ISOBUTYLENE

CAS N°: 115-11-7

 Who is isobutylene ?

• 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

High energy Crucial issues affecting

dehydrogenation Fast catalyst
consumption from deactivation
the high process
temperature Poor isobutane
operation selectivity

Increase the conversion

Oxidative
and/or lower the reaction
dehydrogenation
temperature
 Mild oxidant in the oxidative
Employ CO2
dehydrogentaion of isobutane

Catalyst used: Dehydrogenation is joined with reverse

• 𝐶𝑟2 𝑂3 water gas shift (RWGS):
• VMgO (𝐶𝐻3 )3 𝐶𝐻 = (𝐶𝐻3 )2 𝐶𝐶𝐻2 + 𝐻2 {1}
• FeO 𝐶𝑂2 + 𝐻2 = 𝐶𝑂 + 𝐻2 𝑂 {2}

Yield of isobutene can be enhanced at relatively low

temperature by
• promoting the dehydrogentaion
• Avoiding the deep oxidation of target product with CO2
in the reaction stream
 Applications
- Isobutene is a starting material for various intermediates and final
products such as:
- Butyl rubber (synthetic rubber), polyisobutene (butyl rubber is
based), diisobutene (intermediate), tert.-butanol, alkyl-tert-butyl
ether, MTBE, vitamins, fragrances, isoprene, mercaptans,
alkylphenols, antioxidants, synthetic resins, adhesive resins,
additives for fuels and lubricants, organic acid, methyl
methacrylate

- Butyl rubber lubricant additive resin additive fragrance

 Butyl Rubber (synthetic rubber)
• Butyl rubber are long-chain polymers with special chemical and
physical as well as mechanical properties. These materials have
chemical stability, high abrasion resistance, strength, and good
dimensional stability.
• Many of these properties are imparted to the original polymer
through crosslinking agents and additives.
• Ability to be stretched at least twice their original length and to
return back.
• However, they cannot replace all traditional rubber since they do
not have the wide temperature performance range of thermoset
rubber.
• The major use of rubber is for tire production. Non-tire
consumption includes hoses, footwear, molded and extruded
materials, and plasticizers.
 MTBE & ETBE
 MTBE and ETBE constitute a group of oxygenates that are
currently in high demand for gasoline octane-number
boosters. Both MTBE and ETBE have a similar research octane
number of 118, but the latter ether has a motor octane
number of 102 versus 100 for MTBE.
 However, the oxygen content of MTBE is 18.2% compared to
15.7% for ETBE. The lower oxygen content of ETBE is related to
the air/fuel ratio, which may not require a change in the
automobile carburetors.
 Sustainability
• The present invention concerns a new process for the
sustainable chemical synthesis of isobutene Based on a
chemical
Fermentation of a conversion of
isobutylamine recombinant microorganism an amine to
as starting material an olefin
(alkene)

From an inexpensive • low cost

source of carbon (sugar)
• Human safety Instead gaseous isobutene is
• Environmenta recovered from the
l protection fermenter together with 𝐶𝑂2 ,
• Sustainability the low aqueous solubility of
of the isobutene might also
process minimize product toxicity to
the microorganisms
 Safety Measure
• Isobutene is a highly flammable gas and presents an explosion
danger.
• Usually stored as a compressed, liquefied gas
• If released it may produce an oxygen-deficient atmosphere that
presents an asphyxiation hazard
No action shall be taken Evacuate surrounding
n
involving any personal risk Accidental measure areas
or without suitable training
Keep unnecessary and Shut all ignition Provide adequate
unprotected personnel from sources ventilation
entering
 Evacuate all persons if Move containers from
there is a fire Fire-fighting measure fire area if this can be
done without risk
Use water spray to keep
fire-exposed containers Shut off flow
Fight fire from
cool immediately if it can
protected location
be done without risk
Stop leak
Immediately contact Large/small Spill without risk
emergency
personnel
Use spark-proof tools and
explosion-proof equipment
 Isobutene accident
• Baton Rouge, Louisiana there was a chemical spill caused by an
accident
• Two vehicles wrecked caused a semi truck loaded with 9000
gallons of isobutene, valve to become fractured which began
leaking.
• The people on site did not know how to get the isobutene out
of the truck safely and had to call an expert clear across the
country
• The interstate there was closed to protect people in case the
isobutene ignited.
• Hazardous material is marked on vehicles so that people
driving past or by the semi is aware of the chemical as well as it
tries to make the people want to drive little safer to protect
themselves and other people who are travelling the same road
as them
 Reaction & mechanism
• Major demand for isobutylene = MTBE
• Usually, n-butane is isomerized to get isobutane. Then
dehydrogenated to isobutylene.

• This is mutual beneficial process as, n-butane is

unwanted in the refining process yet, needed to
produce isobutylene.
• Unwanted because….
• Two specifications of gasoline blend
– Gasoline needs to have proper octane
– Proper RVP
 N-butane
• Butane is a relatively inexpensive ingredient in
gasoline, but it has the highest vapor pressure at
around 52 psi.
• 40% FCC gas, 25% straight run gas, 15% alkylate, 18%
reformate, and 2% butane.
• Eg: 10% butane, 5.2 psi contribution to the overall
blend.
• RVP must be less than 14.7psi or, gas tanks boil in open
air.
• Contributes to air polution.
• Some location, in the summer, even set 7.8 psi or 9,
declared by EPA.
 Isomerization of n-butane
• Commercially available processes are:
– BP C4 isomerisation for butane isomerisation
– UOP BUTAMER for butane isomerisation
• Occurs at low T.
• Acid-catalyzed to produce highly branched
hydrocarbon mixtures.

• Typical catalyst, platinum and zeolite base

– Promoting carbonium ion formation
– Hydrogenation-dehydrogenation reactions
 OXIDATION OF ISOBUTYLENE
• Oxidation of isobutylene produces
a) methacrolein (unsaturated aldehyde)
b) methacrylic acid
• Occurs two steps. Due to different characteristics of
reactant and product
Reactant: isobutylene (olefins)
Product: Methacrolein (unsaturated aldehyde)
 First step
Catalyst:
molybdenu
m oxide-
based
catalyst.

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?

• High activity for activating C-H bonds

• High reactivity for rupturing C-C bonds

• All sites of Pt catalyze the ruptures of C-H bonds.
Hence, high selectivity for dehydrogenation
But, another undesired reaction that competes with
dehydrogenation >> COKE FORMATION
Flow Diagram isobutane
Dehydrogenation
• Feed to dehydrogenation 30% isobutylene.
• If isomerization of isobutane or isobutene
occur, cost increase.
• According to a patent, US3470262,
isobutylene dehydrogenation used platinum-
chromium catalyst supported by zinc
aluminate
 isobutane is
containing unconverted
dehydrogenated in the
isobutane along with
presence of steam to
hydrogen and steam, is
isobutylene, after which
oxidized to form
the isobutylene in the
methacrolein
dehydrogenation effluent,

After separation of the

methacrolein, the unreacted Catalyst are chosen from
isobutane and isobutylene are time to time according to
returned to the dehydrogenation its affectiveness, ln, Nd, Sn.
reactor

Motive of choosing catalyst

to reduce or avoid
isomerization within the
process.
 A substantial amount of
it should not be included
unconverted isobutylene
in the feed to the
is found in the isobutane
dehydrogenation reactor
recycled to the
for two reasons
dehydrogenation reactor

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

NFPA fire hazard 4 - Will rapidly or completely vaporize at

normal pressure and temperature, or is
readily dispersed in air and will burn
readily.

NFPA reactivity 1 - Normally stable, but can become

unstable at elevated temperatures and
pressures or may react with water with
*Rating some release of energy, but not
violently.
Health 1 Slight Hazard -
Irritation or minor
reversible injury
possible

Flammability 4 Severe Hazard

Physical 2 Moderate Hazard

• H220 - EXTREMELY FLAMMABLE GAS
• H280 - CONTAINS GAS UNDER PRESSURE; MAY
EXPLODE IF HEATED
• OSHA-H01 - MAY DISPLACE OXYGEN AND CAUSE
RAPID SUFFOCATION.
• CGA-HG04 - MAY FORM EXPLOSIVE MIXTURES
WITH AIR
• CGA-HG01 - MAY CAUSE FROSTBITE.
GHS0 GHS04
2
• Isobutylene is a colorless gas that smells like gasoline or
natural gas
• It is highly flammable and may cause organ damage if
inhaled or swallowed
• Because isobutene boils at 12 degrees at normal air
pressure, it is shipped under pressure to keep it in liquid
form
• If isobutene leaks from a tank, it very rapidly boils and
forms a gas so cold that it may even cause frostbite in
anyone who comes in contact with it
• The resulting vapors are heavier than air and will flow out
along the ground and tend to settle in low-lying areas.
TYPES OF ACUTE HAZARDS PREVENTION FIRST AID /
HAZARD / / SYMPTOMS FIRE FIGHTING
EXPOSURE

Extremely NO open flames, Shut off supply; if

flammable. NO sparks and NO not possible and no
smoking. NO risk to surroundings,
contact with let the fire burn itself
FIRE
oxidizing agents. out. In other cases
extinguish with
water spray, powder,
carbon dioxide.
Gas/air mixtures are Closed system, In case of fire: keep
explosive. Risk of ventilation, drums, etc., cool by
fire and explosion on explosion-proof spraying with water.
contact with electrical equipment Combat fire from a
oxidizing agents or and lighting. Prevent sheltered position.
EXPLOSION
halogens. See build-up of
Chemical Dangers. electrostatic charges
(e.g., by grounding).
Use non-sparking
handtools.
 ACUTE HAZARDS / PREVENTION FIRST AID /
SYMPTOMS FIRE FIGHTING
EXPOSURE

Dizziness. Drowsiness. Use closed system or Fresh air, rest. Artificial

Lethargy. Nausea. ventilation. respiration may be
INHALATION Unconciousness. needed. Refer for medical
Vomiting. attention.

ON CONTACT WITH Cold-insulating gloves. ON FROSTBITE: rinse

LIQUID: FROSTBITE. with plenty of water, do
SKIN NOT remove clothes.
Refer for medical
attention .
See Skin. Wear face shield or eye First rinse with plenty of
protection in combination water for several minutes
with breathing protection. (remove contact lenses if
EYES
easily possible), then
refer for medical
attention.
Do not eat, drink, or
smoke during work.
INGESTION
ENVIRONMENTAL INFORMATION
AIR
• Isobutylene has the potential to degrade rapidly through physical
processes with an estimated half-life of approximately 2 hours.

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%.

• However, the amount of Isobutylene in the air

necessary to have these effects is so high that the
atmosphere would be in the explosive range of
airborne concentrations. No evidence has been found
to suggest that Isobutylene is carcinogenic or toxic to
the reproductive or developmental systems.
 The risk of explosion of the gas clouds
should be minimized
through the following measures:
• Early detection of the release through installation of
leak detection units and other devices;
• Segregating process areas, storage areas, utility areas,
and safe areas, and adopting of safety distances
• Limiting the inventory which may be released by
isolation of the installation from large inventories and
isolation and blow-down of pressurized flammable
gases inventories;
• Removing potential ignition sources;
• Controlling operation and procedures and avoiding
hazardous gas mixtures;
• Removing or diluting the release and limiting the
area affected by the loss of containment;
• Developing, implementing and maintaining a
specific Emergency Management Plan, providing
emergence measures to be implemented to protect
both operators and local communities from toxic
products releases.