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Unit Ii
Unit Ii
PRODUCTION OF OLEFINS
Olefins: ethylene and propylene
The largest volume petrochemicals produced in
which Annually global production of ethylene is
about 120 million tons with a continuous annual
increase of some 4 - 5 %.
Ethylene and propylene have no end use, they are
building blocks for a large variety of chemicals and
petrochemical products.
Polymers are the dominating end-users.
Olefins are major building blocks for petrochemicals. Because
of their reactivity and versatility, olefins especially the light
olefins like ethylene, propylene, butenes, butadiene, etc., there
has been tremendous growth in the demand of the olefins.
Olefins are finding wide application in the manufacture of
polymers, chemical intermediates, and synthetic rubber.
Ethylene itself is basic building block for large number of
petrochemicals and is quoted as king of chemicals.
Some of ethylene manufacturing company and their capacity is
given in Table M-VII 2.1.
The global ethylene capacity at January 1, 2011, net additions
and closings was more than 138 million tones compared with
nearly 130 million tones in 2008 [Oil & gas J. Vol 129, 2011].
Global ethylene capacity is given in Table M-VII 2.2.
STEAM CRACKING FOR PRODUCTION OF OLEFINS
The steam cracker remains the fundamental unit and is the heart
of any petrochemical complex and mother plant and produces
large number of products and byproducts such as olefins
ethylene, propylene, butadiene, butane and butenes, isoprene,
etc., and pyrolysis gasoline.
The choice of the feedstock for olefin production depends on the
availability of raw materials and the range of downstream
products.
Naphtha has made up about 50-55percent of ethylene feedstock
sources since 1992. Although basic steam cracking technology
remain same for naphtha, gas oil and natural gas, different
configuration of steam cracking plant are available from various
process licensors [Petrochemical processes, 2003].
Steam cracking challenges
The steam cracking process has high yields with
high temperature in the cracking furnaces.
Steam cracking furnace valves play an important
role in ensuring proper ethylene process
performance.
Reliable and accurate control, on-off and valve
performance is vital during normal production and
frequent furnace decoking operations to ensure
total process productivity and safety.
The indicated feedstock's (ethane, propane, butane, naphtha
and gas oil) are fed to a pyrolysis (steam cracking) furnace,
where they are combined with steam and heated to
temperatures between approximately 1450 - 1600 F (790 -
870 C). Within this temperature range, the feedstock
molecules "crack" to produce ethylene as well as methane,
hydrogen, ethylene, propylene, butadiene, benzene, toluene
and other co-products.
After the pyrolysis reaction is quenched, the rest of the
plant separates the desired products into streams that meet
the various product specifications.
Process steps include distillation, compression, process gas
drying, hydrogenation (of acetylenes), and heat transfer.
Hot Section:
The cracker furnace may be divided into three sections:
convection zones, radiation zones and quench section.
The hydrocarbon feed stock is preheated by quench water and
steam before entering the convection zone of the furnace where
it is further preheated and mixed with superheated steam, which
is added as a diluent.
The steam minimizes the side reaction responsible for the
formation of coke during pyrolysis and improves the selectivity
to produce desired olefins by lowering hydrocarbon partial
pressure.
The requirement of steam will depend upon the type of
feedstock; the lighter hydrocarbon requires less steam as
compared to heavier feedstock.
The hydrocarbon and steam preheated in convection zone in the
upper part of the furnace enter the radiant section of furnace at
about 6500C & total pressure of 1.7 bar, where pyrolysis of feed
takes place.
The coil length in the radiant section varies from 60m for a
naphtha cracker to 85m for an ethane cracking unit.
The resistance time varies for different feedstock is around 0.15-
1.2 sec and Reynolds number is around 3,00,000.
The effluent leaves at a temperature of 830-8700C and Pressure of
1.7 bar.
The flue gas temperature may be of the order of 12000C with the
inner tube skin temperature of 10080C.
The reaction is endothermic. Here heat flux ranges from 55-
85kJ/m2.
The radiant coil outlet temperature is controlled to achieve desired
ethylene and propylene yield.
Pyrolysis of any hydrocarbon feedstock is always accompanied
by coke formation, which deposits on the walls of the reactor
under typical operating conditions.
the furnace effluent is rapidly quenched in double pipe heat
exchangers and multi-tubular heat exchangers which cools to at
a temperature of 3500C.
The effluent is further quenched by direct contact with quench
oil before entering the quench oil tower where besides cooling
the furnace effluent, the separation of gasoline and lighter
products from fuel oil also takes place.
here quenching is essential in order to restrict the
polymerization reactions.
Ethylene cracking effluent must be quenched uniformly and
rapidly for high product yield.
Quenching is performed in two ways directly by oil or
water (OR) Indirectly by a quench cooler.
The basic requirements for cracked product quench
coolers are rapid and uniform cooling, small pressure
drop, maximum heat recovery, long continuous run
length and low maintenance.
The cracked gas overhead of the quench oil tower is
further cooled in the quench water tower by direct
contact with water and is finally sent to primary
fraction column.
The gases are separated at the top and are sent to
compression section for separation and purification of
cracked products.
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Cracked gas compression and dehydration:
The effluent from primary fraction column is compressed in four or
five stages on centrifugal compressor containing intercoolers and then
to a separator drum.
The condensate from separator drum enters a stripper where the
higher fractions are recovered.
The gas before entering the final stage compression is desulfurized by
passing through a caustic scrubber where the separation of sulphur
compounds and CO2 takes place.
The removal of CO2 from gas is essential in order to meet the product
quality.
The removal of CO2 also avoids corrosion and formation of CO2 ice
in the cold section.
The cracked gases are dried in dehydrators containing molecular sieves
before entering the cold section.
Cold section:
The dried cracked gas after removal of sulphur
compounds, CO2 and moisture are sent to cold section
where it is cooled to -1650C in cascade refrigeration
system using propylene and ethylene.
The cold section contains demethanizer, deethanizer,
acetylene hydrogenation unit, ethylene separation,
depropanizer, C3 hydrogenation and debutanizer.
Here refrigeration system is an important part of any
ethylene plant.
The recovery of ethylene will depend on reliability and
flexibility of the system, as a coolant at different
temperature levels.
Demethanizer:
The cracked gases after cooling to -1650C are sent to
demethanizer which operates at a pressure of about 7 atm
in case of low pressure demethanizer or 355 atm in case of
high pressure demethanizer.
The purpose of demethanizer is to make sharp separation
between methane and ethylene.
Demethanizer operating performance is very much
dependent on its feed condition, temperature, pressure and
flow rates.
Demethanizer operation is most sensitive to flow rates and
temperature and least sensitive to pressure.
Deethanizer:
The demethanizer bottom portion consisting of ethylene and heavier
fraction is sent to deethanizer which is essentially as fractionator
operating pressure of about of 24 kg/cm2 and temperature -100C.
The deethanizer separates the demethanizer bottom into C2 overhead
and C3 sent to depropanizer for separation of propane.
Hydrogen
Utilities Mixed
Butanes
Gasoline
Material Movements
Acid Gas
Methane
Quench
Fuel Oil
Cracking
Naphtha Furnaces
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OPERATING VARIABLES IN STEAM CRACKING
Production of alpha olefins by Thermal cracking
wax
Thermal cracking of wax is carried out in a tubular furnace at 500-
6000C for 5-15 sec.
The products are separated from primary fractionation column and
stabilization column.
Mild condition is used to maximize the yield of alpha-olefins.
Ethylene,
Propylene
Vaporizer and
Purification
Preheater Fractionator
Wax C4-C18
alpha Olefins
C20 +
Shell Higher Olefins Process
Basic info on the SHOP
Oligomerization The process of converting a monomer or a
mixture of monomers into an oligomer (consists of limitted no of
monomers)