Propene

Propene, also known as propylene or methyl ethylene, is an unsaturated organic compound with the chemical formula . It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petroleum-like odor[2]

Not to be confused with propane or propyne.
"Propylene" redirects here. For the unrelated compound referred to as "propolene", see glucomannan.
Propene
Skeletal formula of propene
Propylene
Names
Preferred IUPAC name
Propene[1]
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.693
KEGG
RTECS number
  • UC6740000
UNII
UN number 1077
In Liquefied petroleum gas: 1075
Properties
C3H6
Molar mass 42.081 g·mol−1
Appearance Colorless gas
Density 1.81 kg/m3, gas (1.013 bar, 15 °C)
1.745 kg/m3, gas (1.013 bar, 25 °C)
613.9 kg/m3, liquid
Melting point −185.2 °C (−301.4 °F; 88.0 K)
Boiling point −47.6 °C (−53.7 °F; 225.6 K)
0.61 g/m3
-31.5·10−6 cm3/mol
Viscosity 8.34 µPa·s at 16.7 °C
Structure
0.366 D (gas)
Hazards
Safety data sheet External MSDS
R-phrases (outdated) 12
S-phrases (outdated) 9-16-33
NFPA 704 (fire diamond)
Flammability code 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. propaneHealth code 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
4
1
1
Flash point −108 °C (−162 °F; 165 K)
Related compounds
Related alkenes;
related groups
 Ethylene, Isomers of Butylene;
Allyl, Propenyl
Related compounds
 Propane, Propyne
Propadiene, 1-Propanol
2-Propanol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Bio-propylene is the bio-based counterpart of propylene.[3][4]

Production

Steam cracking
Main article: steam cracking

The dominant technology for producing propylene is steam cracking. The same technology is applied to ethane to ethylene. These two conversions are the #2 and #1 processes in the chemical industry, as judged by their scale.[5] In this process, propane undergoes dehydrogenation. The by-product is hydrogen:

CH3CH2CH3 → CH3CH=CH2 + H2

The yield of propene is about 85 m%. By-products are usually used as fuel for the propane dehydrogenation reaction. Steam cracking is one of the most energy-intensive industrial processes.

The feedstock is naphtha or propane, especially in the Middle East, where there is an abundance of propane from oil/gas operations.[6] Propene can be separated by fractional distillation from hydrocarbon mixtures obtained from cracking and other refining processes; refinery-grade propene is about 50 to 70%.[7] In the United States shale gas is a major source of propane.

Olefin conversion technology

In the Phillips Triolefin or Olefin conversion technology propylene is interconverted with ethylene and 2-butenes. Rhenium and molybdenum catalysts are used:[8]

CH2=CH2 + CH3CH=CHCH3 → 2 CH2=CHCH3

The technology is founded on an olefin metathesis reaction discovered at Phillips Petroleum Company.[9][10] Propene yields of about 90 wt% are achieved.

Main article: Syngas to gasoline plus

Related is the Methanol-to-Olefins/Methanol-to-Propene process. It converts synthesis gas (syngas) to methanol, and then converts the methanol to ethylene and/or propene. The process produces water as by-product. Synthesis gas is produced from |the reformation of natural gas or by the steam-induced reformation of petroleum products such as naphtha, or by gasification of coal.

Fluid catalytic cracking

High severity fluid catalytic cracking (FCC) uses traditional FCC technology under severe conditions (higher catalyst-to-oil ratios, higher steam injection rates, higher temperatures, etc.) in order to maximize the amount of propene and other light products. A high severity FCC unit is usually fed with gas oils (paraffins) and residues, and produces about 20–25 m% propene on feedstock together with greater volumes of motor gasoline and distillate byproducts.

Market and research

Propene production has remained static at around 35 million tonnes (Europe and North America only) from 2000 to 2008, but it has been increasing in East Asia, most notably Singapore and China.[11] Total world production of propene is currently about half that of ethylene.

The use of engineered enzymes has been explored but is of no commercial value.[12]

Uses

Propene is the second most important starting product in the petrochemical industry after ethylene. It is the raw material for a wide variety of products. Manufacturers of the plastic polypropylene account for nearly two thirds of all demand.[13] Polypropylene end uses include films, fibers, containers, packaging, and caps and closures. Propene is also used for the production of important chemicals such as propylene oxide, acrylonitrile, cumene, butyraldehyde, and acrylic acid. In the year 2013 about 85 million tonnes of propene were processed worldwide.[13]

Propene and benzene are converted to acetone and phenol via the cumene process.

Overview of the cumene process

Propene is also used to produce isopropanol (propan-2-ol), acrylonitrile, propylene oxide, and epichlorohydrin.[14] The industrial production of acrylic acid involves the catalytic partial oxidation of propene.[15] Propene is also an intermediate in the one-step propane selective oxidation to acrylic acid.[16][17][18][19] In industry and workshops, propene is used as an alternative fuel to acetylene in Oxy-fuel welding and cutting, brazing and heating of metal for the purpose of bending. It has become a standard in BernzOmatic products and others in MAPP substitutes,[20] now that true MAPP gas is no longer available.

Reactions

Propene resembles other alkenes in that it undergoes addition reactions relatively easily at room temperature. The relative weakness of its double bond explains its tendency to react with substances that can achieve this transformation. Alkene reactions include: 1) polymerization, 2) oxidation, 3) halogenation and hydrohalogenation, 4) alkylation, 5) hydration, 6) oligomerization, and 7) hydroformylation.

Combustion

Propene undergoes combustion reactions in a similar fashion to other alkenes. In the presence of sufficient or excess oxygen, propene burns to form water and carbon dioxide.

2 C3H6 + 9 O2 → 6 CO2 + 6 H2O

When insufficient oxygen is present for complete combustion, incomplete combustion occurs allowing carbon monoxide and/or soot (carbon) to be formed as well.

C3H6 + 2 O2 → 3 H2O + 2 C + CO

Environmental safety

Propene is a product of combustion from forest fires, cigarette smoke, and motor vehicle and aircraft exhaust. It is an impurity in some heating gases. Observed concentrations have been in the range of 0.1-4.8 parts per billion (ppb) in rural air, 4-10.5 ppb in urban air, and 7-260 ppb in industrial air samples.[7]

In the United States and some European countries a threshold limit value of 500 parts per million (ppm) was established for occupational (8-hour time-weighted average) exposure. It is considered a volatile organic compound (VOC) and emissions are regulated by many governments, but it is not listed by the U.S. Environmental Protection Agency (EPA) as a hazardous air pollutant under the Clean Air Act. With a relatively short half-life, it is not expected to bioaccumulate.[7]

Propene has low acute toxicity from inhalation. Inhalation of the gas can cause anesthetic effects and at very high concentrations, unconsciousness. However, the asphyxiation limit for humans is about 10 times higher (23%) than the lower flammability level.[7]

Storage and handling

Since propene is volatile and flammable, precautions must be taken to avoid fire hazards in the handling of the gas. If propene is loaded to any equipment capable of causing ignition, such equipment should be shut down while loading, unloading, connecting or disconnecting. Propene is usually stored as liquid under pressure, although it is also possible to store it safely as gas at ambient temperature in approved containers.[21]

Pharmacology

Propene acts as a central nervous system depressant via allosteric agonism of the GABAA receptor. Excessive exposure may result in sedation and amnesia, progressing to coma and death in a mechanism equivalent to benzodiazepine overdose. Intentional inhalation may also result in death via asphyxiation (sudden inhalant death).

Occurrence in nature

Propene is detected in the interstellar medium through microwave spectroscopy.[22] On September 30, 2013, NASA also announced that the Cassini orbiter spacecraft, part of the Cassini-Huygens mission, had discovered small amounts of naturally occurring propene in the atmosphere of Titan using spectroscopy.[23][24]

See also

References
  1. "Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 31. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. "Propylene".
  3. Bio-based drop-in, smart drop-in and dedicated chemicals
  4. Duurzame bioplastics op basis van hernieuwbare grondstoffen
  5. Giovanni Maggini (2013-04-17). "Technology Economics: Propylene via Propane Dehydrogenation, Part 3". Slideshare.net. Retrieved 2013-11-12.
  6. Ashford’s Dictionary of Industrial Chemicals, Third edition, 2011, ISBN 978-0-9522674-3-0, pages 7766-9
  7. "Product Safety Assessment(PSA): Propylene". Dow Chemical Co. Archived from the original on 2013-06-22. Retrieved 2011-07-11.
  8. Ghashghaee, Mohammad (2018). "Heterogeneous catalysts for gas-phase conversion of ethylene to higher olefins". Rev. Chem. Eng. 34 (5): 595–655. doi:10.1515/revce-2017-0003. S2CID 103664623.
  9. Banks, R. L.; Bailey, G. C. (1964). "Olefin Disproportionation. A New Catalytic Process". Industrial & Engineering Chemistry Product Research and Development. 3 (3): 170–173. doi:10.1021/i360011a002.
  10. Lionel Delaude, Alfred F. Noels (2005). "Metathesis". Kirk-Othmer Encyclopedia of Chemical Technology. Weinheim: Wiley-VCH. doi:10.1002/0471238961.metanoel.a01. ISBN 978-0471238966.CS1 maint: uses authors parameter (link)
  11. Amghizar, Ismaël; Vandewalle, Laurien A.; Van Geem, Kevin M.; Marin, Guy B. (2017). "New Trends in Olefin Production". Engineering. 3 (2): 171–178. doi:10.1016/J.ENG.2017.02.006.
  12. de Guzman, Doris (October 12, 2012). "Global Bioenergies in bio-propylene". Green Chemicals Blog.
  13. "Market Study: Propylene (2nd edition), Ceresana, December 2014". ceresana.com. Retrieved 2015-02-03.
  14. Budavari, Susan, ed. (1996). "8034. Propylene". The Merck Index, Twelfth Edition. New Jersey: Merck & Co. pp. 1348–1349.
  15. J.G.L., Fierro (Ed.) (2006). Metal Oxides, Chemistry and Applications. CRC Press. pp. 414–455.CS1 maint: extra text: authors list (link)
  16. Naumann d'Alnoncourt, Raoul; Csepei, Lénárd-István; Hävecker, Michael; Girgsdies, Frank; Schuster, Manfred E.; Schlögl, Robert; Trunschke, Annette (March 2014). "The reaction network in propane oxidation over phase-pure MoVTeNb M1 oxide catalysts". Journal of Catalysis. 311: 369–385. doi:10.1016/j.jcat.2013.12.008. hdl:11858/00-001M-0000-0014-F434-5.
  17. Amakawa, Kazuhiko; Kolen'Ko, Yury V.; Villa, Alberto; Schuster, Manfred E/; Csepei, Lénárd-István; Weinberg, Gisela; Wrabetz, Sabine; Naumann d'Alnoncourt, Raoul; Girgsdies, Frank; Prati, Laura; Schlögl, Robert; Trunschke, Annette (7 June 2013). "Multifunctionality of Crystalline MoV(TeNb) M1 Oxide Catalysts in Selective Oxidation of Propane and Benzyl Alcohol". ACS Catalysis. 3 (6): 1103–1113. doi:10.1021/cs400010q. hdl:11858/00-001M-0000-000E-FA39-1.
  18. Hävecker, Michael; Wrabetz, Sabine; Kröhnert, Jutta; Csepei, Lenard-Istvan; Naumann d'Alnoncourt, Raoul; Kolen'Ko, Yury V.; Girgsdies, Frank; Schlögl, Robert; Trunschke, Annette (January 2012). "Surface chemistry of phase-pure M1 MoVTeNb oxide during operation in selective oxidation of propane to acrylic acid". Journal of Catalysis. 285 (1): 48–60. doi:10.1016/j.jcat.2011.09.012. hdl:11858/00-001M-0000-0012-1BEB-F.
  19. Csepei, Lénárd-István (2011). Kinetic studies of propane oxidation on Mo and V based mixed oxide catalysts. pp. 3–24, 93. doi:10.14279/depositonce-2972.
  20. For example, "MAPP-Pro"
  21. Encyclopedia of Chemical Technology, Fourth edition, 1996, ISBN 0471-52689-4 (v.20), page 261
  22. Marcelino, N.; Cernicharo, J.; Agúndez, M.; Roueff, E.; Gerin, M.; Martín-Pintado, J.; Mauersberger, R.; Thum, C. (2007-08-10). "Discovery of Interstellar Propylene (CH2CHCH3): Missing Links in Interstellar Gas-Phase Chemistry". The Astrophysical Journal. IOP. 665 (2): L127–L130. doi:10.1086/521398. S2CID 15832967.
  23. "Spacecraft finds propylene on Saturn moon, Titan". UPI.com. 2013-09-30. Retrieved 2013-11-12.
  24. "Cassini finds ingredient of household plastic on Saturn moon". Spacedaily.com. Retrieved 2013-11-12.
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