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PRODUCTION
OF
PETROCHEMICALS
Manufacture of Ethylene Oxide
By direct oxidation Process
Ethylene of 95-98% purity and air are compressed
separately and mixed together giving a mixture of
3-10 vol.% of ethylene.
The mixture is passed through the fixed bed
tubular reactor containing silver catalyst
supported on porous alumina with alkali or
alkaline earth metal as promoter.
The reaction is highly exothermic and the
Manufacture of Ethylene Oxide
Manufacture of Ethylene Oxide
Heat liberated is removed by circulating molten salt around the tubes
within the shell of tubular reactor to maintain the temperature 250-
300 oC. Temperature is the most important critical parameter and is
measured at different parts of the catalyst bed.
Heat from molten salt is recovered in a waste-heat boiler
The undesirable competing reaction is complete oxidation of
ethylene which is highly exothermic (13 times that of ethylene
oxide formation reaction)
CH2=CH2 + 3O2 2CO2 + 2H2O
Hence the temperature of the catalyst bed will increase which again
favours the complete combustion of ethylene, as its activation energy
is high compared to ethylene oxide formation.
To minimize the complete combustion
Restrict the residence time to 1 sec.
Use oxygen acceptors like ethylene dichloride
Rapidly cool the product mixture
Manufacture of Ethylene Oxide
Product from the reactor is cooled, compressed and admitted into
absorber from the bottom. Water is admitted from the top. As they
come into contact in counter current direction, ethylene oxide and other
products get absorbed, leaving from the bottom as solution.
while the unreacted ethylene and air remain unabsorbed, leaving from
the top of the absorber is recycled to the reactor.
The aqueous solution leaving from the bottom of the absorber is
admitted into desorber at reduced pressure. Absorbed Ethylene oxide
along with impurities get desorbed and leave as over head product from
the top of desorber carrying some water vapour. Water leaves from the
bottom is recycled to the absorber.
The overhead from the desorber is compressed and taken to stripper
where water and lighter impurities leave as over head product. Ethylene
oxide along with heavier impurities leave as bottom product
The bottom product from stripper is admitted into fractionation still
where pure ethylene oxide leaves as over head product and heavier
impurities leave as bottom product.
Manufacture of Ethylene Glycol
Mono Ethylene Glycol (MEG) is an important
petrochemical used in the manufacture of
synthetic polyester (PET) and used as anti-freeze.
70% of ethylene oxide is consumed for the
manufacture of MEG
Manufacture of MEG involves hydroxylation of
ethylene oxide with water.
Ethylene oxide and water are mixed in the ratio
1:10
Ethylene oxide-water mixture is preheated to 195
oC and admitted into the adiabatic reactor.
Manufacture of Ethylene Glycol
Manufacture of Ethylene Glycol
Pressure maintained is to avoid vapourisation of ethylene oxide.
Rate of reaction depends on reaction temperature (i.e higher
the temperature, higher the rate), pH and reactants
composition.
In the reactor, sufficient time is allowed for the reaction mixture
for the following reactions to take place.
MEG
DEG
TEG
Manufacture of Ethylene Glycol
Products leaving the reactor containing 88% water
and not exceeding 10 ppm of ethylene oxide(as it
can react with water and can increase the
temperature and pressure in the pipe lines),
enters multiple effect evaporator where the
concentration of glycol is increased to 64 wt%.
Concentrated glycol is admitted into dehydrator
to remove the remaining water.
Then it is separated in to MEG, DEG and TEG in
three vacuum distillation columns.
Manufacture of Propylene Glycol
Propylene Glycol (PG) is an important derivative of propylene
It is mainly used to manufacture Unsaturated Polyester Resins and
Fiber Reinforced Plastics(FRP).
Also used as antifreeze, for making personal care products, paints
and other coatings, plasticizers.
Its manufacture is very similar to manufacture of ethylene glycol
except that ethylene oxide is replaced by propylene oxide and with
modified reaction conditions.
Propylene oxide and water are mixed in the ratio 1:15 in the dilutor
and admitted in to the reactor which is maintained at 190 oC and
2.1 MPa.
Higher amount of water is to increase the yield of monopropylene
glycol(MPG)
Hydroxylation of propylene oxide takes place as per the following
reactions, yielding MPG as the major product and DPG and TPG as
minor products.
Manufacture of Propylene Glycol
Manufacture of Propylene Glycol
Manufacture of Propylene Glycol
Products leaving the reactor enters multiple effect
evaporator where the concentration of glycol is
increased.
Concentrated glycol is admitted into dehydrator
to remove the remaining water.
Then it is separated in to MPG, DPG, TPG and
heavy ends in series of three vacuum distillation
columns.
Manufacture of Phthalic anhydride
Phthalic anhydride is an important aromatic petrochemical
used in the manufacture of plasticizers, alkyd resins etc.
o-xylene(predominantly) and Naphthalene are the raw
materials used in its manufacture
o-xylene after its vapourisation is mixed with preheated air
and admitted into the catalytic reactor which may be fixed or
fluidised bed, maintained around 380 oC and the contact
time is 0.1 to 0.4 seconds.
The catalyst is mixed Vanadium pentoxide and titanium
oxide, supported on inert ceramic rings
As the reaction is highly exothermic, molten salt is used to
transfer the heat from the reactor by circulating it around the
reactor which is in turn recovered for steam production.
Product gases leaving the reactor containing phthalic
anhydride, maleic anhydride, CO2 and water are taken to
coiled switch condenser which combines the operation of
condenser and Melter.
Manufacture of Phthalic anhydride
Manufacture of Phthalic anhydride
Maleic
Anhydride
The coiled switch condenser is comprised of three eccentric
tubes. Through the middle tube, the product gases from the
reactor enters and through the innermost tube, the cooling oil
enters. Products get cooled and phthalic anhydride solidifies into
solid while the rest of the products leave the switch condenser
and enters the scrubber.
Manufacture of Phthalic anhydride
In the scrubber, gases come into contact with water in the
counter current direction. Maleic anhydride gets absorbed
in the water and leaves as solution from the bottom . The
remaining unabsorbed gases are released into atmosphere.
The solidified phthalic anhydride is melted into liquid by
passing the hot oil through the outer most tube while the
passing of cold oil through the inner most tube is stopped.
As cold and hot oil are alternatively passed through the
condenser it is called as coiled switch condenser.
The molten phthalic anhydride flows out of the coiled
switch condenser and is distilled in first distillation column
where lighter impurities are removed.
In the second distillation column heavier impurities get
separated and leave as bottom product. Phthalic anhydride
leave as overhead product which is condensed and flaked.
Manufacture Of Maleic anhydride
Major use of maleic anhydride is in manufacture of
unsaturated polyester resin along with PG which is in turn
used in the manufacture of glass fiber reinforced plastics.
Used in the manufacture of fumaric and malic acids which
are used as food acidulate in soft drinks, soft drink
concentrates and other food products. Fumaric acid is also
used as animal feed particularly for white pigs in South
East Asian Countries.
Maleic anhydride is also obtained as a major byproduct
during the manufacture of phthalic anhydride and
benzaldehyde by the partial oxidation of o-xylene and
toluene respectively.
Major production of maleic anhydride is by the catalytic
vapor phase oxidation of benzene.
Manufacture Of Maleic anhydride
Benzene after its vapourisation is mixed with large
excess of preheated air and admitted into the
tubular bundle reactor containing catalyst (Mixed
Vanadium Pentoxide and Molybdenum trioxide) in
fixed bed, maintained around 350 - 400 oC, 0.1 -
0.2 MPa and the contact time is 0.1 seconds.
2. Butene
Then the product is neutralized with ammonia and then in settler where it
is separated into cyclohexanone oxime.
The Beckman rearrangement is carried out in the presence of oleum at 75-
80 OC.