyl carbonate, methyl acetate, and acetone vapors in CTA and PTMSP: General findings from the GAB Analysis". Journal of Polymer Science Part B: Polymer Physics. 54 (5): 561–569. Bibcode:2016JPoSB..54..561V. doi:10.1002/polb.23945. ISSN 1099-0488.
  21. ^ Vopička, Ondřej; Radotínský, Daniel; Friess, Karel (2016-02-01). "Sorption of vapour mixtures of methanol and dimethyl carbonate in PTMSP: Cooperative and competitive sorption in one system". European Polymer Journal. 75: 243–250. doi:10.1016/j.eurpolymj.2015.12.015.
  22. ^ "Interaction between bromine and tert-butyl methyl ether". UK Chemical Reaction Hazards Forum. Archived from the original on 13 March 2011. Retrieved 13 May 2010.
  23. ^ a b Zeon Corporation Archived 2011-07-22 at the Wayback Machine
  24. ^ CRC Handbook of Chemistry and Physics, 90th edition
  25. ^ Schoenfield LJ, Marks JW (1993). "Oral and contact dissolution of gallstones". Am. J. Surg. 165 (4): 427–30. doi:10.1016/S0002-9610(05)80934-1. PMID 8480875.
  26. ^ "Health Guide: Gallstones". New York Times.
  27. ^ https://www.aetna.com/cpb/medical/data/500_599/0509.html | access-date = June 3, 2024
  28. ^ San Francisco Bay Area Regional Water Quality Control Board Integrated Basin Management Plan (2004) Archived 2008-02-29 at the Wayback Machine
  29. ^ link text Archived 2011-07-28 at the Wayback Machine
  30. ^ 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. S2CID 97168152.
  31. ^ http://www.cnn.com/2005/POLITICS/04/21/energy.bill.mtbe.ap/ Archived 2005-04-22 at the Wayback Machine
  32. ^ "House approves $12 billion energy package". NBC News. 2005-04-22.
  33. ^ 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).
  34. ^ United States. Energy Policy Act of 2005. Pub. L. 109–58 (text) (PDF). Approved 2005-08-08.
  35. ^ "MTBE Cleanup Estimates". SIGMA Weekly Report. Fairfax, VA: Society of Independent Gasoline Marketers of America (SIGMA). 2005-05-23. Archived from the original on 2009-10-09.
  36. ^ "Long Island Utility Fighting to Defeat MTBE Safe Harbor". The MTBE e-Resource. New York, NY: Napoli Bern, LLP. 2004-03-16. Archived from the original on 2007-10-20.
  37. ^ "Oil Companies Pay Santa Monica MTBE Cleanup Costs". Environment News Service. Ecology Prime Media, Inc. 2005-02-17.
  38. ^ Navarro, Mireya (2009-10-20). "City Awarded $105 Million in Exxon Mobil Lawsuit". The New York Times. Retrieved 2010-05-12.
  39. ^ Earle, Sarah (2013-04-09). "Exxon Mobil is Found Negligent in New Hampshire MTBE Use". Bloomberg.
  40. ^ EPA (1998-03-02). "Announcement of the Drinking Water Contaminant Candidate List." Federal Register, 63 FR 10274
  41. ^ EPA (2022-11-14). "Drinking Water Contaminant Candidate List 5―Final." Federal Register, 87 FR 68060
  42. ^ "How EPA Regulates Drinking Water Contaminants". EPA. 2017-05-03.
  43. ^ "MTBE: Regulations and Drinking Water Monitoring Results". Sacramento, CA: California State Water Resources Control Board. 2014-08-04.
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