Flow diagram of a delayed coking unit:5 (1) coker fractionator, (2)

coker heater, (3) coke drum, (4) vapor recovery column.

Fluid Coking
Heated by the produced coke
Cracking reactions occur inside the heater and the
fluidized-bed reactor.
The fluid coke is partially formed in the heater.
Hot coke slurry from the heater is recycled to the
fluid reactor to provide the heat required for the
cracking reactions.
Fluid coke is formed by spraying the hot feed on the
already-formed coke particles. Reactor temperature
is about 520C, and the conversion into coke is
immediate, with complete disorientation of the
crystallites of product coke.
The burning process in fluid coking tends to
concentrate the metals, but it does not reduce the
sulfur content of the coke.

 Characteristics of fluid coke:

high sulfur content,
low volatility, poor crystalline structure, and
low grindability index.

Flexicoking, integrates fluid coking with

coke gasification.
Most of the coke is gasified. Flexicoking
gasification produces a substantial
concentration of the metals in the coke
product.

Flow diagram of an Exxon flexicoking unit:5 (1) reactor, (2)

scrubber, (3) heater, (4) gasifier, (5) coke fines removal, (6)
H2S removal.

CATALYTIC CONVERSION
PROCESSES
Catalytic Reforming
To improve the octane number of a naphtha.
Aromatics and branched paraffins have high octane
ratings than paraffins and cycloparaffins.
Many reactions: e.g. dehydrogenation of naphthenes
and the dehydrocyclization of paraffins to aromatics.

Catalytic reforming is the key process for obtaining

benzene, toluene, and xylenes (BTX).

These aromatics are important intermediates for the

production of many chemicals.

Reformer Feeds
heavy naphtha fraction produced from atmospheric
distillation units.
Naphtha from other sources such as those produced from
cracking and delayed coking may also be used.
Before using naphtha as feed for a catalytic reforming
unit, it must be hydrotreated to saturate the olefins and
to hydrodesulfurize and hydrodenitrogenate sulfur and
nitrogen compounds.
Olefinic compounds are undesirable because they are
precursors for coke, which deactivates the catalyst.
Sulfur and nitrogen compounds poison the reforming
catalyst.
The reducing atmosphere in catalytic reforming promotes
forming of hydrogen sulfide and ammonia. Ammonia
reduces the acid sites of the catalyst, while platinum
becomes sulfided with H2S.

Important is :
Types of hydrocarbons in the feed.
Naphthene content
The boiling range of the feeds
Feeds with higher end points (200C) 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, hydrogenationdehydrogenation 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.

Reforming Catalysts

Pt/Re catalysts are very stable, active, and selective.

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 lowervalue 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

Bronsted acid sites in HY-zeolites mainly originate from protons

that neutralize the alumina tetrahedra. When HY-zeolite (X- and
Y-zeolites are cracking catalysts ) is heated to temperatures in
the range of 400500C, Lewis acid sites are formed.

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 to 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.

Cracking Reactions
A major difference between thermal and catalytic
cracking is that reactions through catalytic cracking
occur via carbocation intermediate, compared to the
free radical intermediate in thermal cracking.
Carbocations are longer lived and accordingly more
selective than free radicals.
Acid catalysts such as amorphous silica-alumina and
crystalline zeolites promote the formation of
carbocations. The following illustrates the different
ways by which carbocations may be generated in the
reactor:

Aromatization Reactions
Dehydrocyclization reaction. Olefinic compounds
formed by the beta scission can form a carbocation
intermediate with the configuration conducive to
cyclization.

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 (RCH=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

450520C, 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 are saturated. i.e.

gasolines from hydrocracking units have lower
octane ratings. They have a lower aromatic content
due to high hydrogenation activity.
-Products from hydrocracking units are suitable for
jet fuel use.
Hydrocracking also produces light hydrocarbon

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 highpressure 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 480C and 35 to 170
atmospheres. Space velocities in the range of 0.5 to 2.0 hr-1
are applied.

Flow diagram of a Cheveron hydocracking unit:29 (1,4) reactors, (2,5)

HP separators, (3) recycle scrubber (optional), (6) LP separator, (7) fractionator.

Hydrodealkylation
Process
Designed to hydrodealkylate methylbenzenes,

ethylbenzene and C9+ aromatics to benzene. The

petrochemical demand for benzene is greater than for
toluene and xylenes.
After separating benzene from the reformate, the higher
aromatics are charged to a hydrodealkylation unit.
The reaction is a hydrocracking one, where the alkyl side
chain breaks and is simultaneously hydrogenated.

 Consuming hydrogen is mainly a function of the number of

benzene substituents.
Dealkylation of polysubstituted benzene increases
hydrogen
consumption and gas production (methane).

Hydrotreatment
Processes
Hydrotreating is a hydrogen-consuming process
to reduce or remove impurities such as sulfur,
nitrogen, and some trace metals from the feeds.

It also stabilizes the feed by saturating olefinic

compounds.
Feeds could be any petroleum fraction, from
naphtha to crude residues.
The feed is mixed with hydrogen, heated to the
proper temperature, and introduced to the
reactor containing the catalyst.

Hydrotreatment Catalysts and

Reactions
The same as those developed in Germany for coal hydrogenation.
The cobalt-molybdenum/alumina is an effective catalyst.

hydrodenitrogenation

Alkylation Process

To produce large hydrocarbon molecules in the gasoline

fraction from small moleucles. (branched hydrocarbons).
Normally acid catalyzed using H 2SO4 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.

Oligomerization of Olefines
(Dimerization)

To produce polymer gasoline with high octane

number.
Acid catalyzed. By phosphoric or sulfuric acid.
The feed is Propylne-propane or propykenebutane mixture.
The alkane is used as diluent.