Dimethyl ether

Not to be confused with dimethoxyethane.
Dimethyl ether
Skeletal formula of dimethyl ether with all implicit hydrogens shown
Skeletal formula of dimethyl ether with all implicit hydrogens shown
Ball and stick model of dimethyl ether
Ball and stick model of dimethyl ether
Names
Preferred IUPAC name
Methoxymethane[1]
Other names
Dimethyl ether[1]
R-E170
Demeon
Dimethyl oxide
Dymel A
Methyl ether
Methyl oxide
Mether
Wood ether
Identifiers
3D model (JSmol)
Abbreviations DME
1730743
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.696 Edit this at Wikidata
EC Number
  • 204-065-8
KEGG
MeSH Dimethyl+ether
RTECS number
  • PM4780000
UNII
UN number 1033
  • InChI=1S/C2H6O/c1-3-2/h1-2H3 checkY
    Key: LCGLNKUTAGEVQW-UHFFFAOYSA-N checkY
  • InChI=1/C2H6O/c1-3-2/h1-2H3
    Key: LCGLNKUTAGEVQW-UHFFFAOYAU
  • COC
Properties
C2H6O
Molar mass 46.069 g·mol−1
Appearance Colorless gas
Odor Ethereal[2]
Density 2.1146 kg m−3 (gas, 0 °C, 1013 mbar)[2]
0.735 g/mL (liquid, −25 °C)[2]
Melting point −141 °C; −222 °F; 132 K
Boiling point −24 °C; −11 °F; 249 K
71 g/L (at 20 °C (68 °F))
log P 0.022
Vapor pressure 592.8 kPa[3]
−26.3×10−6 cm3 mol−1
1.30 D
Thermochemistry
65.57 J K−1 mol−1
−184.1 kJ mol−1
−1460.4 kJ mol−1
Hazards
GHS labelling:[4]
GHS02: Flammable
Danger
H220
P210, P377, P381, P403
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 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
4
1
Flash point −41 °C (−42 °F; 232 K)
350 °C (662 °F; 623 K)
Explosive limits 27 %
Safety data sheet (SDS) ≥99% Sigma-Aldrich
Related compounds
Related ethers
 Diethyl ether

Polyethylene glycol

Related compounds
 Ethanol

Methanol

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 ?)

Dimethyl ether (DME; also known as methoxymethane) is the organic compound with the formula CH3OCH3, (sometimes ambiguously simplified to C2H6O as it is an isomer of ethanol). The simplest ether, it is a colorless gas that is a useful precursor to other organic compounds and an aerosol propellant that is currently being demonstrated for use in a variety of fuel applications.

Dimethyl ether was first synthesised by Jean-Baptiste Dumas and Eugene Péligot in 1835 by distillation of methanol and sulfuric acid.[5]

Production

Approximately 50,000 tons were produced in 1985 in Western Europe by dehydration of methanol:[6]

2 CH3OH → (CH3)2O + H2O

The required methanol is obtained from synthesis gas (syngas).[7] Other possible improvements call for a dual catalyst system that permits both methanol synthesis and dehydration in the same process unit, with no methanol isolation and purification.[7][8] Both the one-step and two-step processes above are commercially available. The two-step process is relatively simple and start-up costs are relatively low. A one-step liquid-phase process is in development.[7][9]

From biomass

Dimethyl ether is a synthetic second generation biofuel (BioDME), which can be produced from lignocellulosic biomass.[10] The EU is considering BioDME in its potential biofuel mix in 2030;[11] It can also be made from biogas or methane from animal, food, and agricultural waste,[12][13] or even from shale gas or natural gas.[14]

The Volvo Group is the coordinator for the European Community Seventh Framework Programme project BioDME[15][16] where Chemrec's BioDME pilot plant is based on black liquor gasification in Piteå, Sweden.[17]

Applications

The largest use of dimethyl ether is as the feedstock for the production of the methylating agent, dimethyl sulfate, which entails its reaction with sulfur trioxide:

CH3OCH3 + SO3 → (CH3)2SO4

Dimethyl ether can also be converted into acetic acid using carbonylation technology related to the Monsanto acetic acid process:[6]

(CH3)2O + 2 CO + H2O → 2 CH3CO2H

Laboratory reagent and solvent

Dimethyl ether is a low-temperature solvent and extraction agent, applicable to specialised laboratory procedures. Its usefulness is limited by its low boiling point (−23 °C (−9 °F)), but the same property facilitates its removal from reaction mixtures. Dimethyl ether is the precursor to the useful alkylating agent, trimethyloxonium tetrafluoroborate.[18]

Niche applications

A mixture of dimethyl ether and propane is used in some over-the-counter "freeze spray" products to treat warts by freezing them.[19][20] In this role, it has supplanted halocarbon compounds (Freon).

Dimethyl ether is also a component of certain high temperature "Map-Pro" blowtorch gas blends, supplanting the use of methyl acetylene and propadiene mixtures.[21]

Dimethyl ether is also used as a propellant in aerosol products. Such products include hair spray, bug spray and some aerosol glue products.

Research

Fuel

Installation of BioDME synthesis towers at Chemrec's pilot facility

A potentially major use of dimethyl ether is as substitute for propane in LPG used as fuel in household and industry.[22] Dimethyl ether can also be used as a blendstock in propane autogas.[23]

It is also a promising fuel in diesel engines,[24] and gas turbines. For diesel engines, an advantage is the high cetane number of 55, compared to that of diesel fuel from petroleum, which is 40–53.[25] Only moderate modifications are needed to convert a diesel engine to burn dimethyl ether. The simplicity of this short carbon chain compound leads to very low emissions of particulate matter during combustion. For these reasons as well as being sulfur-free, dimethyl ether meets even the most stringent emission regulations in Europe (EURO5), U.S. (U.S. 2010), and Japan (2009 Japan).[26]

At the European Shell Eco Marathon, an unofficial World Championship for mileage, vehicle running on 100 % dimethyl ether drove 589 km/L (169.8 cm3/100 km), fuel equivalent to gasoline with a 50 cm3 displacement 2-stroke engine. As well as winning they beat the old standing record of 306 km/liter (326.8 cm3/100 km), set by the same team in 2007.[27]

To study the dimethyl ether for the combustion process a chemical kinetic mechanism[28] is required which can be used for Computational fluid dynamics calculation.

Refrigerant

Dimethyl ether is a refrigerant with ASHRAE refrigerant designation R-E170. It is also used in refrigerant blends with e.g. ammonia, carbon dioxide, butane and propene. Dimethyl ether was the first refrigerant. In 1876, the French engineer Charles Tellier bought the ex-Elder-Dempster a 690 tons cargo ship Eboe and fitted a methyl-ether refrigerating plant of his design. The ship was renamed Le Frigorifique and successfully imported a cargo of refrigerated meat from Argentina. However the machinery could be improved and in 1877 another refrigerated ship called Paraguay with a refrigerating plant improved by Ferdinand Carré was put into service on the South American run.[29][30]

Safety

Unlike other alkyl ethers, dimethyl ether resists autoxidation.[31] Dimethyl ether is also relatively non-toxic, although it is highly flammable. On July 28, 1948, a BASF factory in Ludwigshafen suffered an explosion after 30 tonnes of dimethyl ether leaked from a tank and ignited in the air. 200 people died, and a third of the industrial plant was destroyed.[32]

Data sheet

Routes to produce dimethyl ether

Vapor pressure

Experimental vapor pressures of dimethyl ether[33]
Temperature (K) Pressure (kPa)
233.128 54.61
238.126 68.49
243.157 85.57
248.152 105.59
253.152 129.42
258.16  157.53
263.16  190.44
268.161 228.48
273.153 272.17
278.145 321.87
283.16  378.66
288.174 443.57
293.161 515.53
298.172 596.21
303.16  687.37
305.16  726.26
308.158 787.07
313.156 897.59
316.154 968.55
318.158 1018.91
323.148 1152.35
328.149 1298.23
333.157 1457.5 
333.159 1457.76
338.154 1631.01
343.147 1818.8 
348.147 2022.45
353.146 2242.74
353.158 2243.07
358.145 2479.92
363.148 2735.67
368.158 3010.81
373.154 3305.67
378.15  3622.6 
383.143 3962.25
388.155 4331.48
393.158 4725.02
398.157 5146.82
400.378 5355.8 

See also

References

  1. ^ a b "CHAPTER P-6. Applications to Specific Classes of Compounds". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 703. doi:10.1039/9781849733069-00648. ISBN 978-0-85404-182-4.
  2. ^ a b c Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  3. ^ "Dimethylether". 19 October 2018. Archived from the original on 6 November 2021. Retrieved 10 November 2020.
  4. ^ GHS: Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  5. ^ Ann. chim. phys., 1835, [2] 58, p. 19
  6. ^ a b Manfred Müller, Ute Hübsch, "Dimethyl Ether" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a08_541
  7. ^ a b c "CHEMSYSTEMS.COM" (PDF). www.chemsystems.com. Archived from the original (PDF) on 22 November 2009. Retrieved 1 April 2018.
  8. ^ P.S. Sai Prasad et al., Fuel Processing Technology, 2008, 89, 1281.
  9. ^ "Air Products Technology Offerings". airproducts.com. Archived from the original on 12 December 2007. Retrieved 1 April 2018.
  10. ^ "BioDME". www.biodme.eu. Archived from the original on 10 April 2020. Retrieved 1 April 2018.
  11. ^ "Biofuels in the European Union, 2006" (PDF). europa.eu. Archived (PDF) from the original on 3 December 2019. Retrieved 1 April 2018.
  12. ^ "Oberon Fuels Brings Production Units Online, Launching the First North American Fuel-grade DME Facilities". 7 June 2013. Archived from the original on 2021-05-06. Retrieved 2018-08-04.
  13. ^ "Associated Gas Utilization via mini GTL" (PDF). Archived (PDF) from the original on 2018-08-04. Retrieved 2018-08-04.
  14. ^ Ogawa, Takashi; Inoue, Norio; Shikada, Tutomu; Inokoshi, Osamu; Ohno, Yotaro (2004). "Direct Dimethyl Ether (DME) synthesis from natural gas". Natural Gas Conversion VII, Proceedings of the 7th Natural Gas Conversion Symposium. Studies in Surface Science and Catalysis. Vol. 147. pp. 379–384. doi:10.1016/S0167-2991(04)80081-8. ISBN 9780444515995.
  15. ^ "Home | Volvo Group". Archived from the original on 2009-05-25. Retrieved 2011-11-04.
  16. ^ "Volvo Group - Driving prosperity through transport solutions". www.volvo.com. Archived from the original on 6 June 2020. Retrieved 1 April 2018.
  17. ^ Chemrec press release September 9, 2010 Archived June 12, 2017, at the Wayback Machine
  18. ^ T. J. Curphey (1988). "Trimethyloxonium tetrafluoroborate". Organic Syntheses; Collected Volumes, vol. 6, p. 1019.
  19. ^ "A Pharmacist's Guide to OTC Therapy: OTC Treatments for Warts". July 2006. Archived from the original on 2010-06-17. Retrieved 2009-05-02.
  20. ^ "Archived copy" (PDF). Food and Drug Administration. Archived from the original (PDF) on 2009-04-20. Retrieved 2019-12-16.{{cite web}}: CS1 maint: archived copy as title (link)
  21. ^ "Archived copy" (PDF). Archived from the original (PDF) on 2016-12-20. Retrieved 2016-03-02.{{cite web}}: CS1 maint: archived copy as title (link)
  22. ^ "IDA Fact Sheet DME/LPG Blends 2010 v1" (PDF). aboutdme.org. Archived (PDF) from the original on 24 July 2011. Retrieved 1 April 2018.
  23. ^ Fleisch, T. H.; Basu, A.; Sills, R. A. (November 2012). "The Status of DME developments in China and beyond, 2012". Journal of Natural Gas Science and Engineering. 9: 94–107. doi:10.1016/j.jngse.2012.05.012. Archived from the original on 2022-05-04. Retrieved 2020-11-21.
  24. ^ nycomb.se, Nycomb Chemicals company Archived 2008-06-03 at the Wayback Machine
  25. ^ "Haldor Topsoe - Products & Services - Technologies - DME - Applications - DME as Diesel Fuel". Archived from the original on 2007-10-08. Retrieved 2011-11-04. topsoe.com
  26. ^ "Archived copy" (PDF). Archived from the original (PDF) on 2009-01-07. Retrieved 2011-11-04.{{cite web}}: CS1 maint: archived copy as title (link), Conference on the Development and Promotion of Environmentally Friendly Heavy Duty Vehicles such as DME Trucks, Washington DC, March 17, 2006
  27. ^ "The Danish Ecocar Team - List of achievements". dtu.dk. Archived from the original on 17 October 2009. Retrieved 1 April 2018.
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  29. ^ A history of the frozen meat trade, page 26-28
  30. ^ http://www.ashrae.org/technology/page/1933#et Archived 2012-01-03 at the Wayback Machine ASHRAE list of refrigerants
  31. ^ A comparative study on the autoxidation of dimethyl ether (DME) comparison with diethyl ether (DEE) and diisopropyl ether (DIPE), Michie Naito, Claire Radcliffe, Yuji Wada, Takashi Hoshino, Xiongmin Liu, Mitsuru Arai, Masamitsu Tamura. Journal of Loss Prevention in the Process Industries, Volume 18, Issues 4–6, July–November 2005, Pages 469–473 DOI
  32. ^ Welt im Film 167/1948 Archived 2021-01-29 at the Wayback Machine. filmothek.bundesarchiv.de
  33. ^ Wu, Jiangtao; Liu, Zhigang; Pan, Jiang; Zhao, Xiaoming (2003-11-25). "Vapor Pressure Measurements of Dimethyl Ether from (233 to 399) K". J. Chem. Eng. Data. 49: 32–34. doi:10.1021/je0340046. Archived from the original on 2022-05-04. Retrieved 2022-01-07.