Catalytic

cracking
Catalytic cracking process was developed in 1920
by Eugene Houdry for upgradation of residue and
was commercialized later in 1930. Houdry process
was based on cyclic fixed bed configuration.

There has been continuous upgradation in catalytic

cracking process from its incept of fixed bed
technology to latter fluidized bed catalytic cracking
(FCC)

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
Main reactions involved in
catalytic cracking are
Cracking
Isomerisation
Dehydrogenenation
Hydrogen transfer
Cyclization
Condensation
Alkylation and dealkylation
Paraffins Smaller paraffins +
olefins
Alkyl naphthene naphthene + olefin
Alkyl aromatic aromatic + olefin
Multiring naphthene alkylated naphthene with
fewer rings
Different type of catalytic cracking

(1) Fixed bed, Houdry

(2) Moving beds-Air lift-Thermofer catalytic cracking
houdry flow.
(3) Fluidized Beds
(a)Gulf Resrearch(Fluid catalytic cracking )
(b)Kellog (Ortho flow)
(c)ESSO-Flexi cracking
(d)Standard Ultra cracking.
FLUID CATALYTIC CRACKING
Fluid catalytic cracking is now major secondary
conversion process in Petroleum refinery since
1942. There are more than 400 FCC units in world.
The process provides around 50 percent of all
transportation fuel and 35 percent of total gasoline
pool.

Product Obtained
Light gas -H2, C1, and C2s
LPG C3s and C4s includes light olefins
Gasoline C5+ high octane component for gasoline
Light cycle oil (LCO) blend component for diesel
Heavy cycle oil (HCO) Optional heavy cycle oil product
for fuel
Clarified oil (CLO) or decant oil: slurry for fuel oil
Coke by-product
FCC Catalysts

Major breakthrough in the catalytic cracking process was

development of zeolite catalysts which demonstrated
vastly superior activity, gasoline selectivity, and stability
characteristics compared to original amorphous silica
alumina catalyst.
Acid-treated clays were the first catalysts used.
Replaced by synthetic amorphous silica-alumina,
which is more active and stable.
Incorporating zeolites (crystalline alumina-silica) with the
silica/alumina catalyst improves selectivity towards
aromatics. These catalysts have both Lewis and Bronsted
acid sites that promote carbonium ion formation. An
important structural feature of zeolites is the presence of
holes in the crystal lattice, which are formed by the silica-
alumina tetrahedra. Each tetrahedron is made of four
oxygen anions with either an aluminum or a silicon cation
Catalytic Catalysts
 Zeolite Catalysts
Highly selective due to its smaller pores, which allow
diffusion of only smaller molecules through their pores,
and to the higher rate of hydrogen transfer reactions.
However, the silica-alumina matrix has the ability to
crack larger molecules.
Deactivation of zeolite catalysts occurs due to coke
formation and poisoning by heavy metals.
Deactivation may be reversible or irreversible.
Reversible deactivation occurs due to coke deposition.
This is reversed by burning coke in the regenerator.
Irreversible deactivation results as a combination of four
separate but interrelated mechanisms: zeolite
dealumination,
zeolite decomposition, matrix surface collapse, and
contamination by metals such as vanadium and sodium.
FEED STOCK

Vacuum gas oil (VGO), Hydro-treated VGO, Hydro-

cracker bottom, Coker gas oil (CGO), Deasphalted
oil (DAO), Vacuum residue (VR)

PROCESS STEPS

Three basic functions in the catalytic cracking

process are:
Reaction - Feedstock reacts with catalyst and
cracks into different hydrocarbons;
Regeneration - Catalyst is reactivated by burning
off coke; and recerculated to reactor
Fractionation - Cracked hydrocarbon stream is
separated into various products like LPG and
gasoline, like light cycle oil and heavy cycle oil are
FCC process
Oil is cracked in the presence of a finely divided catalyst, which is
maintained in an aerated or fluidized state by the oil vapours.
The fluid cracker consists of a catalyst section and a fractionating
section that operate together as an integrated processing unit.
The catalyst section contains the reactor and regenerator, which, with
the standpipe and riser, form the catalyst circulation unit. The fluid
catalyst is continuously circulated between the reactor and the
regenerator using air, oil vapors, and steam as the conveying media.
Preheated feed is mixed with hot, regenerated catalyst in the riser
and combined with a recycle stream, vapourized, and raised to
reactor temperature (485-540C) by the hot catalyst.
As the mixture travels up the riser, the charge is cracked at 0.7-2 bar.
Cracked product is then charged to a fractionating column where it is
separated
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.
CATALYST DEACTIVATION

Catalyst deactivation may occur due to coke deposition and

metal accumulation.
Coke Depositions may be due to condensation of poly-
nuclear and olefinic compounds into high molecular weight
which cover active sites. Metal Accumulation occurs at the
pore entrances or near the outer surface of the catalyst

CATALYST REGENERATION

Catalyst regeneration is done by burning off the carbon, and

sulphur and circulation of circulate nitrogen with the
recycle compressor, injecting a small quantity of air and
maintaining catalyst temperature above the coke ignition
temperature.
Fluidized catalytic cracking
Orthoflow catalytic
cracking
MODIFIED CATALYTIC CRACKING PROCESSES

Resid FCC (RFCC)

Process
Deep Catalytic Cracking
(DCC)
Petro FCC Process
HYDROCRACKING
HYDROCRACKING
Hydrocracking is one of the most versatile
processes for the conversion of low quality feed
stocks into high quality products like gasoline,
naphtha, kerosene, diesel, and hydrowax which
can be used as petrochemical feed stock. Its
importance is growing more as a refiners search for
low investment option for producing clean fuel.

feed stocks : naphtha, atmospheric gas oil,

vacuum gas oils, coke oils, catalytically cracked
light and heavy oil, cracked residue, deasphalted
oils

Product : Liquefied petroleum gas (LPG),

Motor gasoline,
Reformer feeds, Aviation turbine fuel, Diesel fuels,
Hydrocracking process is a catalytic cracking process which
takes place in the presence of an elevated partial pressure
of hydrogen and is facilitated by bi-functional catalyst having
acidic sites and metallic sites. During hydrocracking process
hydrotreating reactions and hydrocracking reactions are two
major reactions which take place.
C22 H46 + H2 C16H34 + C6H14

Various hydrotreating reactions are :

hydrodesulphurization, denitrogenation,hydrodeoxygenation,
hydro metallization, olefin hydrogenation, partial aromatics
saturation.
Various hydrocracking reactions are :
splitting of C-C bond , C-C rearrangement reaction
(hydroisomerisation process) Hydrogenation and
dehydrogenation.
Hydrocracking Catalyst

Hydrocracking catalyst is a bi-functional catalyst and

has a cracking function and hydrogenation
dehydrogenation function. The former is provided by an
acidic support whereas the latter is imparted by metals.
Acid sites (Crystalline zeolite, amorphous silica
alumina, mixture of crystalline zeolite and amorphous
oxides) provide cracking activity. Metals [Noble metal
(Pd, Pt) or non noble metal sulphides (Mo, Co, Ni)
provide hydrogenation dehydrogenation activity. These
metals catalyze the hydrogenation of feedstocks
making them more reactive for cracking and hetero-
atom removal as well reducing the coke rate.
Zeolite based hydrocracking catalysts have
advantages of
greater acidity resulting in greater cracking activity;
better thermal/hydrothermal stability;
Various operating parameters affecting hydrocracking
are
Reaction temperature
Hydrogen partial pressure
Hourly feed velocity of the feed
Hydrogen recycle ratio
Once though Hydrocracking
Process
The unit consists of the following
sections:
Furnace
First stage Reactor section
Second stage Reactor section
High pressure separator
Fractionation Section
Light Ends Recovery section
hydrocracking