ooooooooooooooPETROCHEMICAL PROCESSoooooooooooooo
◙ The petrochemical industry produces various kinds of chemical
products such as polymers, fibers or rubber, from such raw
materials as petroleum.
Hydrocarbons
→ source material
→ used to produce variety components including ethylene,
propylene, butadiene and pyrolysis gasoline
Pyrolysis
→ most important process of petrochemical production
→ presents the main source for the majority of basic organic
industrial raw materials
a. Olefin (ethene, propene, isobutene, butene)
b. Butadiene
c. Aromatic Hydrocarbons (BTX = benzene, toluene,
xylene)
→ non-catalyzed process of thermal decomposition
→ performed at high temperatures (750 – 900oC) at normal
pressure
Steam Cracking
→ a petrochemical process in which saturated hydrocarbons
are broken down not smaller unsaturated hydrocarbons
→ principal industrial method for producing lighter alkanes
→ a gaseous or liquid hydrocarbon feed is diluted with steam
and heated in a furnace with the absence of oxygen
→ has reaction temperature at around 850oC with reaction
allowed to take place briefly
◙ Cracking reactions of one or more covalent carbon bonds in
hydrocarbon molecules take place by free radical mechanism.
◙ In modern cracking furnaces, the residence time is reduced to
milliseconds resulting in gas faster than the sound of speed.
◙ After cracking temperature is reached, gas is quenched to
stop reaction in transfer line heat exchanger or quenching
header using quench oil.
oooooooooooooooooooooOLEFINSooooooooooooooooooooo
Olefins
→ also called alkene
→ compound made up of hydrogen and carbon that contains
one or more pairs or carbon atoms linked by a double bond
→ example of unsaturated hydrocarbons
→ can be classified in either or both of the following ways
a. Cyclic or Acyclic (Aliphatic)
◦ the double bond is located between carbon atoms
forming part of a cyclic or an open-chain grouping,
respectively
b. Monoolefins, Diolefins, Triolefins, etc.
◦ number of double bonds per molecule is one, two,
three or some other number
◙ Ethylene and propylene are important sources of industrial
chemicals and plastic products. Butadiene is used in making
synthetic rubber.
ooooooooooooooooooooiETHYLENEioooooooooooooooooooo
Ethylene
→ one of the most important fundamental chemicals in
petrochemical industry
→ source material for products such as polyethylene resin,
ethylene glycol, vinyl chloride resin, acetic acid, styrene, and
alpha olefin
ooooooooooooooooooIIoPROPYLENEoIIoooooooooooooooooo
Propylene
→ used to produce polypropylene resin, acrylonitrile, acrylic
acid, propylene oxide, isopropyl alcohol and acetone
→ important basic chemical in the petrochemical industry as
ethylene
oooooooooooooooooooIIIIIBUTANEoooooooooooooIIIIIoooooo
Butane
→ hydrocarbons with four carbon atoms, primarily butane,
butene, and butadiene which are derived from three main
sources
a. Natural Gas and Oil
b. Steam Cracking of Higher Hydrocarbons
c. Refinery Gases
oooooooooooooooooooiAROMATICSiooooooooooooooooooo
◙ Several stages may be grouped as
a. Feedstock (first – generation petrochemicals)
b. Intermediates (second – generation petrochemicals)
c. Finished Products (third – generation petrochemicals)
Olefins
→ produced from thermal cracking of ethane, propane,
butane, and naphtha
→ starting material for polyolefin plants
→ reacted with other hydrocarbons or non-hydrocarbons to
generate vinyl chloride, ethylene glycol, etc. which are used as
starting material for manufacturing of polymers
Plastics
→ available in forms of extrudates, granules, powders, etc.
→ converted by casting, molding, or blowing machines
→ also known as plastomers with high modulus of elasticity
→ can be classified into two types
a. Thermoplastic (Thermoplast)
◦ linear in molecular structure
◦ can be heated and solidified without loss of original
properties
b. Thermosets
◦ will be permanently transformed to a chemically cross
linked or non-linear structure and cannot be returned to
their original properties during heating and cooling
◙ Synthetic fibers are made from polymers with high modulus of
elasticity.
◙ Rubbers or elastomers are polymers with a low modulus of
elasticity. Raw rubber is available from the polymerization unit in
the form of sheets.
◙ A variety of chemical reactions are involved in the
petrochemical manufacturing processes which are mostly
catalytic with heat effects like
a. Dissociation
◦ occur during thermal and catalytic process
b. Dehydrogenation
◦ occurs catalytically or thermally during cracking
c. Hydrogeneration
d. Addition
◦ like oxidation, chlorination, fluorination and sulfonation
◦ required to make intermediates or monomers
e. Condensation
f. Polymerization
◦ occurs mostly in the presence of initiators or catalysts
with heat evolution
◦ have two types of reaction
i. Addition Polymerization – involves chain reactions
in which monomer join in a chain
ii. Condensation Polymerization – involves two
monomers which combine to form a polymer with
the elimination of small molecular weight by-
products like water
ooooooooooooooooNAPHTHA CRACKINGoooooooooooooooo
Naphtha
→ mixture of hydrocarbons boiling in the range of the lowest
boiling component, C5, to 150oC
→ contains paraffins, naphthene, and aromatics in various
proportions
→ cracked in a tube-still furnace at a temperature above 800oC
◙ Light hydrocarbons obtained from initial cracking further crack
into lighter olefin and propagate until temperature is brought
down
◙ Cracking reaction is carried out in a very short residence time
to avoid undesirable heavy products and coke.
◙ Products are sent to the series of separator units like
demethaniser, de-ethaniser, de-propaniser, and debutanizer
units which are multiplated distillation columns
ooooioooooPRIMARY FRACTIONATOR OR STABILISERooiooooooo
◙ Cracked liquids and gases are separated in a fractionating
column.
◙ The bottom product is the heavy cracked oil rich in high boiling
aromatics while cracked gas, containing hydrocarbons from
methane to C7 emerge from the top which is then compressed
and amine washed to remove H2S and CO2.
oooooooooiiioooooHYDROGEN SEPARATORooiooooioooiooooo
Demethaniser
→ fed by liquified gases from a hydrogen separator
→ methane emerges from the top and is used as fuel for furnace
→ bottom of the column is passed to a de-ethaniser
De-ethaniser
→ separates ethane and ethylene mixture as the top product
Ethane-Ethylene Separator
→ fed with a C2 mixture from the top of de-ethaniser column
→ separates ethylene as the top product and ethane as the
bottom product
→ produces ethylene to be stored and will be used up in the
polyethylene synthesis plant
→ recycles ethane to a small cracking furnace to yield
additional ethylene