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Chapter

Petrochemicals

Introduction to Petrochemicals Industry

• Petrochemicals are an indispensible part of our life and are providing key feedstock
to chemical industry for making thousands of different chemicals (Rubber,
polyethene, etc.) which people usually encounter as end products.

• An increasing demand of growing population and limited resources like coal, cotton,
jute, wood, natural rubber, molasses, and alcohol based chemicals, etc. has resulted in
higher production of synthetic chemicals, derived from petroleum, as a substitute of
natural resources.

• Petrochemical linked industries: Packaging, agriculture, telecommunication,

construction, home appliances, health care, personal care, textile, tyre,
pharmaceuticals, explosives, etc.

• List of chemical feed stocks are given in figure 1.

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Figure 1: Chemical feedstock sources

Table 1: Petrochemical social linkage

• Increase in demand of plastic and rubber after world war II, led to rapid growth of
petrochemicals.
• Around 95% of organic chemicals are based on petrochemicals.
• Petrochemical industry is highly technological and capital-intensive.

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Figure 2: Structure of petrochemical complex

Figure 3: Petroleum and petrochemical interface

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Figure 4: Overall view of petrochemical complex

Olefins Production

• Important olefins produced: Ethylene, Propylene, Butadiene, etc.

• Major building blocks for petrochemicals due to their reactivity and versatility

• Applications areas: In manufacture of polymers, chemical intermediate, synthetic

rubber, etc.

• Major technologies for olefin productions: Steam cracking, Fluid catalytic

cracking, Oxidative coupling of methane, Catalytic dehydrogenation, Deep catalytic
cracking, methanol to olefin technology, etc.

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Steam Cracking for Production of Olefins

• Steam cracker in petrochemical complex produces large number of products other

than light olefins, as butane, isoprene, pyrolysis gasoline, etc.
• Various feed stocks used in steam cracker: Naphtha, natural gas liquid, gas oil,
ethane, propane and ethane-propane mixture

• Cracking reaction temperature: 700-900°C (Depending on type of feed stock)

• Choice of feedstock depends on its availability and range of downstream production.

• Olefins plants are complex as well as costly and both increase with increase in
heaviness of feed.
• Still, heavier feedstock is gaining importance because of more production output
from it.

Naphtha/NGL Cracker Unit

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Hot Section of Cracker

• Feed is preheated by quench water and steam before entering to furnace.

• Further, preheated and mixed with super heated steam (as diluent) in furnace.

• Steam minimizes the side reactions responsible for formation of coke, improves the
selectivity to produce desired olefins by lowering partial pressure.

• Lighter feedstock required less steam as compared to heavy one.

• Temperature of radiant section of furnace = 650°C

• Residence time = 0.15-1.2 S

• Indirect and direct quenching to control the reaction

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Cracked gas compression and dehydration

• Top effluent from primary fractionator to multi-stage compressor
• Gas before final compression stage is de-suphurized and CO2 removal through
caustic scrubber.
• This removal also avoids corrosion and formation of CO2 ice in cold section at later
stage.
• Cracked gases are dried in dehydrator before entering cold section.

Cold section
• Dried cracked gas is cooled to −165°C in cascade refrigeration system.
• Cold section contains demethanizer, deethanizer, acetylene hydragenation unit,
ethylene separation, depropanizer, C3 hydrogenation and debutanizer.

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• Feed temperature to deethanizer = −10°C

• Acetylene hydrogenation unit: Pd Catalyst, 40°C temperature
• Ethylene separator: Distillation column at −35°C
• Debutanizer: Pyrolysis gasoline is important source of gasoline.

Aromatic Production
• Important (aromatic) petrochemicals generally produced: Benzene, toluene and
xylene (BTX), ethyl benzene, etc.

• Products which use above basic aromatics as one of the raw materials: Synthetic
fibres, elastomers, explosives, pesticides, dyes, detergents, resins, etc.

• Major sources of benzene: Catalytic reformer, pyrolysis gasoline from steam cracker,
toluene disproportionation and coal

• Major sources of xylene: Catalytic reformer, pyrolysis gasoline from steam cracker,
toluene disproportionation

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• Catalytic reforming: Converts low octane naphtha (BP in range of 60-180°C) to high
octane gasoline and aromatics rich in BTX

• Steam cracking of naphtha: Produce liquid product (pyrolysis gasoline) rich in

aromatics containing about 65% aromatics about 50% of which is benzene.

• Toluene disproportionation: Conversion of toluene in benzene and xylene

• Coal carbonization (Coke oven plant): Heating of coal in absence of air, light oil is
obtained as by product which contains 2-8 kg benzene, 0.5-2 kg toluene and 0.1-0.5
kg xylene per tonne of coal

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Derived Polymers
• Polymers: Material of choice due to their versatility, their physical and chemical
strengths, lightness in weight, chemical and corrosion resistance, economic viability,
easy processability, attractiveness and durability in all weather conditions

• Uses:
• Elastomers
• Plastics
• Fibres
• Surface coatings
• Adhesives, etc.

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• Polymers are produced by intermolecular reaction of molecules having a

functionality of two or more.

• Thermoplastic market: 10% of global chemical industry (Olabisi, 1997)

• Poly-olefins: Largest group of thermoplastic polymers (e.g. LDPE, LLDPE, HDPE,

Polypropylene)

• Major success factors of poly-olefins: Easy accessibility, reasonable raw materials,

low production cost, non-polluting processes, resource saving products,
environmentally safe products, energetically exploitable after usage, broad product
portfolio, etc.

Polyethylene (PE)
• Largest volume thermoplastic resin in the world with growth rate of 3-5%
• Second largest commodity player used in India, after PVC
• Applications: Packaging, foam, insulation, containers, toys, car parts, etc.
• Major types of PE: LDPE, LLDPE, HDPE, metallocene polyethylene
• LDPE (Low density polyethylene): Prepared by high pressure using tubular or
stirred autoclave reactors
• LLDPE (Linear low density polyethylene), HDPE (High density polyethylene):
Prepared at low pressure in fluidized beds in presence of suitable catalyst
• LLDPE offers improved tensile strength, puncture resistance, higher elongation,
exceptional draw down, improved stress crack resistance, low temperature
brittleness.

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Union Carbide (HDPE and LLDPE) Process

• Gas phase using fluidized bed reactor

• Bed consists of catalyst plus newly
formed and growing PE
• H2 to control molecular weight
• High gas recycle rate with conversion to
PE of about 2% per pass only
• Single stage compressor
• Granular product flows intermittently into
discharge tank where unreacted gas
separates and return to reactor.
• Hydrocarbon remaining with product are
removed by purging with N2.

BTX Derivatives
• Benzene, toluene and xylene (BTX) and Ethyl benzene: Major feedstock for large
number of intermediate which are used in production of synthetic fibres, resins,
synthetic rubber, explosives, pesticides, detergents, dyes, intermediates, etc.
• Major application of Benzene: A source of styrene, alkyl benzene, cumene, large
number of aromatic intermediate and pesticides, etc.
• Major application of Toluene: A major solvent, manufacture of benzoic acid, chloro
derivatives, nitro toluene, toluene sulphonic acid, benzaldyhyde, etc.
• Major application of p-Xylene: Feed stock for DMT/TPA,
• Major application of o-Xylene: Manufacture of Phthalic anhydride
• Styrene: Versatile monomer exclusively used for manufacture of plastic including
polystyrene (PS), expandable polystyrene (EPS), acrylonitrile butadiene styrene
copolymer (ABS), Styrene acrylonitrile resin (SAN), Styrene butadiene rubber
(SBR)
• Above derivatives account for 75-80% of total styrene consumption.

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Manufacture of Polystyrene
• Important thermoplastic having
wide application: In consumer
durable goods, electronics,
packaging, toys, structural foams,
wall tiles, shoe soles, lenses,
bottle caps, wire and cable
sheathing, automobile interior
parts, etc.
• Properties: Inexpensive, hard,
rigid and transparent, easily
coloured, moulded and fabricated,
good electrical and moisture
resistance, low moulding
temperature
• Suspension polymerization
process

• Agitation catalyst and

chain transfer agents are
also added in reactor.

• Polymerization reaction is
controlled by temperature
and chain transfer agents.

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Thanks

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