Thermal and Catalytic cracking

Coking and thermal process, delayed coking,

Catalytic cracking, cracking reactions, cracking
feedstock, Effect of process, FCC cracking,
catalyst ,New designs for fluidized bed catalytic
cracking
• Two major factors that have increased the need
for cracking are the depletion of old, light crudes
and the increasing demand for gasoline.

• The principal purpose of a cracking unit is to

break high molecular weight hydrocarbons into
smaller pieces of lower boiling point fractions,
especially gasoline.
 Cracking
• It is a endothermic process , so external heat is required. Main
parameters affecting cracking: Pressure Temperature and time of
cracking.
• Pressure has no direct effect on velocity of the reaction. If more
gases to be produced then low pressures are desirable. With
higher pressures gas to gasoline ratio becomes less.
• Reaction velocity is directly dependent upon temperature .
• Dissociation of high molecular weight hydrocarbon into a smaller
fragments through agency of heat alone is termed as thermal
cracking or pyrolysis.
• Can also be done in presence of catalyst.
•   CnH2n+2Cn/2Hn+2 + Cn/2Hn (T= 400o C)
C12C6 + C6
C6C4 + C2 /C3 + C3  
• Cracking
• temperature (degree C) Nature of operation Products

• 425-460 Visbreaking Fuel oil

• 460-520 Thermal cracking Gas, gasoline, Tar oils

circulating oils
• 520-600 Low temperature coking Gas, asoline , soft
coke
• 800-1000 High temperature Gas , heavy aromatics

• Above 1000 decomposition H 2, gas, carbon black

• Thermal cracking
  Properties of cracked materials   Product properties
are extensively dependent on the conditions of
racking.
properties changes during cracking :
a) Characterization factor (decreases due to high
aromatic content)
b)Boiling point , viscosity, pour point decreases.
C)Unsaturation and Aromatization increases.
d)Octane number of gasoline increases.
e) Sulphur content in the cracked product increases
as the rule although the maximum amount in
heavier portion only.
 Theory of cracking
• Thermal cracking proceeds via free radical mechanism
• Free radicals : atom or group of atom with bare unpaired electron.  
• RCH2CH3  →  RCH2O + CH3O  
• Unpaired electrons are very active and try to form stable compound
by acquiring unpaired electrons from sources available.
HC (charged) ions are usually referred as carbonium ions.
• Paraffins =  rate of reaction increases with increase in carbon number.
• olefins = cracks much faster compared to paraffins.
• Large molecules made into smaller Fragments with double bond
Hydrogen demand net through creation of double bond by means of
• Hydrogen Transfer
• Cyclization
• Aromatization
• Initiation
• A single molecule breaks apart into two free
radicals.
• Only a small fraction of the feed molecules actually
undergo initiation
• But these reactions are necessary to produce the
free radicals that drive the rest of the reactions.
• In steam cracking, initiation usually involves
breaking a chemical bond between two carbon
atoms, rather than the bond between a carbon and
a hydrogen atom.
• CH3CH3 → 2 CH3•
• Hydrogen abstraction
• In these reactions a free radical removes a hydrogen
atom from another molecule, turning the second
molecule into a free radical.
• CH3• + CH3CH3 → CH4 + CH3CH2•
• Radical decomposition
• In these reactions a free radical breaks apart into
two molecules, one an alkene, the other a free
radical. This is the process that results in alkene
products.
• CH3CH2• → CH2=CH2 + H•
• Radical addition
• In these reactions, the reverse of radical decomposition
reactions, a radical reacts with an alkene to form a single, larger
free radical. These processes are involved in forming the
aromatic products that result when heavier feedstocks are used.
• CH3CH2• + CH2=CH2 → CH3CH2CH2CH2•
• Termination
• In these reactions two free radicals react with each other to
produce products that are not free radicals. Two common forms
of termination are recombination, where the two radicals
combine to form one larger molecule, and disproportionation,
where one radical transfers a hydrogen atom to the other, giving
an alkene and an alkane.
• CH3• + CH3CH2• → CH3CH2CH3 CH3CH2• + CH3CH2• → CH2=CH2 +
CH3CH3
•  Effect of pressure on cracking:  
• Pressure retards cracking reactions.
• But in practice a positive pressure of 10 to 15
Kg/cm2 is used to minimize coke formation.
• Recycling increases refractory nature of stocks and
hence recycling should not exceed 2 to 3 times of
fresh stock for economic operation.
 COKING
• Coking - severe form of thermal cracking
• Converts the heaviest low value residue - valuable distillates
and petroleum coke.
• Recycle is used to further convert heavy distillate fractions to
lighter products .
• Mechanism of coke formation:
• Distortion of colloidal suspension of the asphaltenes and resin
compounds - resulting in precipitation of highly cross linked
structure of amorphous coke.
• The compounds are also subjected to cleavage of the
aliphatic groups.
• Polymerisation and condensation of the free aromatic
radicals, grouping a large number of these compounds to such
a degree that dense high grade coke is eventually formed
• Various types of coking processes are
• delayed coking, fluid coking and flexi coking.
• Delayed coking process - Crack heavy oils into more valuable
light liquid products with less valuable gas and solid coke as
byproducts
• Thermal cracking of heavy residue in empty drum where
deposition of coke takes place.
• The product yield and quality depends on the typed feedstock
processed.
• A furnace to preheat the feed, coking drum - fractionation of the
product.
• The feed - preheated in furnace where the desired cooking
temperature is achieved
• Fed to the coking drums installed in pairs where the cracking
reaction takes place and the coke is deposited in the bottom of
the reactor.
• The coke drums overhead vapour flows to the fractionating
column where they are separated into overhead streams
containing wet gas LPG and naphtha
• Recycled stream from the fractionating column combines
with the fresh feed in the bottom of the column and is
further preheated incoke heaters and flows to the coke
drums.
• When a coke drum is filled, the heated streams from the
coke heated are sent to the other drum.
• Reaction -partial vaporization and partial cracking, cracking
of two vapour phase in the coke drum and successive
cracking used polymerization of liquid Phase resulting in
formation of coke in the drum.
• Feed: Vacuum residue, FCC residual, or cracked residue.
Studies show that feedstock quality
• severity on conversion impact the stability of visbreaker
residue
• Product: Gases, Naphtha, Fuel oil, Gas oil and Coke
• Low feed stock characterization factor and high carbon
residue increase coke yield and quality of gas oil end
point.
• Operating Variables
• Feed stocks variables:
• Characterization factor, degree of reduction, carbon,
sulphur content, Metallic constituents. Low feed stock
characterization factor and high carbon residue increase
coke yield and quality of gas oil end point
• Engineering Variables :Batch, Semi continuous or continuous ,
Capacity and size factors, Coke removal equipment, Coke
handling, Storage and Transportation
• Operating Variables: temperature, pressure, recycle ratio,
transfer temperature, and coke chamber pressure.
• Higher temperature: Results in more vaporization of the inlet
material causing low coke yield. A furnace outlet temperature
of 485-505 degree C is maintained. High temperature results in
hard coke while coke is soften when too low temperature is
maintained.
• Higher pressure: Results in an increase in coke and gas yields
which is undesirable as basic objective is to improve the yield of
distillation with less coke.
• Higher recycle ratio: Results in higher coke and gas yields.
Lower recycle ratio is always desirable for higher yield of liquid
product
Delayed Coking
• Fluid Coking: where residue is coked by spraying into a
fluidized bed of hot, fine coke particles.
• Higher temperature with shorter contact time than delayed
coking results in increased light and medium hydrocarbons
with less cake generation.
• Shorter residence time can yield higher quantities of liquid
less coke, but the product have lower value.
• Flexi Coking: It is continuous process involves thermal
cracking in a bed fluidized coke and gasification of the coke
produced at 870 degree C.
• This process contains an additional step of gasification
• The gases leaving the gasifier is low calorific value fuel gas at
800-1500 kcal/m3 (4200 to 5000 kJ/std m3 ) and is burned
in the furnace or power plants. It can be applied to wide
variety of feed stocks.
 Visbreaking

• Reduction in viscosity is Visbreaking.

• Materials like residuum are not of direct utility or
stocks decided with difficulties due to high pour
point , from palpable feed stock for this operation.
• Liquid products may be used as cycle stocks for
crackers commercially valuable main products know
as fuel oil.
• Light fraction gas and gasoline.
• Cracking temperature and residence time Soaker
type (more gas) or coil type visbreaker(more
gasoline due to for short residence time)
• High temperature soaker visbreaking
• Soaker drum : Large vessel designed to allow for a
long residence time for the feedstock.
Cracking in the furnace is minimized by using high
liquid velocity and steam injection.
With increase in T and cracking time : light fraction
increase => fuel oil yield decrease.  
• High conversion soaker visbreaking  
• Gives higher conversion and more stable residue
compare to conventional soaker visbreaking.
• Feed stocks : Heavy crude oil, oil shale, long and
short residue, visbroken residue.
 Operating conditions and products
• Increase in cracking time and temperature increases the lighter
fraction and decreases the fuel oil yield.
• Pressure has negligible effect on velocity of reaction. At high pr.
gas / gasoline ratio is less.
• Pressure retards cracking reactions
• Feed stock: Asphalt, Short residuum to residuum, and medium
oil  
• Steps:  
1)Preheating of feed upto 250oC
2)Heating in furnace up to 470o C.
3)Pressure 10-15 kg/cm2 necessary to avoid coke formation.
Steam admission in to feed stocks also checks coke formation.
4) Fraction (Light and heavy) from quencher goes to distillation
column.  
 Catalytic cracking

• Improved yield distribution

• Higher yield and quality of gasoline
superior product properties
• Single reactor
• More control over the products by breaking large
hydrocarbons more towards the middle minimizing the yield
of light hydrocarbons and maximizing the yield of gasoline.
• Feed stock for catalytic cracking - light gas oil from vacuum
distillation column.
• Catalytic cracking cracks low value high molecular weight
hydrocarbons to more value added products (low molecular
weight) like gasoline, LPG Diesel along with very important
petrochemical feedstock like propylene, C4 gases like
isobutylene, Isobutane, butane and butane.
 Main reactions involved in catalytic cracking are
• Cracking

• Isomerization

• Dehydrogenenation

• Hydrogen transfer

• Cyclization

• Condensation

• Alkylation and dealkylation

• Major primary reactions taking place in catalytic
cracking
• Paraffins Smaller paraffins + olefins
• Alkyl naphthene naphthene + olefin
• Alkyl aromatic aromatic + olefin
• Multiring naphthene alkylated naphthene with
fewer rings
 FLUID CATALYTIC CRACKING

• Introduction of zeolite catalyst during 1960 which

has resulted in lower residence time
• Introduction of ultra stab le Y-zeolite in mid 60’s
• Switch over from bed cracking to riser cracking
• Introduction of large number of additives for
boosting of gasoline octane/yield of light naphtha
• SOx control
• Nickel and vanadium passivation
• FCC is a multi-component catalyst system with circulating fluid
bed reactor system with reactor regenerator system configuration
• FEED STOCK
• Vacuum gas oil (VGO), Hydro-treated VGO, Hydro-cracker bottom,
Coker gas oil (CGO), De-asphalted oil (DAO), Reduced crude oil
(RCO), Vacuum residue (VR)

• Typical feedstock consists of Vacuum and Atmosphere gas oil but

may include other heavy stream.

• Major contaminant in the feed includes carbon residue and

metals.

• While FCC process feed containing up to 4% Conradson carbon.

Process Steps
• Three basic functions in the catalytic cracking process
• 1)Reaction
• - Feedstock reacts with catalyst and cracks into
different hydrocarbons;
• 2)Regeneration
• - Catalyst is reactivated by burning off coke; and re
circulated to reactor
• 3)Fractionation
• Cracked hydrocarbon stream is separated into various
products like LPG and gasoline, like light cycle oil and
heavy cycle oil are withdrawn as side stream
• Reactor and Regenerator Section:
• Catalyst section = reactor and regenerator

• The feed to unit along with recycle streams is preheated to temperature of

365 degree C-370 degree C and enters the riser where it comes in cont act
with hot regenerated catalyst ( at a temperature of about 640-660 degree C.
Finely divided catalyst is maintained in an aerated or fluidized state by the oil
vapors.

• The catalyst section contains the reactor and regenerator & catalyst re
circulates between the two.

• Spent catalyst is regenerated to get rid of coke that collects on the catalyst
during the process.
• Spent catalyst flows through the catalyst stripper to the regenerator, where
most of the coke deposits burn off at the bottom where preheated air and
spent catalyst are mixed.
• Fresh catalyst is added and worn-out catalyst removed to optimize the cracking
process
 Fractionation -

• Cracked hydrocarbon stream is separated into various

products. LPG and gasoline are removed overhead as
vapor. Unconverted product like light cycle oil and heavy
cycle oil are withdrawn as side stream. Overhead product
is sent to stabilization section where stabilized gasoline is
separated from light products from which LPG is
recovered.

• Typical operating parameter of FCC

• Raw oil feed at heater inlet : 114 cubic meter /h
• Furnace outlet temperature : 291degree C
• Reactor feed temperature : 371degree C
• Reactor Vapour temperature : 549degree C
• Product Obtained

• Light gas –H2, C1, and C2s

• LPG C3sand C4s– includes light olefins

• Gasoline C5
• + high octane component for gasoline pool or light fuel

• Light cycle oil (LCO) blend component for diesel pool or light fuel

• Heavy cycle oil (HCO) Optional heavy cycle oil product for fuel oil or cutter stock

• Clarified oil (CLO) or decant oil: slurry for fuel oil

• Coke by-product consumed in the regenerator to provide the reactor heat

demand
 FCC Catalysts
• zeolite catalysts - vastly superior activity, gasoline
selectivity, and stability characteristics compared to original
amorphous silica alumina catalyst
• Today’s FCC catalysts Porous spray dried micro-spherical
powder Particle size distribution of 20 -120 micron &
particle density ~ 1400 kg/m3
• Comprising Y zeolite in many derivatives of varying
properties
• Supplied under various grades of particle sizes & attrition
resistance
• Continuing improvement metal tolerance, coke selectivity
• New catalyst - high metal tolerance with high matrix
catalyst , better accessibility, regenerability and
strippability
 MODIFIED CATALYTIC CRACKING PROCESSES
• Resid FCC (RFCC) Process:
• The RFCC process uses similar reactor technology as the FCC
process and is targeted for residual feeds greater than 4 wt-%
Conradson carbon.
• A two stage regenerator with catalyst cooling is used to control
the higher coke production and resulting heat.
• Deep Catalytic Cracking (DCC):
• Milli Second Catalytic cracking (MSCC) Process:
• Improvements in riser termination devices have led to
significant decreases in post-riser residence time and post-riser
cracking. The benefits of shorter catalyst-and oil contact time
have been lower dry gas yields, lower delta coke on catalyst and
more selective cracking to gasoline and light olefins.
• Due to improvement in reactor design there is lower
regenerator temperature and higher catalyst recovery.
• Petro FCC Process
• The Petro FCC process - production of
petrochemical feedstock rather than fuel products.
This new process, which utilizes a uniquely designed
FCC unit, can produce very high yields of light
olefins and aromatics when coupled with aromatics
complex.
• The catalyst section of the Petro FCC process uses a
high-conversion, short-contact time reaction zone
that operates at elevated reactor riser outlet
temperatures
 Indmax Technology
• Residue to Olefin was developed by IOC R&D center and has been
successfully commissioned in IOC. Special features of the technology
are:

• Very high cat/oil ratio(15-25)

• Higher riser temperature (>5500C)
• Higher riser steam rate
• Relatively lower regeneration temperature.

• Benefits
• LPG 35-65 wt%
• Propylene 17-25 wt% feed
• High octane gasoline (95+)
• Multifunctional proprietary catalyst
• Higher propylene selectivity
• Superior metal tolerance
• Lower coke mate