Propylene is a product of combustion from forest fires, cigarette smoke, and motor vehicle and aircraft exhaust.[4] It was discovered in 1850 by A. W. von Hoffman's student Captain (later Major General[5]) John Williams Reynolds as the only gaseous product of thermal decomposition of amyl alcohol to react with chlorine and bromine.[6]
The dominant technology for producing propylene is steam cracking, using propane as the feedstock. Cracking propane yields a mixture of ethylene, propylene, methane, hydrogen gas, and other related compounds. The yield of propylene is about 15%. The other principal feedstock is naphtha, especially in the Middle East and Asia.[7]
Propylene can be separated by fractional distillation from the hydrocarbon mixtures obtained from cracking and other refining processes; refinery-grade propene is about 50 to 70%.[8] In the United States, shale gas is a major source of propane.
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% (by mass) of propene on feedstock together with greater volumes of motor gasoline and distillate byproducts. These high temperature processes are expensive and have a high carbon footprint. For these reasons, alternative routes to propylene continue to attract attention.[12]
Other commercialized methods
On-purpose propylene production technologies were developed throughout the twentieth century. Of these, propane dehydrogenation technologies such as the CATOFIN and OLEFLEX processes have become common, although they still make up a minority of the market, with most of the olefin being sourced from the above mentioned cracking technologies. Platinum, chromia, and vanadium catalysts are common in propane dehydrogenation processes.
Market
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.[13] Total world production of propene is currently about half that of ethylene.
Research
The use of engineered enzymes has been explored but has not been commercialized.[14]
There is ongoing research into the use of oxygen carrier catalysts for the oxidative dehydrogenation of propane. This poses several advantages, as this reaction mechanism can occur at lower temperatures than conventional dehydrogenation, and may not be equilibrium-limited because oxygen is used to combust the hydrogen by-product.[15]
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. Polypropylene manufacturers consume nearly two thirds of global production.[16] 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.[16]
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,[19] now that true MAPP gas is no longer available.
Foundational to hydroformylation, alkene metathesis, and polymerization are metal-propylene complexes, which are intermediates in these processes. Propylene is prochiral, meaning that binding of a reagent (such as a metal electrophile) to the C=C group yields one of two enantiomers.
The majority of propene is used to form polypropylene, a very important commodity thermoplastic, through chain-growth polymerization.[16] In the presence of a suitable catalyst (typically a Ziegler–Natta catalyst), propene will polymerize. There are multiple ways to achieve this, such as using high pressures to suspending the catalyst in a solution of liquid propene, or running gaseous propene through a fluidized bed reactor.[20]
Propene is a product of combustion from forest fires, cigarette smoke, and motor vehicle and aircraft exhaust.[4] 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.[8]
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.[8]
Propene has low acute toxicity from inhalation and is not considered to be carcinogenic. Chronic toxicity studies in mice did not yield significant evidence suggesting adverse effects. Humans briefly exposed to 4,000 ppm did not experience any noticeable effects.[22] Propene is dangerous from its potential to displace oxygen as an asphyxiant gas, and from its high flammability/explosion risk.
Bio-propylene is the bio-based propylene.[23][24]
It has been examined, motivated by diverse interests such a carbon footprint. Production from glucose has been considered.[25] More advanced ways of addressing such issues focus on electrification alternatives to steam cracking.
Storage and handling
Propene is flammable. 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.[26]
Occurrence in nature
Propene is detected in the interstellar medium through microwave spectroscopy.[27] 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.[28][29]
^Rasmussen, Seth C. (2018), Rasmussen, Seth C. (ed.), "Introduction", Acetylene and Its Polymers: 150+ Years of History, SpringerBriefs in Molecular Science, Cham: Springer International Publishing, pp. 1–19, doi:10.1007/978-3-319-95489-9_1, ISBN978-3-319-95489-9, retrieved 2023-12-30
^Ashford's Dictionary of Industrial Chemicals, Third edition, 2011, ISBN978-0-9522674-3-0, pages 7766-9
^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. S2CID103664623.
^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.
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