Thermal Cracking of Naphtha

NAPHTHA STEAM
CRACKING
ETHYLENE
MANUFACTURING
PREPARED BY
SAMARJIT CHOWDHURY
CONTENTS
 INTRODUCTION
 STEAM CRACKING MAJOR REACTIONS
 PROCESS BLOCK FLOW DIAGRAM
 FURNACE SECTION
 COMPRESSION SECTION
 SEPERATION SECTION
INTRODUCTION
 Cracker is called the mother plant of Petrochemicals. It is a very complex and
large unit almost covers all kind of unit operations except few.
 The unit is sometimes called Steam Cracker. Both Liquid and gas feed can be
cracked in this unit. Naphtha , Ethane , Propane , Diesel , Kerosene, Unconverted
Oil from Refinery etc etc can be the feed for cracking.
 The basic purpose of steam cracking of these feeds are to produce olefins –
mainly Ethylene and Propylene. H2 , C4 mix and C5 olefins are also produced as
by product of the process.
 The major technology Licensors for Steam Cracker are : Lummus , Technip, KBR
and Linde.
STEAM CRACKING MAJOR
REACTIONS
 Paraffin Decomposition by free radical chain reactions
Rxo + RnH RH+ Rno
Rno CmH2m + Rn’o
Rn’o Cm’H2m’ + Cm’’H2m’’ + Cm’’’H2m’’’ + ……….+ Ro
In general at the conditions of temperature and partial pressure normally used for
ethylene production. Free radicals continue to decompose in the above manner
into olefin molecules until the remaining radical Ro is either a hydrogen atom , a
methyl radical or an ethyl radical.
REACTIONS
Free Radical
Generation Propagation Termination
(Scission) (Hydrogen Abstraction) (Coupling)

(Disproportionation) (Decomposition & Addition)
REACTIONS
 β radicals (small radicals; primarily in bimolecular reactions, e.g. H,

CH3)
 μ radicals (large radicals; primarily in unimolecular reactions, e.g. n-

C4H9)
 Bi-radicals (e.g. CH2-CH2)

YIELD FROM DIFFERENT FEEDSTOCKS
ETHYLENE
PROPYLENE
FEED
STEAM CRACKER
GAS:ETHANE /PROPANE/ROG
LIQUID :NAPHTHA /LPG/GAS OIL
HYDROGEN
FUEL GAS
MIXED C4s
PY-GASOLINE
NOTE: BASED ON FEED STOCK, CRACKING SEVERITY AND
STEAM CRACKER CONFIGURATION, PRODUCT YIELD AND FUEL OIL
SELECTIVITY VARIES
CBFS
100
80 FUEL GAS
/FUEL OIL
GASOLINE
60 BTX
I-BUTENES/
1 BUTENE
40 BUTADIANE
PROPYLENE
20 ETHYLENE
ETHANE PROPANE BUTANE NAPHTHA HCR VGO

COMPARISON BETWEEN SPECIFIC
ENERGY & UTILITY REQUIREMENT
AREA &UTILITY REQUIREMENT FOR
COMPARISON OF SP. ENERGY
CONSUMPTION FOR DIFF. FEED 1200 KTA STEAM CRACKER
STOCKS ETHANE MIXED LIQUID
CRACKER FEED CRACKER
FEED STOCK SP. ENERGY
CRACKER
CONSUMPTION
(Kcal/Kg Ethylene) AREA 20 25-30 25-30
(acres)
ETHANE 3100 POWER 8 20-25
(import in
PROPANE 4100 MW)
CW 24000 85000
(m3/hr)
ETHANE/PROPANE 3600
MIX Steam 0 100 (HP
(import in level)
NAPHTHA 5000 ton/hr)
FG (import 3.5 (NG) 0
in tons/hr)
BRIEF DESCRIPTION OF STEAM CRACKER
FURNACE
FURNACE
FURNACE SECTION
FURNACE SECTION
 Furnace section is the main energy consuming section of Steam cracker Unit.
 Normally two type of heaters are considered in this section – as
A) Naphtha/Heavier Feed Heater : Coil Configuration is different for Lighter Feed
heater. Normally feed molecules have lesser residence time inside the coil
(approx. 240-300 millisecond ). Number of passes are less (2 pass normally)
B) Ethane/Propane/ Recycle Heater : Coil Configuration is different for heavier
Feed heater. Normally feed molecules have higher residence time inside the
coil (approx. 900 millisecond ). Number of passes are high (6-10 pass normally)
FURNACE SECTION
FURNACE SECTION
 Steam to oil ration is very important factor for ethylene production.

Increased steam partial pressure promotes the forward reaction for
ethylene production, whereas lower steam to oil ratio demotes the
forward reaction for ethylene production.
 Transfer Line exchanger is designed to produce steam and kill the
cracking reaction as soon as possible. Transfer line exchangers are
very special kind of counter current exchanger to rapidly cool the
cracked gas.
 Gasoline Fractionator is designed to separate the heavier oil from
the cracked gas. For the Gas cracker GF is not required as there is
no heavy component is the cracked gas.
FURNACE SECTION
 Furnaces are controlled fired by four type of Burners.
a) Primary Burner : At furnace floor
b) Secondary Burner : At furnace floor
c) Pilot Burner : At furnace floor
d) Wall burner : At furnace wall. Provides 10% of total heat duty
 Fire box pressure is maintained as negative draft with overhead induced draft
fan (fixed / Variable speed) and overhead damper opening . Air enters from the
bottom as required (10% more than the stoichiometric requirement) with the help
of negative draft maintained inside the firebox.
FURNACE SECTION
 Temperature inside the firebox is kept nearly 1125 C , whereas the

main controlling parameter Coil Outlet Temperature (COT) is
maintained from 810 C- 840 C as per the feed composition and
steam to oil ratio.
 Once the tube metal temperature reaches 1125 C , furnace is taken
out of the operation and prepared for Decoking to remove the
coke from inner surface of the radiant coils. Normally for heavier
feed, the run length is approx. 60 days and for ethane feed it is
approx. 45 days.
 Decoking procedure takes almost 32 hours to controllably burn out
the coke with steam and air. Air is increased slowly and steam is
decreased slowly to avoid any abrupt rise in temperature.
COMPRESSOR SECTION
COMPRESSOR SECTION
 Compressor section is basically consists of Charge Gas Compressor and Caustic
tower.
 Once the Cracked gas quenched up to approximately 38-40 C ( to strip off oil,
gasoline and oily water from it) , the gas enters the suction of Charge Gas
Compressor.
 Charge gas compressor is a five stage or three stage compressor based upon
the Chilling Train pressure requirement for separation.
 Caustic Tower is placed inter-stage of Charge Gas Compressor to get rid of acid
gas from charge gas. Normally at more than 10 kg/cm2g pressure is favourable
for Caustic solution to absorb acid gas e.g. CO2.
 Charge gas compressor has inter-stage coolers to cool down the heat of
compression.
COMPRESSOR SECTION
 Charge Gas Compressor can be motor driven or Steam turbine

driven.
 Refrigeration compressor also there in this section. Refrigeration
predominantly requires in Separation section to chill down the
charge gas.
 Basically three types of refrigeration compressions are found in the
steam cracker units :
a) Propylene Refrigeration – provides temperature up to -42 C
b) Ethylene Refrigeration – provides temperature up to – 98 C
c) Methane Refrigeration – provides temperature up to -132 C
Now Binary or Tertiary refrigeration are being used in order to reduce
CAPEX and maintenance cost ; but it also reduces the reliability.
SEPARATION SECTION
SEPARATION SECTION
 Compressed Charge Gas dried up to less than 1 ppm level of moisture before
entering in to separation section of steam cracker unit.
 Chilling train is a series of Plate and Fin Exchangers which provide very high
surface area. This exchangers are very delicate exchangers and can not
withstand very high pressure drop across it. These exchangers are made of
brazed aluminium and therefore often written as BAHX.
 Refrigerant streams cools down the charge gas stream along the series of BAHX
up to – 132 C . Further chilling is done up to -172 C (approx.) by adiabatic
flashing of high pressure streams to low pressure by Joule Thompson Effect.
SEPARATION SECTION
 As the temperature goes down, heavier components starts to

condense and collected into Demethanizer feed drums
sequentially.
 At the last the liquid composition becomes mostly methane (liquid)
and send as top most feed for Demethanizer. From this vessel
methane and hydrogen gets separated.
 In the similar fashion, the separation section strips of each
components based on their boiling point difference.
SEPARATION SECTION
 Demethanizer – separates the methane (C1) from Cracked gas.

 Deethanizer – Separates the C2 (Ethylene and Ethane and Acetylene)
 Depropanizer – Separates C3 ( Propylene, Propane and MAPD)
 Debutanizer – Separates C4 (Butane/Butylene/Butadiene etc as C4mix)
 Depentanizer – Separates C5
Ethylene and Propylene is further separated from the C2 mix and C3 mix subsequently.
SEPARATION SECTION
 Ethylene , Ethane and Acetylene mix. Is separated. Firstly the acetylene is
converted to ethylene by acetylene hydrogenation in Acetylene Converter
reactor section. Different technology licensors use different positioning of the
Acetylene Converter. Based up on the positioning of acetylene converter in the
process flow diagram it is called ‘Front end Acetylene Converter’ ( before
Chilling train) or ‘Tail end Acetylene Converter’.
 Too high temperature must be avoided in order to avoid ethylene loss in the
reactor, so that Ethylene Gain of the reactor are kept high. Too high temperature
and too high H2 ( more than stoichiometric) may convert desired ethylene to
undesired ethane.
 Once the C2 mix is acetylene free it is sent to Ethylene Fractionator to separate
Ethylene and Ethane.
 Ethylene is taken out as product and normally Ethane is recycled back to Ethane
Furnace ( which is called Recycle Heater).
SEPARATION SECTION
 Propylene, Propane and MAPD mix. Is separated. Firstly the MAPD is converted to
propylene by MAPD hydrogenation in MAPD Converter reactor section. Different
technology licensors use different positioning of the MAPD Converter. Based up
on the positioning of MAPD converter in the process flow diagram it is called
‘Front end MAPD Converter’ ( before Chilling train) or ‘Tail end MAPD Converter’.
Now a days catalyst are available for Frontend Configuration to convert
Acetylene and MAPD both in same reactor.
 Too high temperature must be avoided in order to avoid Propylene loss in the
reactor, so that Propylene Gain of the reactor are kept high. Too high
temperature and too high H2 ( more than stoichiometric) may convert desired
Propylene to undesired propane.
 Once the C3 mix is MAPD free it is sent to Propylene Fractionator to separate
Propylene and Propane.
 Propylene is taken out as product and normally Propane is recycled back to
Ethane Furnace ( which is called Recycle Heater).
THANK
YOU ALL
LET’S TAKE A MOMENT TO THANK ALL DOCTORS ,
NURSES AND HEALTHCARE STUFFS WHO ARE
FIGHTING CORONA VIRUS ON THE FRONTLINES

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NAPHTHA STEAM

Rno CmH2m + Rn’o

Rn’o Cm’H2m’ + Cm’’H2m’’ + Cm’’’H2m’’’ + ……….+ Ro

(Scission) (Hydrogen Abstraction) (Coupling)

 β radicals (small radicals; primarily in bimolecular reactions, e.g. H,

 μ radicals (large radicals; primarily in unimolecular reactions, e.g. n-

 Bi-radicals (e.g. CH2-CH2)

ETHANE PROPANE BUTANE NAPHTHA HCR VGO

 Steam to oil ration is very important factor for ethylene production.

 Temperature inside the firebox is kept nearly 1125 C , whereas the

 Charge Gas Compressor can be motor driven or Steam turbine

 As the temperature goes down, heavier components starts to

 Demethanizer – separates the methane (C1) from Cracked gas.

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