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• 𝐂𝟒 𝐇𝟖
• Also known as 2-methylpropene
Before that, lets get to know more of
n-butylene family
• Isomers of C4 H8 .
About isobutylene
• It is a four-carbon branched alkene (olefin), one of the four
isomers of butylene. At standard temperature and pressure it
is a colorless flammable gas.
• Alkylation with butane produces isooctane, another fuel
additive
• isobutene obtained from the refinery gas as a by-product of
naptha steam cracking or fluidized catalytic cracking as well
as produced by the dehydrogenation of isobutane
• Attention has drawn to the dehydrogenation of isobutane to
isobutene due to the increasing demand of isobutene
Process Background (Exxonmobil)
• Isobutylene is produced commercially by catalytic or thermal
cracking of high boiling petroleum fractions or steam cracking of a
mixture of saturated hydrocarbons.
• Isobutylene (13 to 28% of the product stream of C4 hydrocarbons)
is separated from the resultant product mixture of C4 hydrocarbons
• either by extraction into 45 to 65% sulfuric acid with subsequent
regeneration of the isobutylene by steam tripping or by the
removal of normal butenes by adsorption on molecular sieves.
• Other processes that may be used to produce isobutylene include
the dehydration of ter-butyl alcohol and the thermal
dehydrogenation of isobutane. World-wide, isobutylene
production from all sources exceeds 10,000 kilotonnes/year (Lacson
et al., 2002).
• For the year 2000, production in Japan was estimated at
1,000 kilotonnes.
• In 2001, Western Europe produced 995 kilotonnes and the
United States 8,300 kilotonnes (Lacson et al., 2002).
• It is mainly used as a monomer or copolymer for the
production of synthetic rubber and various plastics.
• Approximately 72% of available isobutylene is used for the
production of butyl rubber.
• Approximately 17% is used for the production of
antioxidants for food, food packaging, supplements and for
plastics.
• Approximately 9% is used for the production of (polymer)
fuel oil or lube oil additives.
• Approximately 2% is used for various other intermediate
applications.
• Endothermic Performed at
Why dehydrogenation
• Volume-expanding high
of isobutane?
reaction temperature
Pressure:
higher than Temperatur
atmospheric e range:
pressure, 350-400°C
alittle.
Second step
Methacrolei
n is further
oxidized into
methaacrylic
acid
Catalyzed by
molybdenu
Temperatu
m
re range:
compound
250-350°C
and specific
promoter
• Methacrylic acid further esterified with
methanol. >> methyl methacrylate monomer.
• Methacrylic acid and methacrylates can also
produced by hydrocyanation of acetone, then
hydrolysis and esterification.
• Ammoxidation of isobutylene >>
methacrylonitrile.
Epoxidation of isobutylene
• Product : isobutylene oxide.
• Liquid phase with no catalyst.
• Yield, low. 28.7% with lots of by-products like acetone, ter-
butyl alcohol, isobutylene glycol.
• yield of isobutylene: 82%
• chlorohydrination route > Calcium hydroxide.
• Under catalyst thallium acetate stoichiometric in aqueous
acetic acid solution.
Hydrolysis
• Direct catalyzed liquid phase oxidation of isobutylene
with oxygen and presence of water. (Wacker-catalyst)
>> isobutylene glycol
ETBE
• Ethyl-ter-butyl ether (ETBE) is also produced
by the reaction of ethanol and isobutylene
under similar conditions with a heterogeneous
acidic ion-exchange resin catalyst
MTBE
• Isobutylene is most wanted to produce MTBE. MTBE is
important gasoline additive due to, high octane rating.
• Added to gasoline, to improve combustion and reduce carbon
monoxide and HC exhaust emmisions.
• This is done by reducing aromatics in gasolines.
• High T, increase rxn rate, but decrease conversion level.
• Rxn, at 50°C, solid acid catalyst.
• Side rxn : hydration to tertiary butyl alcohol, methanol
dehydration, formation of dimethyl ether and water. (small
amount)
MTBE unit designed with two reactor (BP process). Most
etherification achieved in 1st reactor. Finished at
thermodynamically favorable lower T, in 2nd reactor.
CATALYTIC DEHYDROGENATION OF
ISOBUTANE
• Catalytic dehydrogenation: reaction used commonly
in industry
• Above are the reaction steps for Pt-based catalysts
on dehydrogenation of isobutane.
• Deuterium is produced. H*
• side reaction: hydrogenolysis.
• Dehydrogenation of isobutane to olefins that is
isobutylene
• Process used catalysts like Platinum +one of Tin,
indium or rhenium on a support of zinc aluminate
(nonacidic support) .
• Process was carried out with molar ratios of
isobutane to steam between 1:1 and 1:10
• Temperature of process carried out at 400-700°C
• Pressure of process is low, only up to about
10kg/cm2 gauge or 0.14 to 2 bar
Why platinum?
second, it will be
reduces the yield of
structurally isomerized, at
isobutylene per pass
least in part, to n-butenes
isobutylene
were hydrated
in the presence
of an acid
catalyst,
the resulting
tertiary
butanol would
be a suitable
feed for
oxidation to
methacrolein
alternativel
y, it could
be purified
and used as
a gasoline
additive
• Reducing the isobutylene content in the
dehydrogenation feed will ultimately lower
the loss of fresh feed isobutane to structural
isomerization and cracking
• since isobutylene is more susceptible to such
reactions.
ISOBUTYLENE MSDS
NFPA health hazard 2 - Intense or continued exposure could
cause temporary incapacitation or
possible residual injury unless prompt
medical attention is given
LAND
• Isobutylene entering aquatic and terrestrial habitats will rapidly
partition to the air because it is a gas.
WATER
• Isobutylene is a gas thus it will migrate rapidly from water and soil
to air, residual concentrations in aquatic and terrestrial habitats will
be very short lived, acute and chronic toxicity are not expected.
HEALTH INFORMATION
• Exposure to Isobutylene is through inhalation.
• Isobutylene believed to have low acute
toxicity at the levels found in the workplace.
• At high concentrations, Isobutylene is an
asphyxiant
• High level exposure can also lead to
drowsiness - dizziness - may cause central
nervous system depression.
• There are no specific exposure limits for Isobutylene.
Isobutylene is a simple asphyxiant (SA). Oxygen levels
should be maintained above 19.5%.