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Feeds with higher end points (≈200°C) are favorable because some
of the long-chain molecules are hydrocracked to molecules in the
gasoline range. These molecules can isomerize and dehydrocyclize
to branched paraffins and to aromatics, respectively.
Reforming Catalysts
• Bi-functional to provide two types of catalytic
sites, hydrogenation-dehydrogenation sites
and acid sites.
• platinum, is the best known hydrogenation-
dehydrogenation catalyst
• Alumina, (acid sites) promote carbonium ion
formation
• The two types of sites are necessary for
aromatization and isomerization reactions.
• Pt/Re catalysts are very stable, active, and selective.
Reforming Catalysts
• Trimetallic catalysts of noble metal alloys are also used for the
same purpose.
• The increased stability of these catalysts allowed operation at
lower pressures.
Reforming Reactions
Aromatization
• The reaction is endothermic i.e. favoured @ higher temp and
lower pressures.
• Effect of temp on the conversion and selectivity:
Catalytic Cracking
• Catalytic cracking (Cat-cracking): To crack lower-value stocks
and produce higher-value light and middle distillates.
• To produce light hydrocarbon gases, which are important
feedstocks for petrochemicals.
• To produce more gasoline of higher octane than thermal
cracking. This is due to the effect of the catalyst, which
promotes isomerization and dehydrocyclization reactions.
• Feeds vary from gas oils to crude residues
• Polycyclic aromatics and asphaltenes peoduce coke.
Catalytic Catalysts
• 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 in the center. Each oxygen anion
with a (II) oxidation state is shared between either two silicon,
two aluminum, or an aluminum and a silicon cation.
Catalytic Catalysts
Once cyclization has occurred, the formed carbocation can lose a proton,
and a cyclohexene derivative is obtained. This reaction is aided by the
presence of an olefin in the vicinity (R–CH=CH2).
Cracking Process
• Most catalytic cracking reactors are either fluid bed or moving
bed.
• In FCC, the catalyst is an extremely porous powder with an
average particle size of 60 microns.
• Catalyst size is important, because it acts as a liquid with the
reacting hydrocarbon mixture.
• In the process, the preheated feed enters the reactor section
with hot regenerated catalyst through one or more risers
where cracking occurs. A riser is a fluidized bed where a
concurrent upward flow of the reactant gases and the catalyst
particles occurs.
• The reactor temperature is usually held at about 450–520°C,
and the pressure is approximately 10–20 psig.
• Gases leave the reactor through cyclones to remove the
powdered catalyst, and pass to a fractionator for separation of
the product streams. Catalyst regeneration occurs by
combusting carbon
• deposits to carbon dioxide and the regenerated catalyst is then
returned
Typical FCC reactor/regenerator
Isomerization
Reactions leading to skeltal rearrangements over Pt catalysts
Hydrocracking
A hydrogen-consuming reaction that leads to higher gas
production
Hydrdealkylation
A cracking reaction of an aromatic side chain in presence of
hydrogen
Deep Catalytic Cracking
• Deep catalytic cracking (DCC) is a catalytic cracking process
which selectively cracks a wide variety of feedstocks into light
olefins.
• It produces more olefines than FCC.
Hydrocracking Process
• It is a cracking process in presence of hydrogen.
• The feedstocks are not suitable for catalytic cracking because
of their high metal, sulfur, nitrogen, and asphaltene contents.
• The process can also use feeds with high aromatic content.
• Products from hydrocracking processes lack olefinic
hydrocarbons.
• The product slate ranges from light hydrocarbon gases to
gasolines to residues.
• The process could be adapted for maximizing gasoline, jet
fuel, or diesel production.
Hydrocracking Catalysts and Reactions
• Bifunctional noble metal containing zeolites are used.
• This promote carbonium ion formation.
• Catalysts with strong acidic activity promote isomerization.
• The hydrogenation-dehydrogenation is promoted by catalysts
such as cobalt, molybdenum, tungsten, vanadium, palladium,
or rare earth elements. As with
• catalytic cracking, the main reactions occur by carbonium ion
and beta scission, yielding two fragments that could be
hydrogenated on the catalyst surface.
• The first-step is formation of a carbocation over the catalyst
surface:
The carbocation rearrange, eliminate a proton to produce an
olefin, or crack at a beta position to yield an olefin and a new
carbocation.
- Products from hydrocracking units are suitable for jet fuel use.
Hydrocracking also produces light hydrocarbon gases (LPG)
suitable as petrochemical feedstocks.
Hydrocracking Process
• Mostly single stage, with the possibility of two operation
modes. Once-through and a total conversion of the
fractionator bottoms by recyling.
• In once-though operation, low sulfur fuels are produced and
the fractionator bottom is not recycled.
• In the total conversion mode the fractionator bottom is
recylced to the inlet of the reactor.
• In the two-stage operation, the feed is hydrodesulfurized in
the first reactor with partial hydrocracking. Reactor effluent
goes to a high-pressure separator to separate the hydrogen-
rich gas, which is recycled and mixed with the fresh feed. The
liquid portion from the separator is fractionated, and the
bottoms of the fractionator are sent to the second stage
reactor.
• Hydrocracking reaction conditions vary widely, depending on
the feed and the required products. Temperature and
pressure range from 400 to 480°C and 35 to 170 atmospheres.
Space velocities in the range of 0.5 to 2.0 hr-1 are applied.
hydrodenitrogenation
Alkylation Process
• To produce large hydrocarbon molecules in the gasoline fraction
from small moleucles. (branched hydrocarbons).
• Normally acid catalyzed using H2SO4 or abhydrous HF.
• The product is known as the alkylate.
Some recent research has been devoted to replace the
homogeneous acid catalysts by heterogeneous solid
catalysts employing zeolites and alumina, or zirconia.
Isomerization process
• Small volume but important refinery process.
• Acid catalyzed. To produce branched alkanes.
• Bifunctional catalysts activated by inorganic chelorides are
used.
• Pt/zeolite is a typical isomerization catalyst.