CRACKING PROCESSES

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Cracking
• Cracking; in petroleum refining, is the process by
which heavy hydrocarbon molecules are broken up
into lighter molecules by means of heat and usually
pressure and sometimes catalyst.
• The original incentive to develop cracking processes
arose from the need to increase gasoline supplies and
to increase the octane number of gasoline.

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Cont.
• Moving down on the side streams of the distillation
column, heavy gas oil constitutes the next fraction
in line.
• Some generic conversion processes for the heavy
distillates, such as heavy gas oil (consisting of C 20 to
C25 hydrocarbons).
• These processes, aimed at reducing the molecular size
or the boiling point of gas oil compounds, and involve
thermal cracking or catalytic cracking.

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Cont.

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Cont.
• A mild thermal cracking process, called
visbreaking, is applied to reduce the viscosity
of the feedstock, and it is more frequently
applied to residual fractions, such as vacuum
distillation residue.
• A more severe thermal cracking of heavy gas oil
can be used to produce LPG and ethylene and
light and middle distillates from heavy gas oil.

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Cont.
• A highly aromatic byproduct from thermal cracking is
called ethylene tar.
• Ethylene is an important petrochemical feedstock,
while ethylene tar can be used as feedstock to
produce carbon blacks
• Catalytic cracking is more frequently used for
conversion of heavy gas oil to gasoline

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Catalytic Cracking

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Catalytic Cracking
• Catalytic cracking is basically the same as thermal
cracking, but it differs by the use of a catalyst.
• The feedstocks for catalytic cracking can be any
one (or blends) of the flowing:
– Straight gas oil
– vacuum gas oil
– atmospheric residuum and
– vacuum residuum.

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Cont.

• If blends of the above feedstocks are employed,

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Cont.
ii. demetallation, i.e., removal of nickel, vanadium,
and iron to prevent catalyst deactivation
iii. Use of a short residence time as a means of
preparing the feedstock, and
iv. Hydrotreating or mild hydrocracking to prevent
excessive coking in the fluid
catalytic cracking unit

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Cont.
• There are three basic types of catalytic crackers:
– Fluid bed
– Moving bed
– Fixed bed

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Cont.
• The fixed-bed process was the first to be used
commercially and uses a static bed of catalyst in
several reactors, which allows a continuous flow of
feedstock to be maintained.
• Thus, the cycle of operations consists of:
– flow of feedstock through the catalyst bed
– discontinuance of feedstock flow and removal of
coke from the catalyst by burning and
– insertion of the reactor on-stream.

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Cont.
• The moving-bed process uses a reaction vessel in
which cracking takes place and a kiln in which the
spent catalyst is regenerated, catalyst movement
between the vessels is provided by various
means.
• The fluid-bed process differs from the fixed-bed
and moving-bed processes insofar as the
powdered catalyst is circulated essentially as a
fluid with the feedstock.

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Cont.
• Zeolites are the most common catalyst because of:
i. Higher activity
• Ability to achieve higher conversion without over
cracking.
• Permit short residence (reaction) time (good for riser
cracking operations).
ii. Higher selectivity
• Produce higher gasoline yield for a given conversion.
• Produce gasoline containing more paraffins and aromatics.
• Produce more isobutene (higher ON).
• Lower coke yield (less catalyst fouling/deactivation) which
means higher throughput at a given conversion.
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Cont.
• The high activity of zeolite cracking catalyst allows
for shorter residence time.
• Basic nitrogen compounds, iron, nickel, vanadium,
and copper in the oil act as poisons to cracking
catalysts.
• The nitrogen reacts with the acid centers on the
catalyst and lowers it’s activity.
• The metals deposit and accumulate on the catalyst
and cause a reduction in throughput.
• By increasing coke formation and decreasing the
amount of coke burn-off per unit air.
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Cont.
• This is due to the catalysis effect of the metal where
the coke is converted to carbondioxide rather carbon
monoxide.
• It is generally accepted that nickel has four times the
effect on catalyst selectivity as vanadium
• Although nickel and vanadium deposits reduce the
catalyst activity by occupying the catalyst’s active sites.
• The major effects are the promotion of the formation
of gas and coke and reduce the gasoline yield
• Metals removal processes can be used to reactivate
the catalyst
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Cont.
• Catalytic cracking has a number of advantages over
thermal cracking:
– Gasoline produced by catalytic cracking has a higher octane
number and consists largely of iso-paraffins and aromatics.
– The iso-paraffins and aromatic produced have high octane
numbers and greater chemical stability than mono-olefins
and diolefins.
– The olefins and diolefins are present in much greater
quantities in gasoline produced by thermal cracking
processes.
– Further, substantial quantities of olefin gases and smaller
quantities of methane, ethane, and ethylene are produced
by catalytic cracking.
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Cont.
– The olefin gases are suitable for polymer gasoline
manufacture.
– Sulfur compounds are changed in such a way that the
sulfur content of gasoline produced by catalytic cracking
gasoline is lower than the sulfur content of gasoline
produced by thermal cracking.
– Catalytic cracking produces less residuum and more of the
useful gas oil constituents than thermal cracking.
– Finally, the process has considerable flexibility, permitting
the manufacture of both motor gasoline and aviation
gasoline and a variation in the gas oil production to
meet changes in the fuel oil market.
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Catalytic Reforming

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Catalytic Reforming
• Catalytic reforming is a process whereby light petroleum
distillates (naphthas) are contacted with a platinum-containing
catalyst at elevated temperatures and hydrogen pressures
ranging from 345 to 3,450 kPa (50–500 psig) for the purpose of
raising the octane number of the hydrocarbon feed stream.
• The low octane, paraffin-rich naphtha feed is converted to a
high-octane liquid product that is rich in aromatic compounds.
• Hydrogen and other light hydrocarbons are also produced as
reaction by products.

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Cont.
• In addition to the use of reformate as a blending
component of motor fuels, it is also a primary
source of aromatics used in the petrochemical
industry.
• The need to upgrade naphthas was recognized early
in the 20th century.
• Thermal processes were used first but catalytic
processes introduced in the 1940s offered better
yields and higher octanes.

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Feedstocks
• Naphtha feedstocks to reformers typically contain
paraffins, naphthenes, and aromatics with 6–12
carbon atoms.
• Most feed naphthas have to be hydrotreated to
remove metals, olefins, sulfur, and nitrogen, prior to
being fed to a reforming unit.
• A typical straight run naphtha from crude distillation
may have a boiling range of 150–400◦F (65–200◦C).

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Cont.
• In addition to naphthas from crude distillation,
naphthas can be derived from a variety of other
processes that crack heavier hydrocarbons to
hydrocarbons in the naphtha range.
• Cracked feedstocks may be derived from catalytic
cracking, hydrocracking, thermal cracking, as well as
visbreaking.
• Light paraffinic naphthas are more difficult to reform
than heavier naphthenic hydrocarbons

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Cont.
• Common poisons for reforming catalysts that are
found in naphtha are sulfur, nitrogen, and oxygen
compounds.
• Removing these requires breaking of a carbon-sulfur,
-nitrogen or -oxygen bond and formation of
hydrogen sulfide, ammonia, or water respectively.
• Hydrotreaters will also remove olefins and metal
contaminants.

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Cont.
• The reformate stream from a catalytic reforming unit is
invariably used either as a high octane gasoline blending
component or as a source of aromatics — BTX (benzene,
toluene, and xylene), and C9+ aromatics.
• Reforming for motor fuel applications requires “full range”
naphthas, i.e hydrocarbons with 6–12 carbon atoms.
• Reforming units for the production of aromatics are often
called BTX reformers.
• Naphthas for these units are specified to contain mostly
naphthenes and paraffins of 6–8 carbons.

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Reformate Properties
• For motor fuel applications, the octane number is the
dominant parameter of product quality.
• A higher octane number reflects a lower tendency of the
hydrocarbon to undergo a rapid, inefficient detonation
in an internal combustion engine.
• This rapid detonation is heard as a knocking sound in the
engine, so octane is often referred to as the antiknock
quality of a gasoline.
• In BTX production, the objective is to transform paraffins
and naphthenes into benzene, toluene, and xylenes.

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Catalyst
• The platinum must be dispersed over the alumina
surface.
• The interaction of the platinum with the alumina
surface is such that the platinum clusters are
relatively immobile and do not agglomerate during
reforming.

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Cont.
• Deactivation mechanisms for reforming catalysts
include:
– coking
– poisoning and
– agglomeration of the platinum.

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