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C5 Hydrocarbon: Isoprene

1. History
1905- Chemists discovered that the chain molecules of elastic material are made up of
multiple strings of isoprene molecules.
1906- German company Bayer offered 20,000 gold marks for a chemist in their company
to invent a rubber substitute. The results were to be delivered within three years - to
counteract the depleting stocks of rubber that were insufficient to cover the growing
demands of the automotive industry.
1909- Bayer’s chief chemist, Fritz Hoffman, succeeded in producing methyl-isoprene in
which started the development of synthetic rubber.
1909- The world's first synthetic rubber was patented on 12 September 1909.
1910- The first rubber polymer synthesized from butadiene was created in 1910 by the
Russian scientist Sergei Vasiljevich Lebedev.
1927- A less costly variety of synthetic rubber was introduced since during World War I
synthetic rubber was too expensive
1931- Neoprene was created by DuPoint scientists after attending a lecture by Belgian
priest and chemistry professor Dr. Julius Nieuwland.
1933- German scientists IG Farben’s Walter Bock and Eduard Tschunku developed
Buna-S rubber, a synthetic rubber made from styrene and butadiene, just before World
War II. Mainly used for car tires.
1940-The Soviet Union had the largest synthetic rubber industry - mostly of polybutadiene
rubber, according to the IISRP.
1940- B. F. Goodrich Company scientist Waldo Semon developed a new and cheaper
version of synthetic rubber known as Ameripol.
During the mid-1950s - After the war, Caltech researchers started to investigate the use
of synthetic rubbers to replace asphalt in their solid fuel rocket motors and large missiles
were being built with synthetic rubber as the base for solid fuels.
In the early 1960s- Additional improvements to the process of producing synthetic rubber
continued after the war, leading to a reduction in the need for rubber. The quantity of
synthetic rubber exceeded the production of natural rubber.
Present Day- Synthetic rubber accounts for around two-thirds of the world’s overall
rubber production.
Mainly used as the component for tires on bicycles, airplanes and automobiles, synthetic
rubber is also widely used as a rubber matting option and a versatile flooring solution.
This year, it is anticipated that the global revenues produced from the sale of these
rubbers are likely to rise to around £40 million.
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2. Uses
Isoprene (2-methyl-1.3-butadiene) is a common organic compound with the
formula CH2=C(CH3) CH=CH2 and is used mainly to make synthetic rubber. Under
standard conditions it is a colorless liquid. However, this compound is highly volatile
because of its low boiling point. Isoprene is the monomer found in natural rubber and is
also a common structure in a wide variety of other natural compounds, collectively termed
terpenoids. Isoprene is a useful building block for various chemicals and intermediates.

MAIN AREAS OF APPLICATION:

• Isoprene related polymers (cis-polyisoprene, trans-polyisoprene, liquid

polyisoprene rubbers)
• Isobutylene polymers (regular butyl, halogenated butyl rubbers)
• Raw materials for urethanes (MPD (3-Methyl-1,5-Pentanediol), ND (1.9-
Nonanediol))
• Thermoplastic elastomers (TPE) (SiS block copolymers)
• Solvent
• Raw material for cosmetics (Isoprene Glycol)
• Raw material for chemicals (butyl alcohol isobutene)
• Agrochemical intermediate (Isoprenol, prenol, MPM)
• Aroma chemicals (Citral)

3. An overall block flow diagram from which this product is derived starting
with its raw material (crude oil, natural gas etc.)
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(Source: Retrieved from

https://biotechnologyforbiofuels.biomedcentral.com/articles/10.1186/s13068-018-1230-
9/figures/1)

(Source: Retrieved from https://ihsmarkit.com/pdf/IHS-Chemical-C5SpecialReport-

Prospectus_235023110913044932.pdf)
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4. Reaction mechanism
a. Oxidative dehydrogenation of isopentane to isoprene

b. Isoprene from propylene

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c. Isoprene production from propylene

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d. Synthesis from Isobutylene and formaldehyde

5. Process Description
Below are some of the methods for isoprene synthesis used on an industrial scale:
1. Synthesis from Isobutylene and formaldehyde.
2. Dehydration of isopentane.
3. Oxidative dehydration of isopentane.
4. Synthesis from propylene.
5. Synthesis from acetylene and acetone
6. Recovery of isoprene from C5 fraction of liquid petroleum pyrolysis.
7. Liquid phase oxidation of hydrocarbons

Synthesis from Isobutylene and formaldehyde

Figure 1 is a flow diagram for the synthesis of isoprene from isobutylene and
formaldehyde. Dimethyldioxane vapour is mixed with steam and sent to reactor (2) to
which steam heated to 973K from the steam heater (1) is supplied. The gas mixture enters
the cascade of heat exchangers (3), in which the products are condensed. The
condensate consisting of two phases –the organic and aqueous, is allowed to settle in
(4). The oily layer gets washed out in (5) where the extraction of dissolved formaldehyde
takes place. The washed stream is sent to rectification column (6), where the lighter
products, mainly isobutylene and isoprene are separated from the decomposed dimethyl
dioxane and other less volatile substances. The stream from (6) then enters the
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rectification column (7), where highly concentrated isobutylene is collected and returned
for synthesis of dimethyl dioxane. The distillate from (7) – raw isoprene is sent to columns
8, 9 for further rectification in order to remove impurities with high boiling points, mainly
cyclopetadiene and carbonyl compounds, which are washed out in column (10). The
distillate from column (11) is sent to vacuum column (12) in which by-products with high
boiling points, mainly isoprene oligomers or green oil from the second stage of the
synthesis are removed from the recycled dimethyldioxane. An extragent (made up of the
mixture of isopropyl alcohol and dimethyldioxane) can be recovered for the extraction of
the byproducts of the first stage of the process from the recycled dimethyldioxane, by
rectification.
The contact gas from the reactor goes for condensation, while the condensate is
sent to the settler where stratification into oily and aqueous layers is carried out. The oily
layer undergoes rectification in a double column system, which gives yields to iso-
butylenes (which is returned to the first stage of the synthesis), fraction of raw dimethyl
dioxane, and isoprene distillate which contains traces of carbonyl compounds (mainly
aldehydes). The raw isoprene is sent for rectification (distillation), in order to get isoprene
distillate, which is further rinsed with condensate in order to get rid of carbonyl
compounds. Finally, polymerization inhibitors are added to prevent the polymerization of
isoprene in the distillation columns.

Synthesis from propylene

Figure 3 is a flow diagram for the synthesis of isoprene from propylene. The raw
material used is propane – propylene fraction, which is pre-dried and purified. The reactor
unit consists of two units. At the exit of reactor (1), the feed mixture is throttled to a
pressure level close to atmospheric, condensed in the cooling units and then fed to the
separation units. Conversion of propylene in the described conditions is 70 – 85% at 97%
yield of dimmers based on the reacted olefin. The condensed feed enters the evaporation
column (2), where the catalyst is separated from higher oligomers of propylene which
accumulate in the system as a result of continuous operation. A small portion of the
catalyst (tripropylaluminum) is removed from the reactor and replaced with freshly
prepared catalyst and sent for regeneration due to poisoning and thermal decomposition.
2-methylpentene-1, along with other light hydrocarbons and unreacted propylene is
distilled from the top of the evaporation column (2) and enters the rectification column (3),
where the separation of low boiling hydrocarbons takes place. 2-methyl pentene goes
through a system of rectification columns and then into the reactor (4) for isomerization.
The reaction mixture enters the pyrolysis furnace (6) to which over heated steam
is also fed. Furthermore, the separation of the hydrocarbon and aqueous phases take
place with hydrogen bromide dissolved in the later. Aqueous solution of hydrogen
bromide is mixed again with fresh feed. Methane and light hydrocarbons are released
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from the hydrocarbon fraction while the target fraction is sent for purification and
subsequently the separation of isoprene.

Extraction of isoprene from C5 fraction of liquid petroleum pyrolysis

This is the simplest method of isoprene production which involves its extraction
from C5 fraction of liquid petroleum pyrolysis containing about 15 – 20% isoprene. This
fraction is produced as a by – product in the production of ethylene and propylene.
However, the transportation of raw materials from different refineries for the industrial
realization of this method creates some difficulties. Environmental issues are also there
to be tackled especially with the recent tightening of environmental laws

Figure 5 is a flow diagram for the isolation of isoprene from a C5 cracking fraction.
The first step in the separation is a combination of a liquid – liquid extraction with an
extractive distillation, an approach particularly suited to C5 fractions with a low isoprene
concentration. Preconcentration of isoprene occurs in Liquid-liquid Extraction column (a).
Crude isoprene is removed as a side stream from the extractive distillation column (b),
after which it is freed from piperylenes and cyclopentadiene in a second extractive
distillation step incorporating columns (c) and (d). Final purification of isoprene to
polymerization grade occurs in Butyne distillation columns (e) and Isoprene distilling
cloumn (f). C5 fractions that contain cyclopentadiene can be used in this process because
the cyclopentadiene is removed together with the piperylenes.
Incorporation of relevant equipment in this process allows the isolation of
cyclopentadiene or the commercially valuable cyclopentene. Introduction of a
supplementary column permits recovery of pure piperylenes. The high-quality
specifications that are required for isoprene used in the preparation of poly(cis-1,4-
isoprene) are met with the aid of modern separation facilities.
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6. Process Flow Diagram

(Source: Retrieved from https://sci-hub.tw/10.2478/cse-2013-0006)

(Source: Retrieved from https://sci-hub.tw/10.2478/cse-2013-0006)

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(Source: Retrieved from https://sci-hub.tw/10.2478/cse-2013-0006)

(Source:
http://www.ugr.es/~tep028/pqi/descargas/Industria%20quimica%20organica/tema_3/iso
preno_a14_627.pdf)
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7. References
De Guzman, D. (2008, 5 July). History of the synthetic rubber industry. Retrieved from
https://www.icis.com/explore/resources/news/2008/05/12/9122056/history-of-the-
synthetic-rubber-industry/

Ezinkwo, G. O., Tretjakov, V. F., Talyshinky, R. M., Ilolov, A. M., & Mutombo, T. A.
(2013). Overview of the Catalytic Production of Isoprene from different raw
materials; Prospects of Isoprene production from bio-ethanol. Catalysis for
Sustainable Energy, 1. doi:10.2478/cse-2013-0006

Morton, M. (1981). History of Synthetic Rubber. Journal of Macromolecular Science: Part

A - Chemistry, 15(7), 1289–1302. doi:10.1080/00222338108056786

The History of Synthetic Rubber. (2016, 9 December). [Blog post] Retrieved from
https://www.coruba.co.uk/blog/the-history-of-synthetic-rubber/

Isoprene- the organic compound for synthetic rubber. (2012, 12 March). Retrieved from
http://dhard.ucp-is.com/docs/specs/feedstocks/low.olefins/im/

IHS Chemical. (2015). C5 Value Chain Study: From Cracker to Key C5 Derivative
Applications for Isoprene, DCPD and Piperylene. Special Report Prospectus.
Colorado, USA.

Weitz, H. M., & Loser, E. (2000). Isoprene. Ullmann’s Encyclopedia of Industrial

Chemistry. doi:10.1002/14356007.a14_627

Wilson, J., Gering, S., Pinard, J. et al. Bio-production of gaseous alkenes: ethylene,
isoprene, isobutene. Biotechnol Biofuels 11, 234 (2018).
https://doi.org/10.1186/s13068-018-1230-9