Unit III

Unit-III
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
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
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.
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
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.
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.
o-xylene 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.
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.
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.
The Undesirable side reaction is Complete

oxidation (i.e combustion)
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 maleic
anhydride, CO2 and water are taken to separator
which is a coiled switch condenser.
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 much of the maleic anhydride
solidifies into solid while the rest of the products
leave the switch condenser and enters from the
bottom of the absorber(Wash Column).
The solidified maleic 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.
In the absorber, gases comes into contact with water in the
counter current direction. Remaining Maleic anhydride gets
absorbed in the water and leaves from the bottom as solution.
The remaining unabsorbed gases are released into atmosphere.
Maleic anhydride solution leaving the absorber is concentrated
in an evaporator.
The molten maleic anhydride flowing out of the coiled switch
condenser and the concentrated maleic anhydride solution from
evaporator are taken to the distillation column where the pure
maleic anhydride distills out as overhead product.
Alternative raw materials
1. n-butane
2. Butene
Catalyst: Vanadyl Phosphate

Temperature: 360-440 oC
Manufacture of Acetaldehyde
Acetaldehyde is one of the important
intermediate for the manufacture of wide range
of organic chemicals like acetic acid, acetic
anhydride, peracetic acid, vinyl acetate etc.
Commercial Processes available
1. Liquid phase hydration of acetylene
2. Dehydrogenation of ethanol
3. Partial Oxidation of ethanol
4. Liquid phase oxidation of ethylene (Most
commonly used method)
High purity ethylene and oxygen are fed to the
reactor containing the catalyst solution
maintained at 0.3-0.5 MPa and 120-130 oC.
Catalyst is a solution of palladium chloride and
copper chloride in dilute hydrochloric acid.
During the oxidation of ethylene to acetaldehyde
palladium ion in PdCl2 is reduced to metallic palladium which is reoxidised
to palladium (II) ion by the Copper (II) ion in CuCl2 and itself gets reduced
to Copper (I) ion. Copper (I) is reoxidized to Copper (II) by oxygen.
The reaction is exothermic and result in evaporation of the product mixture
which leaves the reactor and enters the vessel where the catalyst gets
separated and recycled to the reactor.
The rest of the products is taken to scrubber(absorber) where it comes into
contact with water in the counter current direction. The unreacted
ethylene and oxygen remains unabsorbed in the water and leaves from the
top of the scrubber which is recycled into the reactor. Other products
which get absorbed in the water and leave from the bottom as aqueous
solution.
The aqueous solution is taken to the first distillation column where lighter
impurities get separated and leave as overhead product. Bottom product is
taken to the second distillation column where pure acetaldehyde gets
separated from heavier impurities and collected as overhead product.
Crotonaldehyde is collected as middle product.
Manufacture of Acetic Acid
One of the most widely used organic acid.
Major use of acetic acid is to manufacture esters
like vinyl acetate, ethyl acetate etc., purified
terephthalic acid (0.08 tone of acetic acid
consumed per tone of purified terephthalic acid
manufactured), monochloro acetic acid.
Major methods of manufacture of acetic acid are;
Carbonylation of Methanol
Oxidation of acetaldehyde (Most commonly used)
Oxidation of n-butane
Manufactured by liquid phase oxidation of acetaldehyde using
Manganese acetate in Acetic acid as catalyst at 60-70 oC.
The reactor is a aluminium column and the solution of
acetaldehyde and catalyst is introduced at the lower part of the
column.
Oxygen is fed along the entire height of the column.
First acetaldehyde is oxidised to unstable Peracetic acid.
CH3CHO + O2 CH3COOOH
The peracetic acid reacts with another acetaldehyde to form a
peroxide compound which is decomposed to acetic acid by the
catalyst. O
CH3COOOH + CH3CHO II
CH3C-O-O-CH-CH3 2 CH3COOH
I
OH
Product mixture leaving the oxidation column
is cooled by water.
The acetaldehyde is condensed and recycled
to the oxidation column.
Acetic acid leaving the oxidising column is
distilled to purify it.
Manufacture of Methanol
Methanol is the highest amount of chemical
produced in the world
71% of methanol produced is consumed for the
manufacture of formaldehyde, acetic acid, methyl
methacrylate and dimethyl terephthalate
Methanol also has potential energy applications
such as fuel in fuel cells, auto fuels and in electric
power generation.
Futuristic applications include Methanol to
Gasoline (MTG), Methanol to Dimethyl ether, a
potential fuel in diesel engines and Methanol to
olefins.
75% of methanol is produced by the catalytic
hydrogenation of CO (i.e syngas)
Syngas of composition H2/CO ratio of 2.25 is compressed
to 200-350 atm and fed into high pressure copper lined
steel reactor containing Zinc Oxide-Chromium Oxide in
fixed bed as catalyst maintained at 300-375 oC.
CO + 2H2 CH3OH
Following side reactions occur when the pressure is less
and temperature is higher than the values specified above:
CO + 3H2 CH4 + H2O
2CO + 2H2 CH4 + CO2
2CO CO2 + C
CO + H2 HCHO
CH3OH + nCO + 2nH2 CH3(CH2)nOH + nH2O
Higher alcohols
The gaseous products leaving the reactor are cooled
first by heat exchange with reactants and then with
water.
Methanol gets condensed to liquid under the
prevailing pressure
Crude liquid methanol is depressurized and purified
by permanganate to remove traces of ketones,
aldehydes and other impurities.
Then it is sent to ether tower, where lighter products
like dimethyl ether leave as overhead product
Bottom product is fractionated in methanol tower
where methanol is collected as over head product,
water is collected as bottom product and higher
alcohols are collected from the middle of the tower.
Manufacture of Chloromethanes
Chloromethanes include methyl chloride, methylene
chloride, chloroform and carbon tetrachloride.
They are mainly used as solvents and as intermediates
Ex:
1.CH3Cl as methylating agent
Tetramethyl lead is an important antiknocking additive
in petrol next only to Tetraethyl lead.
In the manufacture of methyl cellulose
2. For the synthesis of chlorofluoro carbons used as
refrigerants.
Thermal chlorination is carried out in a reactor that is
fixed in a jacket maintained between 370 to 410 oC .
Product composition depends on the CH4/Cl2 ratio.

Heat of reaction is used to preheat the inlet feed to
280 oC by passing it through the jacket.
Product stream leaving the reactor is cooled and methane
is recycled back to the reactor.
Rest of the products are admitted to the bottom of the
absorber and water is admitted from the top. HCl gas gets
dissolved in water and leave from bottom of the absorber
as hydrochloric acid.
Products leaving the absorber is admitted to the bottom of
the neutraliser. From the top, NaOH solution is admitted
which neutralizes any HCl gas left and any CO2 present and
dissolve them as NaCl and sodium carbonate.
The rest of the products leaving the top of the neutraliser is
cooled and compressed .
The compressed products are dried with Con. Sulphuric
acid and recycled back to the reactor if CCl4 is the desired
product or else sent to the rectification column for
separation into different chlorinated products.
Manufacture of Acrylonitrile
It is a petrochemical produced in moderate amount
Mainly consumed for the manufacture of acrylic
fibers, Acrylonitrile-Butadiene-Styrene (ABS),
Styrene-Acrylonitrile plastic (SAN), Nitrile rubber
(Butadiene-acrylonitrile)
Produced by ammoxidation of propylene.
The gas mixture containing 5-8% Propylene, 5-9%
NH3, steam and excess of air is compressed to 1.5-3
atm and admitted into the reactor containing
Molybdenum-Bismuth mixed oxide catalyst in
fluidized form maintained at 400-500 oC.
Contact time is 2-4 Seconds
As the reaction is exothermic, heat released due to
the reaction is removed by circulating molten salt
which in turn is utillised to produce steam.
Along with acrylonitrile, Hydrogen cyanide and

acetonitrile are also formed as valuable by products.
Products leaving the reactor is taken through the
waste heat boiler to cool it and for heat recovery.
Then it is admitted to the bottom of the absorber and
from the top sulphuric acid is flown down to react
with unreacted ammonia present in the product and
recovered as ammonium sulphate.
Unabsorbed products leaving the top of the absorber are
admitted into the bottom of the scrubber and water from the
top. Both of them come into contact in the counter current
direction, dissolving the products except unreacted propylene
which leaves from the top.
The aqueous solution leaving the bottom of the scrubber is
taken to splitter from which lighter products leave from the
top and heavier products leave from the bottom.
Lighter products are subjected to azeotropic distillation which
results in HCN as the overhead product. Bottom product is
subjected to distillation resulting in pure acrylonitrile as over
head product and heavier products as bottom product.
Heavier products leaving the bottom of the splitter is also
subjected to azeotropic distillation which separates water
from others and leave as bottom product. The overhead
product is distilled to get acetonitrile as overhead product
and heavy products as bottom product.
Manufacture of Phenol
Phenol is one of the oldest commercial organic
chemical produced.
More than half of phenol produced is consumed
for the manufacture of phenolic resins(i.e
Bakelite) and the rest is consumed for the
manufacture of salicylic acid, xylenols etc.
Methods of manufacture
1. From Benzene by sulphonation route
2. From Chlorobenzene
3. From Benzoic acid
4. From Cumene (Most commonly used)
Purified cumene is mixed with purified recycle
cumene and fed to the oxidizer along with a dilute
soda ash solution, in order to maintain the pH
between 8.0 and 10.5. The mixture is contacted
with air and held at 110 and 115C until 20 to 25%
of the cumene is converted to the cumene
hydroperoxide.
Heat released due to the reaction is removed by
vapourisation of the reaction mixture which is
condensed and recycled back to the reactor.
The crude mixture from the oxidizer is fed to a
reactor in which the cumene peroxide is cleaved to
phenol and acetone in the presence of sulphuric
acid catalyst at 55-65 oC.
Product mixture is taken to separator where it gets

separated into two layers. Aqueous layer is recyled
to the cleavage reactor. Organic layer containing
Phenol, acetone, acetophenone and -methyl styrene is
washed with water to remove any acid present in the
layer.
Washed organic layer is distilled at atmospheric
pressure where the acetone gets separated and leave
as overhead product. The bottom product is distilled
under vacuum, where the unreacted cumene leave as
over head product which is recycled to the oxidiser.
Bottom product is distilled under still lower vacuum
where the -methyl styrene leave as overhead
product which is recycled to the oxidiser or sent for
sales. Bottom product is distilled under much lower
vacuum where the phenol leaves as overhead
product and is purified by crystallisation.
Acetophenone leaves as bottom product.
Manufacture of Linear Alkyl Benzene (LAB)
LAB is the basic raw material for the production of most of
the detergents
LABs properties as surfactant depend on the chain length,
position of phenyl group and degree of branching of alkyl
chain
For light house hold applications, LAB with alkyl chain of
carbon numbers C11 C12 are used and for heavy duty
applications C13 C14 are used.
Various steps involved in the manufacture of LAB are;
Prefractionation: The kerosene cut (140-270 oC) is distilled
where lighter ends leave as overhead product. Bottom product
is fractionated in the second column from which the overhead
product obtained which contain C10 C14 range of hydrocarbons
(170-225 oC) is taken to the hydrotreating unit and heavier ends
leave as bottom product.
Manufacture of LAB
Manufacture of LAB
Hydrotreatment: For the removal of sulphur, nitorgen
and Oxygen containing compounds
n-Paraffin separation: Separation of n-paraffins from
branched and cyclic hydrocarbons by adsorption
process using molecular sieves as adsorbents Ex: Molex
Process:
Dehydrogenation:
Product from n-paraffin separation unit mainly
containing C10 C14 paraffins and solvent mixture. After
separating out the solvent, C10 C14 paraffins is fed
into the dehydrogenation unit containing Pt on alumina
as a fixed bed catalyst. The reaction conditions are;
Temperature: 480 oC ; Pressure: 2 kg/cm2
H2:Hydrocarbon ratio: 8:1 ; LHSV: 20 h-1
Water: 2000 ppm
Manufacture of LAB
Ex: Pacol Process
90 92% of n-paraffin are dehydrogenated to mono
olefins.
Any aromatics formed are removed by solvent extraction.
Ex: PEP process
Diolefins formed are converted by selective
dehydrogenation to mono olefins. Ex: DeFine Process
Alkylation:
The product of dehydrogenation unit is admitted into the
alkylation unit containing solid acid catalyst like zeolite
along with benzene. LAB is formed and the product
mixture is distilled in series of three columns where
Benzene, paraffins and LAB are collected as overhead
product respectively.
Ex: Detal Process
Thermoplastics
Manufacture of Polyethylene
Polyethylene or Polyethene (PE) is the largest volume of
thermoplastic resin produced in the world.
PE is the largest consumed commodity plastic in India and part of
is met by import.
Important classes of PE
Low Density Polyethylene (LDPE) - 0.910 to 0.940 g/cm3
High density polyethylene (HDPE) > 0.941 g/cm3
Linear Low Density Polyethylene (LLDPE) - 0.915 to 0.925 g/cm3
LDPE is branched polymer prepared at high temperature, high
pressure by free radical addition polymerization using molecular
oxygen or peroxides initiators.
HDPE is linear, high crystallinity having high melting point,
prepared at low pressures and low temperatures by Ziegler-Natta
catalysts following non-free radical mechanism.
LLDPE is a copolymer of ethylene with -olefins of C4 - C10, with
controlled branches and excellent combination of properties,
prepared by using Ziegler-Natta catalysts or by gas phase process.
Manufacture of LDPE
Manufacture of LDPE
High purity ethylene and small amount of oxygen or
peroxide are compressed to 1000-2500 atm. and heated to
the reaction temperature(100-300 oC).
The mixture is admitted into the autoclave reactor where
free radical polymerization occurs.
n CH2=CH2 (CH2-CH2)n
Rate and degree of polymerization depends on the
temperature, pressure and initiator concentration
Products are taken to separator from where unreacted
ethylene leaves from the top and recycled. The molten
polyethylene leaves from the bottom of separator which is
chilled, chopped and sent to storage bin.
Major use of LDPE is in packaging.
Manufacture of Polypropylene(PP)
Polypropylene is the second most important
polyolefin having excellent environmental profile.
Consumption polypropylene is again mainly in
packaging at the expense of polystyrene and PVC
due to their toxicity issues and problem of waste
disposal. Consumption of polypropylene is on the
increase owing to fiber and filament segment (PP
woven sacks in the fertilizer, pesticides,
agricultural products packaging, carpets),
automobiles etc.
Manufacture of Polypropylene
Propylene is treated for the removal of sulphur
compounds, light ends and traces of oxygen
(compounds containing oxygen deactivate the
Ziegler-Natta catalyst).
Zigeler-Natta catalyst is prepared by reacting triethyl
aluminium and titanium tetrachloride to produce a
complex which is finely divided into a slurry in
saturated paraffin liquid (C5-C7).
Purified propylene and catalyst slurry are
continuously pumped into the reactor maintained at
70 oC and 7 atm. where the coordination
polymerisation occurs resulting in stereoregular
polymer.
Structure of Polypropylene
More than 90% of polypropylene formed is of
isotactic structure.
Product from the reactor is taken through series of
flash drums to remove the solvent as vapours. The
remaining product leaving the flash drum is filtered
to separate the polymer and the catalyst.
The catalyst is treated with water to destroy it since
dry catalyst is highly flammable.
The solvent vapours are dried, distilled and recycled
to the catalyst preparation unit.
Polypropylene solids left in the filter are withdrawn,
dried, extruded and finished to required form like
pellets, flakes or powder.
Manufacture of Teflon
Highly dense, excellent chemical and electrical
resistance, low coefficient of friction, tough and
heat resistant
Used for making wire & cable insulation, coating of
frying pans, non-lubricating bearings, insulators for
motors, generators, spark plug etc.
Manufactured by solution polymerisation using
water as solvent, initiated by free radical initiators
under pressure in a batch reactor.
Teflon formed is washed with water.
Made in to the form granular or pellet form or
aqueous dispersion.
Manufacture of Teflon
Thermosetting Plastics
Manufacture of Phenol-Formaldehyde Resin
Phenol-formaldehyde resin is an important
example of thermosetting resin.
It has high strength, rigidity, chemical resistance,
thermal stability, adhesiveness etc.
Hence used in making electrical switches, plugs, as
binder in plywood manufacture, moulded
products like cabinets of electronic consumer
durables, varnishes, lacquers etc.
It is manufactured by
(i) a single stage process involving base catalysed
addition of formaldehyde to phenol to yield
phenol-formaldehyde resin called Resole
Conditions:
Temperature: 160 oC
Catalyst: Sodium or Ammonium Hydroxide
Phenol: Formaldehyde Ratio= 1:1.25 to 2.0
Cross linking to Bakelite is achieved by simple pH adjustment
(ii) A two stage process involving an acid catalysed
addition of formaldehyde to phenol to yield a
linear phenol-formaldehyde resin called Novoloc.
Conditions:
Temperature: 100 oC; Catalyst: Oxalic acid
Phenol:Formaldehyde = 1:0.8
Crosslinking is achieved by adding cross linking agent
like hexamethylene tetramine which decomposes and
form methylene bridges at the time of moulding.
Phenol, formaldehyde and catalyst are mixed together in a
jacketed autoclave (resin kettle) and heated with steam.
After the reaction starts, heat of reaction is removed by
refluxing and water cooling.
Heavier viscous resin separates as a bottom layer with
aqueous layer at the top.
Dehydration is done by heating and by applying vacuum.
Fused resin at 130-150 oC is removed from the kettle,
cooled and ground to fine powder.
Then it is mixed with fillers, colouring agents, lubricants,
cross-linking agent in a blender or ball mill.
Then heated on a pair of differential heating rolls to get fast
curing commercial phenolic molding powder.
Manufacture of Epoxy Reins
Epoxy resins have
Chemical stability
Excellent adhesion
Good abrasion resistance
Curing and moulding without evolution
of gas with low shrinkage
Dimension stability
Good electrical properties like
dielectric strength
Main Uses:
Binders and laminating agents
Adhesives and sealant
Automotive bodies
Chemical plant equipment
Epoxy resins manufactured largely by batch process
using solvent polymerisation.
Bisphenol-A and excess of epichlorohydrin are brought
into contact in the presence of alkaline catalyst at
elevated temperature.
After the reaction, solvent is removed and the resin is
purified and dried.
The resins are cured anhydrides or amines
Synthetic Rubber
Manufacture of SBR
The most widely used rubber is the Styrene-Butadiene
Rubber (SBR).
It is produced by hot or cold emulsion polymerization.
The monomer mixture comprised of styrene and butadiene
are mixed with soap solution, catalyst (Hydrogen
perroxide), activator and modifier are continuously fed into
the reactor and polymerization is carried out.
Controlling parameters of the reaction are temperature,
flow rate and speed of agitation.
Reaction is stopped when 60-70% polymerization gets
completed by adding terminating agent.
Milky white emulsion called latex is withdrawn from the
reactor and unreacted butadiene is recovered through blow
down pressure flash tank and vacuum flask tank.
Manufacture of SBR
Manufacture of SBR
Unreacted styrene is recovered by steam
stripping in the latex column.
Finally the latex is stabilized with antioxidants (n-
phenyl naphthylamine) and sent to blending
section.
Finally coagulation is carried out using sulphuric
acid and NaCl solution and carbon black is added
during coagulation to improve its properties.
Then it is passed over screen and washed with
water, dewatered by vacuum filter, dried and
shipped.
Manufacture of Nitrile Rubber
Co-polymer of acrylonitrile Butadiene
containing 15-50% acrylonitrile is commonly
known as Nitrile Rubber or Buna-N
Presence of nitrile group makes it resistant to
oil & solvents and improved abrasion
resistance.
Major application is in the automotive
industry and in military.
Manufactured by cold and hot (50 oC) emulsion
polymerization
Monomers are emulsified in water and mixed with
emulsifying agent like soap and free radical initiators like
Benzoyl peroxide, hydrogen peroxide etc.
The monomers are oriented in the form of micelles and
initiators initiate the polymerisation which is carried out in
series of reactors.
The polymer formed is transferred to the monomer
recovery tank where the unreacted monomers are
recovered and recycled. Antioxidant like phenyl--
naphthylamine is added to stabilise the latex.
The latex is coagulated into fine crumble by the addition of
salt and acids.
Then it is washed and dried.
Manufacture of Butyl rubber
Owing to its excellent impermeability for air, it is used
for the manufacture of tubes.
Due to high electrical resistance, used for making high
voltage cables
Due to chemical resistance, used in the lining of
reactors and hoses.
Manufactured by co-polymereising isobutylene with
small amount ( 0.5-2.5%) of isoprene by cationic
addition polymerization using Tetraalkyl aluminium as
catalyst and vanadium oxychloride as co-catalyst.
Monomers and catalyst are dissolved in methyl
chloride and taken to the reactor maintained at 9 oC.
The heat released due to polymerization is removed by
vapourising the solvent.
Manufacture of Butyl Rubber
Manufacture of Butyl Rubber
Polymer slurry flows out into the flash drum which

contains hot water to agitate the polymer and flash
off (i.e vapourises) the unreacted monomers which is
recycled.
Polymer is washed with water and filtered.
Manufacture of Butyl rubber
Heat of polymerisation is removed by the
vapourisation of methylchloride to maintain the
reaction temperature.
Polymer slurry is transferred to flash drum which
contains hot water to agitate the polymer and
flash(i.e Vapour) of hydrocarbons and the solvent
methyl chloride which are recovered and recycled.
Polymer mass is washed and filtered to separate
the polymer
Synthetic Fibers
Synthetic Fibers
Natural fibers have been in use since ancient times.
Eighteen and nineteen centuries during which
industrial revolution took place mainly owing to
fibers production.
Synthetic fibers are indirect consequence of
spectacular growth in petrochemical industry.
Shortage and higher price of cotton resulted in
synthetic fiber becoming the dominant player in
textile industry.
Important Synthetic fibers
Polyamides (Nylon-6 and Nylon-6,6) 1929
Polyester (PET) 1941
Acrylic Fibers 1944
Manufacture of Polyester (PET)
Polyester is one of the most popular synthetic fiber
It is produced by two routes
(i) Oxidising p-xylene to Terephthalic acid followed by
esterification with Monoethylene Glycol (MEG) to
to PET
(ii) Converting p-Xylene to Dimethyl
terephthalate(DMT) followed by its
transesterification with ethylene glycol to PET.
(This was the most commonly used route initially
and described here)
Manufacture of DMT
Mixture containing p-xylene, recycled p-
methyl toluate, Cobalt Naphthenate (0.05 to
0.2%) and air are fed into the oxidiser.
Temperature: 140-180 oC, Pressure: 0.6-1 MPa
Manufacture of DMT
Manufacture of DMT
Oxidation of p-Xylene to p-toluic acid and p-methyl toluate to
monomethyl terephthalate takes place in the oxidiser
Products leaving the oxidiser enters the Esterification column
where methanol is admitted.
Temperature: 250 oC ; Pressure: 2.5 MPa
Conversion of p-toluic acid to p-methyl toluate and monomethyl
terephthalate to dimethyl terephthalate take place.
Products of esterifier are taken to the methanol separation
column where crude DMT leaves as bottom product. The
overhead product is taken to methanol column where methanol
gets separated and leave as over head product and is recycled to
esterifier and part of it, is used in the centrifuge for washing.
The bottom product is p-methyl toluate which is recycled to
oxidizer.
Raw DMT leaving the bottom of the methanol separation
column is admitted into the Raw ester distillation column where
p-methyl toluate any is separated out as overhead product
which is recycled back to the oxidizer.
Manufacture of DMT
Bottom product of raw ester distillation column is
taken to the heavy end distillation unit where the
DMT distills out as overhead product and the
heavier ends leave as bottom product(residue).
The DMT leaving the Heavy end distillation is
taken to Vacuum crystallizer where DMT
crystallizes out.
The crystals are washed with methanol in
centrifuge.
Recrystallized DMT is further purified in the DMT
purification column and used as the feed in
polyester plant.
Manufacture of Polyester
DMT is reacted with excess monethylene glycol
(MEG) at 150 oC in the presence of sodium
acetate and manganese acetate catalyst (0.01-
0.07 wt%). The reaction is carried out in two
reactors in sequence.
Methanol is formed during the reaction, which is
removed by distillation by raising the
temperature to 210 oC. Methanol removed is
used in the DMT production.
Products are transferred to the polymerization
reactor where the antimony dioxide catalyst and
phosphoric or phosphorus acid stabiliser are
added.
Polyethylene terephthalate formed is then sent
to spinning section where it is spurn into fibers.
Manufacture of Polyamide Fibers
Two important polyamide fibers are Nylon-6,6
and Nylon-6
Nylon-6,6 has superior high temperature strength
compared to Nylon-6.
Manufacture of Nylon-6,6
Manufactured by condensation polymerization of
adipic acid and hexamethylene diamine.
Manufacture of adipic acid is possible by different
routes:
Phenol Cyclohexanol Adipic acid
Butadiene Route
Cyclohexane Route
Manufacture of Adipic Acid
Manufacture of Adipic Acid
Oxidation of cyclohexane to cyclohexanol and
cyclohexanone at 160 oC with air in the presence
of Cobalt naphthenate catalyst.
Oxidation of mixture of cyclohexanol and
cyclohexanone to adipic acid using nitric acid in
the presence of ammonium metavenadate and
copper scrap at 60-80 oC.
Adipic acid formed is crystallized, centrifuged
and dried with hot air.
Manufacture of Nyon-6,6
Hexamethylene diamine and adipic acid are
dissolved in water and pH is adjusted to 7.8
The solution is concentrated under vacuum and
charged into autoclave
The remaining water is removed by heating gradually
to 280 oC where by the polycondensation takesplace.
The nylon-6,6 leave the autoclave and extruded as
ribbon on the chilling rolls then to chipper to
produce small chips.
They are then extruded by melt spinning into fibers
and wound on bobbins at the speed of 750 m/min.
Manufacture of Caprolactam
Caprolactam is the raw material for Nylon 6 which is used as fibers,
floor covering and as engineering plastics.
Caprolactam is manufactured by first oxidizing cyclohexane in a
multicompartment reactor at 160 oC and 10 atm. Pressure using
cobalt salt as catalyst.
Cyclohexane Cyclohexanol Cyclohexanone

Product stream is treated with NaOH to neutralize acids, saponify
esters and to decompose peroxide. Which form a separate layer
from organic layer in gravity settler and separated;
Organic layer is distilled through three distillation columns. In the
first column, heavy ends are separated as bottom product.
Overhead product is fed into the second distillation column where
cyclohexane gets separated as overhead product which is recycled
to the oxidizer.
Cyclohexanone is oxidized to cyclohexanone oxime in a multi-compartment reactor.
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.
Then it is neutralised with ammonia during which ammonium sulphate is

formed as byproduct.
Caprolactum and aqueous ammonium sulphate are passed through extractor using
toluene as solvent. Ammonium sulphate collected from the extractor bottom is
purified, crystallized, centrifuged and dried. Caprolactum is concentrated in
evaporator and purified.
Manufacture of Nylon-6
First caprolactam is melted and mixed with additives.
Caprolactam is polymerized to Nylon 6 by either batch or
continuous process.
In a continuous process, aqueous caprolactam solution is
mixed with catalyst, stabilizer, optical brighteners and
introduced into the top of the stainless steel
polymerization column maintained at 240-270 oC and
inert atmosphere.
First the ring structure of caprplactam opens to form
aminocaproic acid.
Caprolactam Aminocaproic acid

The aminocaproic acid undergoes polymerization
to yield Nylon 6.
.
Aminocaproic acid Nylon 6
The Nylon 6 formed is cut into chips.

The chips are spurn into Nylon 6 yarn by melt
spinning
Manufacture of Acrylic Fiber
is the third major class of synthetic fiber produced from
mainly from acrylonitrile along with co-monomers like
methyl acrylate, vinyl acetate, vinyl chloride etc..
They have hardness, rigidity, sunlight resistant, chemical
resistance.
Mostly used as substitute for wool
Manufacture of acrylic fiber involves broadly two parts;
1. Polymerization 2. Spinning
First the acrylonitrile, co-monomer, free radical initiator are
dissolved in water in a mixing tank.
Then it is taken to the batch or continuous reactor where the
polymerization is carried out.
Product from the reactor is taken to stripper where
unreacted monomers are removed and recycled.
Then the slurry is centrifuged to separate the polymer.
Polymer is dried and sent to storage.
Acrylic polymer is spurn into fiber by solution spinning,
either by wet or dry spinning.
First the acrylic polymer is dissolved in solvent (Ex:
Dimethyl formamide, dimethyl acetamide) .
In wet spinning the polymer solution is forced through the
spinneret whereby it is extruded as liquid threads which
move through the non-solvent(i,.e Precipitates the
polymer from the solution into solid) which is the aqueous
solution of solvent. The acrylic polymer get coagulated into
solid which is washed, dried, crimped and annealed in wet
spinning.
In dry spinning, polymer solution is forced through the
spinneret as liquid threads and the solvent is evaporated in
a stream of hot inert gas. The fiber formed is crimped and
annealed.

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Unit-III

o-xylene Phthalic anhydride

The Undesirable side reaction is Complete

Catalyst: Vanadyl Phosphate

Product composition depends on the CH4/Cl2 ratio.

Along with acrylonitrile, Hydrogen cyanide and

Product mixture is taken to separator where it gets

Polymer slurry flows out into the flash drum which

Cyclohexane Cyclohexanol Cyclohexanone

Then it is neutralised with ammonia during which ammonium sulphate is

Caprolactam Aminocaproic acid

Aminocaproic acid Nylon 6

The Nylon 6 formed is cut into chips.

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