PETROLEUM TECHNOLOGY

THE PROCESS & TECHNOLOGY OF CRACKING

Introduction:
In context to refinery processes for petroleum, “cracking” is defined as decomposition induced by
elevated temperatures (>350° C, >660° F), whereby the higher molecular weight constituents of
petroleum are converted to lower molecular weight products. Cracking reactions involve carbon-
carbon bond rupture & are thermodynamically favored at high temperatures.

Although cracking basically involves converting large oil molecules into low boiling materials,
during the actual process some smaller molecules may combine to give a product of higher
molecular weight.

A number of products may be formed during cracking of the petroleum feedstock such as
gasoline, coke & fuel oil. Some material obtained during cracking & having a boiling range
intermediate between gasoline & fuel oil is referred to as “recycle” stock, which is recycled back
into the cracking equipment until conversion is complete.

Chemistry of Cracking:
Two general types of reaction occur during cracking:

1. The decomposition of large molecules into small molecules (primary reactions):

CH3 –CH2 –CH2 – CH3 CH4 + CH3 –CH=CH2

Butane methane propene

Or

CH3 –CH2 –CH2 – CH3 CH3 –CH3 + CH2=CH2

Butane ethane ethylene

2. Reactions by which some of the primary products react to form higher molecular weight
materials (secondary reactions):

CH2=CH2 + CH2=CH2 CH3 –CH2 –CH=CH2

Ethylene butene
Or

R –CH= CH2 + R’ –CH= CH2 tar, heavy oil, coke, etc.

Methodology of cracking:
There are several methods of performing cracking reactions & are described below:
1. Thermal Cracking: This involves the noncatalytic conversion of higher-boiling petroleum
stocks into lower-boiling products by application of temperatures above 350° C. From the
reaction point of view thermal cracking is a free radical chain reaction, a free radical being
defined as an atom or group of atoms with an unpaired electron. For free radical reactions of
various kinds involving hydrocarbons, refer page 255-257 of “The Chemistry & Technology of
Petroleum “ by James G. Speight or any standard organic chemistry textbook.

2 Catalytic Cracking: This is nothing but thermal decomposition similar to thermal cracking
except that the cracking process occurs in the presence of a catalyst, which is not (in theory)
consumed in the process & directs the course of the cracking reactions to produce more of
the desired higher-octane hydrocarbon products. Nowadays most gasoline fractions are
produced by this method superseding the older thermal cracking process. The chemistry of
catalytic cracking is an ionic process involving carbonium ions which are hydrocarbon ions
having a positive charge on a carbon atom. For details of chemical reactions involving

Page 1 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
catalytic cracking, refer page 255-257 of “The Chemistry & Technology of Petroleum“by
James G. Speight or any standard organic chemistry textbook.

3. Visbreaking: Viscosity breaking or visbreaking is a mild thermal cracking operation used to

reduce the viscosity & pour point of residual or asphaltic feed stocks. This operation produces
a large amount of partially cracked gas oil which could then be processed in a conventional
catalytic cracking plant.

4. Coking: Coking is again a variation of the thermal cracking process in which the time of
cracking is so long that coke is produced as the bottom product. It is used for the continuous
conversion of heavy, low-grade oils into lower products. The feedstock can be material such
as reduced crude, straight-run residua, or cracked residua, & the products are gases,
naphtha, fuel oil, gas oil, & coke. The coke obtained is usually used as fuel, but also finds
specialty uses such as electrode manufacture, production of chemicals, & metallurgical coke,
thus increasing its value.

5. Hydrocracking: This is an advancement in catalytic cracking process (>350° C) in which

hydrogenation accompanies cracking. It is characterized by the cleavage of carbon-to-carbon
linkages accompanied by hydrogen saturation of the fragments to produce lower-boiling
products. Relatively high hydrogen pressures (100 to 2000 psi) are required to minimize
polymerizations & condensations leading to coke formation.

6. Hydrotreating: This is again a variation of the catalytic cracking process, except that, although
catalysts are employed for hydrotreating, there is very little cracking involved & the process
actually is used for selective hydrogen addition to olefins & aromatics in order to saturate
them. Another important purpose of hydrotreating is removal of sulfur & nitrogen compounds
present in the feedstock by selective hydrogenation. The temperatures & pressures
employed are generally moderate compared to hydrocracking.

Description of Cracking processes:

1. Thermal Cracking: Thermal cracking of higher-boiling materials to motor or high-octane

gasoline is now becoming an obsolete process, since these days the requirement of high-
octane & low levels of deleterious sulfur & nitrogen compounds has proved to be a serious
limitation for this process. New units are now practically not installed & many of the older
operating refineries have either shutdown these units or have gone for revamping the older
units to the more modern catalytic processes. Nevertheless, a brief description of the
commercial thermal cracking processes is given for better understanding
The Dubbs Process: This is a typical application of the thermal cracking process. The
feedstock (reduced crude) is preheated by direct exchange with the cracked products in the
fractionating columns. Cracked gasoline & heating oil are removed from the upper section of
the column. Light & heavy distillate fractions are removed from the lower section & are
pumped to separate heaters. Higher temperatures are used to crack the more refractory light
distillate fraction. The streams from the heaters are combined & sent to a reaction chamber
where a certain residence time allows the cracking reactions to be completed. The cracked
products are then separated in a low-pressure flash chamber where a heavy fuel oil is
removed as bottoms. The remaining cracked products are sent to the fractionating column.

Low pressures (<100 psi) & temperatures of 500° C or greater, produce low molecular weight
hydrocarbons than those produced at higher pressures (400-1000 psi) & at temperatures
below 500° C. The reaction time is also important; light feeds (gas oils) & recycle oils require
longer reaction times than the readily-cracked heavy residues. Mild cracking conditions, with
a low conversion per cycle, favor a high yield of gasoline components, with low gas & coke
production, but the gasoline quality is not high, whereas more severe conditions give
increased gas & coke production & reduced gasoline yield (but of higher quality).

Page 2 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING

Gas

Feedstock (topped crude)

Gasoline

Reaction chamber

Fractionator
Flasher
Heater Furnace
Oil
Residuum
Recycle

Mixed-Phase Cracking: Mixed-phase cracking (also called liquid-phase cracking) is a continuous

thermal decomposition process for the conversion of heavy feedstocks to products boiling in the
gasoline range. The process generally employs rapid heating of the feedstock (kerosene, gas oil,
reduced crude, or even whole crude), after which it is passed to a reaction chamber & then to a
separator where the vapors are cooled. Overhead products from the flash chamber are
fractionated to gasoline components & recycle stock, while flash chamber bottoms are withdrawn
as a heavy fuel oil. Coke formation, which may be considerable at the process temperatures (400
to 480° C), is minimized by use of pressures in excess of 350 psi.

Gas

Gasoline
Reaction Chamber

Fractionator
Flasher

Feed
Stock
Heater

Residuum
Mixed-phase thermal cracking

Page 3 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
Vapor-Phase Cracking: Vapor-phase cracking is a high temperature (545 to 595° C), low-
pressure (< 50 psi) thermal conversion process which favors dehydrogenation of feedstock
(gaseous hydrocarbons to gas oils) to olefins & aromatics. Coke is often deposited in heater
tubes causing shutdowns - relatively large reactors are required for these units.

Gas

Gasoline

Reaction chamber

Fractionator
Flasher
Heater

Heater

Feed
Stock

Heavy fuel oil

Recycle

Vapor-phase thermal cracking

Selective Cracking: This is a thermal conversion process, which utilizes optimum conditions of
temperature & pressure for maximum product yield solely depending on the nature of the
feedstock. For example, heavy oil might be cracked at 495 to 515° C & 300 to 500 psi, while
lighter gas oil may be cracked at 510 to 530° C & 500 to 700 psi. It eliminates the accumulation of
stable low-boiling material in the recycle stock & also minimizes coke formation from high-
temperature cracking of the higher-boiling material. The end result is the production of fairly high
yields of gasoline, middle distillates, & olefinic gases. Gas

Feedstock
(topped crude)
Gasoline

Middle
Distillate
Reaction chamber

Fractionator
Flasher
Heater

Residuum
Light oil (recycle) Heavy oil (recycle)

Page 4 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
Naphtha Cracking: The thermal cracking of naphtha involves the upgrading of low-octane
fractions of catalytic naphtha to higher-quality material. The process is designed for upgrading
heavier portions of naphtha, which contain uncracked virgin feedstock & to remove napthenes, as
well as paraffins. During the process, small quantities of heavier aromatics are formed by
condensation reactions, & the product stream contains substantial quantities of olefins.

2. Catalytic Cracking: As mentioned earlier, catalytic cracking differs from thermal cracking by
use of catalyst & also is a much more efficient process compared to the non-catalytic thermal
cracking. The catalytic & thermal methods are compared in the table below:

Sr. Catalytic Cracking Thermal Cracking

No.
1 The gasoline produced by this method Comparatively lower octane number gasoline
has a higher octane number. produced.
2 The gasoline produced consists largely Gasoline contains more mono-olefins &
of isoparaffins & aromatics, which diolefins which are relatively less stable.
contribute to the higher octane number
& also are chemically more stable.
3 Catalytic cracking produces substantial Quantity of olefinic gases is smaller in
quantities of olefinic gases suitable for thermal cracking.
polymer gasoline manufacture along
with small amounts of methane, ethane,
& ethylene.
4 Catalytic cracking is a more selective Not a very selective process & end products
cracking process & gives lesser end are more.
products.
5 Gives a more economically salable Coke quality is not very high.
coke.
6 It has greater capability to accept high- High-sulfur feedstocks can prove to be a
sulfur feedstock. Also, gasoline limitation.
produced by this method has a lower
sulfur content.

Catalytic cracking, as a commercial process thus involves contacting a gas oil fraction with an
active catalyst under suitable conditions of temperature, pressure, & residence time so that a
substantial part (> 50%) of the gas oil is converted into gasoline & lower-boiling products, usually
in a single pass operation.

A limitation of the catalytic cracking process is the deposition of carbonaceous material on the
catalyst, reducing the catalyst activity. The removal of the coke or carbonaceous deposit is
therefore an important factor in the design of such units, one method being the burning of the
catalyst bed or layer in the presence of air for regenerating the catalyst.

A brief description of the various commercial catalytic cracking processes including the early ones
is given below for better understanding:

a. Houdry Fixed-Bed Catalytic Cracking: This was the first of the modern catalytic processes &
went into commercial operation in 1936. In this fixed-bed process, the catalyst in the form of
small lumps or pellets was made up of layers or beds in several (four or more) catalyst-
containing drums called converters. Feedstock vaporized at about 450°C & under 7 to 15-psi
pressure passed through one of the converters where the cracking reactions took place. After
a short time, deposition of coke on the catalyst rendered it ineffective, and, using a
synchronized valve system, the feed stream was diverted to the adjacent converter while the

Page 5 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
catalyst in the first converter was regenerated by carefully burning the coke deposits with air.
After about 10 minutes, the catalyst was ready to go on stream again.

In the present age, fixed-bed processes have been replaced with the more versatile moving-
bed or fluid-bed processes.

Product
fractionation

Flue Gas

Air
Feedstock
(heated)
Houdry fixed-bed catalytic cracking

b. Fluid-bed Catalytic Cracking: This is presently the most widely used catalytic cracking
process & is characterized by the use of a finely divided silica/alumina-based catalyst, which
is moved through the processing unit. The catalyst particles are of such a size that when
“aerated” with air, or hydrocarbon vapor, the catalyst behaves like a liquid & can be moved
through pipes. Thus, vaporized feedstock & fluidized catalyst flow together into a reaction
chamber where the catalyst, still dispersed in the hydrocarbon vapors, forms beds in the
reaction chamber & the cracking reactions take place. Because of the even flow distribution
of the catalyst & because of its high specific heat in relation to the vapors reacting, the entire
reaction can be maintained at a remarkably constant temperature. The cracked vapors pass
through cyclones located in the top of the reaction chamber, thereby removing the catalyst
from the vapors by centrifugal action. The cracked vapors out of the reaction chamber enter
the fractionating towers where fractionation into light- & heavy-cracked gas oils, cracked
gasoline, & cracked gases takes place.

Due to the contamination of the catalyst in the reaction chamber with coke, its activity is
reduced, & it has to be regenerated. Thus, the separated spent catalyst flows via steam
fluidization from the reaction chamber to the regenerator vessel, where the coke is removed
by controlled burning. In the course of burning the coke, a large amount of heat is liberated.
Most of this heat of combustion is absorbed by the regenerated catalyst & is sufficient to
vaporize the fresh feed entering the reaction chamber.

The fluid-bed catalytic cracking units abbreviated as “FCCU” are large-scale processes & unit
throughputs are typically in the range of about 10,000 to 130,000 barrels per day which
corresponds to catalyst circulation rates of 7 to 130 tons per minute. The large circulation
rates of hot, abrasive catalyst constitute a very significant challenge to the mechanical
integrity of the reactor, the regenerator & their associated internal equipment.

Page 6 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
Gases &
gasoline

Flue gas

Steam
Water Products Light gas
Oil

Fractionator
Fresh Catalyst

Regenerator
Heavy gas

Reactor
Oil

Bottoms

Catalyst Steam
make-up
Regenerated
Air catalyst

Spent catalyst
Feedstock

Flowsheet for fluid-bed catalytic cracking

c. Model IV Fluid-Bed Catalytic Cracking Unit: This unit involves a process in which the catalyst
is transferred between the reactor & regenerator by means of U-bends, & the catalyst flow
rate can be varied in relation to the amount of air injected into the spent-catalyst U-bend.
Regeneration air, other than that used to control circulation, enters the regenerator through a
grid, & the reactor & regenerator are mounted side by side. This design was preceded by the
Model III balanced pressure design, the Model II downflow design, & the original Model I
upflow design.

Flue gas Product

fractionation
Regenerator

Reactor

Feedstock

Regenerated catalyst Steam

Air
Spent Catalyst

Flowsheet for Model IV fluid-bed catalytic cracking

d. Orthoflow Fluid-Bed Catalytic Cracking: This process uses the unitary vessel design, which
provides straight-line flow of catalyst & thereby minimizes erosion encountered in pipe-bends.

Page 7 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
Commercial Orthoflow designs are of three types: Models A & C, with the regenerator beneath
the reactor, & model B, with the regenerator above the reactor. In all cases the catalyst-
stripping section is located between the reactor & the regenerator; all designs employ the
heat- balanced principle incorporating fresh feed–recycle feed cracking.

Flue gas

Regenerator
Air

Product fractionation

Reactor

Recycle

Steam

Feedstock

Air

Model B Orthoflow fluid-bed catalytic cracking process

Product fractionation
Reactor

Steam

Flue gas
Regenerator

Air

Feedstock Recycle

Model C Orthoflow fluid-bed catalytic cracking unit

Page 8 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
e. Universal Oil Products (UOP) Fluid-bed Catalytic Cracking: This process is adaptable to the
needs of both large & small refineries, & its important distinguishing features include 1)
elimination of the air riser with its attendant large expansion joints, 2) elimination of
considerable structural steel supports, & 3) reduction in regenerator & in air-line through use
of 15 to 18 psi pressure operation.

Product fractionation

Reactor
Flue gas Catalyst stripper

Regenerator
Steam

Air

Feedstock
Flowsheet for UOP fluid-bed catalytic cracking

f. Shell Two-Stage Fluid-Bed Catalytic Cracking: This two-stage fluid catalytic process allows
greater flexibility in shifting product when dictated by demand. Thus, virgin feedstock is first
contacted with cracking catalyst in a riser reactor, that is, a pipe in which fluidized catalyst &
vaporized oil flow concurrently upward, & the total contact time in this first stage is of the
order of seconds.

Light products Light products

Middle distillate

Heavy distillate
Fractionator
Fractionator

Regenerator

Air
Separator
Reactor

Stripper
Reactor

Steam

Regenerated catalyst
Feedstock
Flowsheet for Shell two-stage catalytic cracking

Page 9 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
High temperatures 470 to 565° C are employed to reduce undesirable coke lay-down on
catalyst without destruction of gasoline by secondary cracking. Other operating
conditions in the first stage are a pressure of 16 psi & catalyst-oil ratio of 3:1 to 50:1, &
volume conversion ranges between 20 & 70% have been recorded.

All or part of the unconverted or partially converted gas-oil product from the first stage is
then cracked further in the second-stage fluid-bed reactor. Operating conditions are 480
to 540° C & 16 psi with a catalyst-oil ratio of 2 to 12/1. Conversion in the second stage
varies between 15 & 70% with an overall conversion range of 50 to 80%.

g. Airlift Thermofor Catalytic Cracking (Socony Airlift TCC process): This process is a
moving-bed, reactor-over-generator continuous process for conversion of heavy gas oils
into lighter high-quality gasoline & middle distillate fuel oils. Feed preparation may consist
of flashing in a tar separator to get vapor feed, & the tar separator bottoms may be sent to
a vacuum tower from which the liquid feed is produced.

The gas-oil vapor-liquid flows downward through the reactor concurrently with the
regenerated synthetic bead catalyst. The catalyst is purged by steam at the base of the
reactor, & gravitates into the kiln or regeneration is done by the use of air injected into the
kiln. Approximately 70% of the carbon on the catalyst is burned in the upper kiln burning
zone & the remainder in the bottom burning zone. Regenerated, cooled catalyst enters the
lift pot, where low-pressure air transports it to the surge hopper above the reactor for reuse.

Regenerated
catalyst
hopper
Surge

(liquid)

Feedstock
Reactor

(vapor) Product
fractionation
Steam

Flue gas

Air
(hot)
Kiln

Kiln

Air (lift)

Flowsheet for airlift thermofor catalytic cracking

Page 10 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
h. Houdriflow Catalytic Cracking: This is a continuous, moving-bed process employing an
integrated single vessel for the reactor & regenerator kiln. The charge stock, sweet or sour,
can be any fraction of the crude boiling between naphtha & soft asphalt. The catalyst is
transported from the bottom of the unit to the top in a gas lift employing compressed flue gas
& steam.

The reactor feed & catalyst pass concurrently through the reactor zone to a disengager
section, in which vapors are separated & directed to a conventional fractionation system.
The spent catalyst, which has been steam purged of residual oil, flows to the kiln for
regeneration, after which steam & flue gas are used to transport the catalyst to the reactor.

Feedstock
Steam

Products
Flue gas
Reactor

Catalyst storage
Catalyst
Lift
Kiln

Air

Flowsheet for Houdriflow catalytic cracking

i. Houdresid Catalytic cracking: Houdresid catalytic cracking is a process that uses a variation
of the continuous-moving catalyst bed designed to get high yields of high-octane gasoline &
light distillate from reduced crude charge.

Residuum cuts ranging from crude tower bottoms to vacuum bottoms, including residua high
in sulfur or nitrogen can be employed as the feedstock, & the catalyst is synthetic or natural.
Though the equipment employed is similar in many respects to that used in Houdriflow units,
novel process features modify or eliminate the adverse effects on catalyst & product
selectivity usually resulting when heavy metals –iron, nickel, copper, & vanadium – are
present in the fuel. The Houdresid catalytic reactor & catalyst-regenerating kiln are contained
in a single vessel. Fresh feed plus recycled gas oil are charged to top of the unit in a partially
vaporized state & mixed with steam. Refer flowsheet below:

Page 11 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING

Light
products

Houdresid unit
Middle
distillates

Fractionator

Fractionator
Feedstock Redu ced
crude

Fuel stocks

Recycle

Flowsheet for Houdresid catalytic cracking

j. Suspensoid Catalytic Cracking: This was developed from the thermal cracking process
carried out in tube & tank units. Small amounts of powdered catalyst or a mixture with the
feedstock & the mixture are pumped through a cracking coil furnace. Cracking
temperatures are 550 to 610° C with pressures of 200 to 500 psi. After leaving the furnace,
the cracked material enters a bubble tower where they are separated into two parts, gas oil
& pressure distillate. The latter is separated into gasoline & gases. The spent catalyst is
filtered from the tar, which is used as a heavy-industry fuel oil.

The process is a compromise between catalytic & thermal cracking. Here the catalyst
allows a higher cracking temperature & assists mechanically in keeping coke from
accumulating on the walls of the tubes. The normal catalyst employed is spent clay
obtained from the contact filtration of lubricating oils (2 to 10 lb. per barrel of feed).

Products (gasoline, gases)

Catalyst
Fractionator
Heater

Feedstock

Heavy fuel
Filter

oil

Catalyst

Flowsheet for Suspensoid catalytic cracking

Page 12 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
3. Visbreaking: As explained earlier visbreaking is a mild thermal cracking operation employed
for viscosity reduction of residual or asphaltic feed stocks.

Visbreaking conditions range from 455 to 510°C & from 50 to 300 psi at the heating-coil
outlet. Liquid-phase cracking takes place at these low-severity conditions. Besides fuel oil
(major product), material in the gas oil & gasoline boiling range is also produced. The gas oil
produced may be diverted to catalytic cracking units or used as heating oil.

Thus, a crude oil residuum is passed through a furnace where it is heated to a temperature of
480°C, the outlet pressure controlled at about 100 psi. The furnace is designed in a manner
such that it contains a soaking section of low heat density, where the charge can be held until
the visbreaking reactions are completed. The cracked products are then passed into a flash-
distillation chamber. The overhead material from this chamber is then fractionated to produce
a low-quality gasoline as an overhead product & light gas oil as bottoms. The liquid products
from the flash chamber are cooled with a gas oil flux & then sent to a vacuum fractionator.
This yields a heavy gas oil distillate & a residual tar of reduced viscosity.
Gasoline
Feedstock
Heavy
gas oil

Vacuum fractionator
Fractionator
Reactor

Flasher

Tar

Light gas oil

Flowsheet for Visbreaking operations

4. Coking: As mentioned earlier coking processes generally utilize longer reaction times than
thermal cracking processes. To accomplish this, drums or chambers (reaction vessels) are
employed. Normally two or more such vessels are provided, in order to simultaneously
decoke the off-line vessel without interrupting the semicontinuous type of process. The
various type of coking processes are described below:

a. Delayed Coking: This is a semicontinuous process in which the heated charge is

transferred to large soaking (or coking) drums, which provide the long residence time
needed to allow the cracking reactions to be completed. The feed to these units is
normally an atmospheric residuum although cracked tars & heavy catalytic oils may also
be used.

The process flow is as follows:

The feedstock enters the product fractionator where it is heated & lighter fractions are
removed as side streams. The fractionator bottoms, including a recycle stream of heavy
product, are then heated in a furnace whose outlet temperature varies from 480 to 515°C.
The heated material enters one of a pair of coking drums where the cracking reactions are
completed. The cracked products leave as overheads, & coke deposits form on the
the inner surface of the drum. Two drums allow for continuous operation, with one on stream
while the other is being cleaned. The temperature in the coke drum ranges from 415 to 450°C

Page 13 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
at pressures from 15 to 90 psi. The overheads from the coking drum go to the fractionator,
where naphtha & heating oil fractions are recovered. The heavy recycle material is material is
combined with preheated fresh feed & returned to the reactor.

The coke drum is usually on stream for about 24 hours before becoming filled with porous
coke, & the following procedure is used to remove the coke: 1) the coke deposit is cooled with
water; 2) one of the heads of the coking drum is removed to permit the drilling of a hole
through the center of the deposit; & 3) a hydraulic cutting device, which uses multiple high
-pressure jets, is inserted into the hole, & the wet coke is removed from the drum. These
cleaning operations normally require 24 hours before the drum can be put into reuse.

Gas
Gasoline (naphtha)
Gas oil

Feedstock
Fractionator

Coking drum

Coking drum
(soaker)

(soaker)
Coke

Operative Nonoperative

Flowsheet for Delayed coking

b. Fluid Coking: Fluid coking is a continuous process, which uses the fluidized-solids technique
to convert residua, including vacuum pitches, to more valuable products. The residuum is
coked by being sprayed into a fluidized bed of hot, fine coke particles, which permit the
coking reactions to be conducted at higher temperatures & shorter contact times than can be
employed in delayed coking. Moreover, these conditions result in decreased yields of coke
with greater quantity of more valuable liquid product being recovered.

Fluid coking uses two vessels, a reactor & a burner; coke particles are circulated between
these to transfer heat (generated by burning a portion of the coke) to the reactor. The reactor
holds a bed of fluidized coke particles, & steam is introduced at the bottom of the reactor to
fluidize the bed. The pitch feed at, for example 260 to 370°C is injected directly into the
reactor. The temperature in the coking vessel ranges from 480 to 565°C, & the pressure
nearly atmospheric causing the incoming feed to partly vaporize & partly deposit on the
fluidized coke particles. The material on the particle surface then cracks & vaporizes, leaving
a residue, which dries to form coke. The vapor products pass through cyclones, which
remove most of the entrained coke.

The vapor is discharged into the bottom of a scrubber where the products are cooled to
condense a heavy tar, which contains substantial quantity of coke dust & is recycled back to
the reactor. The upper part of the scrubber tower is a fractionating zone from which coker gas

Page 14 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
oil is withdrawn for feeding to a catalytic cracking unit. The naphtha & gas from the
fractionating zone are taken overhead to condensers.

In the reactor, the coke particles flow down through the vessel into a stripping zone at the
bottom. Steam displaces the product vapors between the particles & the coke then flows into
a riser, which leads to the burner. Steam is added to the riser to reduce the solids loading &
induce upward flow. The average bed temperature in the burner is 590 to 650°C, & air is
added as needed to maintain the temperature by burning part of the product coke. The
pressure in the burner may range from 5 to 25 psi. Flue gases from the burner pass through
cyclones & discharge to the stack. Hot coke from the bed is returned to the reactor through a
second riser assembly.

Coke is one of the products of the process, & it must be withdrawn from the system in order
to keep the solids inventory from increasing. The net coke produced is removed from the
burner bed through a quench elutriator drum, where water is added for cooling & cooled coke
is withdrawn & sent to storage. During the course of the coking reaction the particles tend to
grow in size. The size of the coke particles remaining in the system is controlled by a grinding
system within the reactor.

Fuel gas

Cracked gasoline

Gas oil Flue gas

Fractionator

Burner

Coke

By-product coke
Reactor

Feedstock
Air

Coke

Steam

Flowsheet for Fluid coking

c. Decarbonizing: The decarbonizing thermal process is designed to minimize coke & gasoline
yields but, at the same time, to give maximum yield of gas oil. The process is essentially the

Page 15 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
same as the delayed coking process, but lower temperatures & pressures are employed. For
example, pressures range from 10 to 25 psi while heater outlet temperatures maybe 485°C &
coke drum top temperatures maybe of the order of 415°C.

Gas

Gasoline

Gas oil
Fractionator

Coke drum

Coke drum
Feedstock

Flowsheet for Decarbonizing

d. Low-Pressure Coking: Low-pressure coking is a process designed for a once-through, low

pressure operation. The process is similar to delayed coking except that recycling is not
practiced & the coke chamber operating conditions are 435°C, 25 psi. Excessive coking is
inhibited by the addition of water to the feedstock.

Gas and
gasoline
Coke chamber

Coke chamber

Fractionator
Flasher

Gas oil

Feedstock
Fuel oil

Flowsheet for Low-pressure coking

e. High-Temperature Coking: This is a semicontinuous thermal conversion process designed for

high-melting asphaltic residua which yield coke & gas oil as the primary products. The coke
may further be treated to remove sulfur to produce a low-sulfur coke ( 5%), even though the
feedstock could have as much as 5% wt/wt sulfur.
The process flow is as follows:

Page 16 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
The feedstock is fed into the pitch accumulator, then to the heater (370°C, 30 psi), & finally to
the coke oven where temperatures may be as high as 980 to 1095°C. Volatile materials are
fractionated, and, after the cycle is complete, coke is collected for sulfur removal & quenching
prior to storage.

Gas

Gasoline

accumulator
Pitch

Gas oil

Coke
oven
Coke

Flowsheet for High-temperature coking

5. Hydrocracking: Hydrocracking is similar to catalytic cracking, with hydrogenation

superimposed & with the reactions taking place simultaneously or sequentially. The purpose
hydrocracking is to convert high-boiling feedstocks to lower-boiling products by cracking the
hydrocarbons in the feed & hydrogenating the unsaturated materials in the product streams.
The polycyclic aromatics are first partially hydrogenated before cracking of the aromatic
nucleus takes place. Also, the majority of sulfur & nitrogen is converted to hydrogen sulfide &
ammonia. The reaction rates are facilitated by use of catalysts.

Large quantities of hydrogen sulfide & ammonia are formed when using high sulfur & nitrogen
feedstocks for hydrocracking units. These are removed by the injection of water in which,
under the high-pressure conditions employed, both hydrogen sulfide & ammonia are very
soluble compared with hydrogen & hydrocarbon gases.

6. Hydrotreating: The purpose of the process is the removal of sulfur & nitrogen compounds
without appreciable alteration in the boiling range or in other words it is selective
hydrogenation of the feedstock for removal of sulfur & nitrogen with very little cracking
involved.

Hydrotreating catalysts are usually cobalt plus molybdenum or nickel plus molybdenum in the
sulfide forms, impregnated on an alumina base.

The operating conditions of 1000 to 2000 psi hydrogen pressures & 370°C temperatures are
such that appreciable hydrogenation of aromatics will not occur.

Commercial Processes for Hydrocracking & Hydrotreating: Since commercial processes for
hydrocracking & hydrotreating operate essentially in the same manner i.e., feedstock is
passed along with hydrogen gas into a tower or reactor filled with catalyst pellets the
commercial processes have not been classified separately as hydrocracking & hydrotreating.
The processing conditions i.e., the temperature & pressures decide whether a lot of cracking
reactions are taking place along with the hydrogenation or just removal of nitrogen & sulfur is
taking place.

Hydrofining: This process can be applied to lubricating oils, naphthas, & gas oils. The
feedstock is heated in a furnace & passed with hydrogen through a reactor containing a

Page 17 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
suitable metal oxide catalyst, such as cobalt & molybdenum oxides on alumina. Reactor
operating conditions range from 205 to 425°C & from 50 to 800 psi, depending on the
feedstock & the degree of treating required. Higher-boiling feedstocks, high sulfur content, &
maximum sulfur removal require higher temperatures & pressures.

After passing through the reactor, the treated oils cooled & separated from the excess
hydrogen, which is recycled through the reactor. The treated oil is pumped to a stripper tower
where hydrogen sulfide, formed by the hydrogenation reaction, is remove by steam, vacuum,
or flue gas, & the finished product leaves the bottom of the stripper tower. In this process the
catalyst is usually not regenerated & is replaced after about a year’s use.

This process is used to upgrade low-quality, high-sulfur naphthas. The sulfur content of
kerosenes can be reduced with improved color, odor, & wick-char characteristics. The
tendency of kerosene to form smoke is not affected since aromatics, which cause smoke., are
not affected by the mild hydrofining conditions. Cracked gas oils with high sulfur content can
be converted to excellent furnace fuel oils & diesel fuel oils by reduction in sulfur content & by
removal of components that form gum & carbon residues.

Hydrogen

Water (vapor)
Furnace

Reactor

Stripper

Drier

Feedstock
Product stream

Hydrogen

Flowsheet for Hydrofining

Unifining: This is regenerative, fixed-bed, catalytic process to desulfurize & hydrogenate

refinery distillates of any boiling range. Contaminating metals, nitrogen compounds, & oxygen
compounds are eliminated, along with sulfur. The catalyst is a cobalt –molybdenum-alumina
type which may be regenerated in situ with steam & air.

Ultrafining: It is a regenerative, fixed-bed, catalytic process to desulfurize & hydrogenate

refinery stocks from naphthas through lube stocks. The catalyst is cobalt-molybdenum on
alumina & may be regenerated in situ using an air-stream mixture. Regeneration requires 10
to 20 hours & may be repeated 50 to 100 times for a given batch of catalyst; catalyst life is 2
to 5 years depending on the feedstock.

Page 18 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
Autofining: The autofining process differs from other hydrorefining processes in that an external
source of hydrogen is not required. Sufficient hydrogen to convert sulfur to hydrogen sulfide is
obtained by dehydrogenation of naphthenes in the feedstock.

The processing equipment is similar to that used in Hydrofining. The catalyst is cobalt &
molybdenum oxides on alumina, & operating conditions are usually 340 to 425°C at pressures of
100 to 200 psi. Hydrogen formed by dehydrogenation of naphthenes in the reactor, is separated
from the treated oil & is then recycled through the reactor. The catalyst is regenerated with steam
& air at 200-to-1000-hour intervals, depending on whether light or heavy feedstocks have been
processed. The process is used for the same purpose, as Hydrofining but is limited to fractions
with end points not higher than 370°C.

Feedstock Flue gas

(preheated)

Fractionator
Accumulator
Knockout
Reactor

drum

Product
stream

Heavy fuel oil

Flowsheet for Autofining

Isomax: The Isomax process is a two-stage, fixed-bed catalyst system which operates under
hydrogen pressures from 500 to 1500 psig in a temperature range of 205 to 370°C, for example
with middle distillate feedstocks. Exact conditions depend on the feedstock & product
requirements, & hydrogen consumption is of the order of 1000 to 1600 SCF per barrel of feed
processed. Each stage has a separate hydrogen recycle system. Conversion may be balanced to
provide products for variable requirements & recycle can be taken to extinction if necessary.
Fractionation can also be handled in a number of ways to yield desired products.

Recycle
Hydrogen Fuel gas hydrogen Fuel gas
Feedstock recycle Fuel gas
Butanes
Stabilizer
Reactor

Reactor

Light gasoline
Heavy gasoline
Diesel fuel

Bottoms
Feedstock recycle

Flowsheet for Isomax hydrocracking process

Page 19 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
H-Oil: The H-Oil process is basically a catalytic hydrogenation technique in which, during the
reaction, considerable hydrocracking takes place. The process is used to upgrade heavy sulfur-
containing crudes & residual stocks to high-quality sweet distillates, thereby reducing fuel oil
yield. A modification of H-Oil called Hy-C cracking will convert heavy distillates to middle
distillates & kerosene.

Oil & hydrogen are fed upward through the reactors as a liquid-gas mixture at a velocity such that
catalyst is in continuous motion. Catalyst of small particle size can be used, giving efficient
contact among gas, liquid, and solid with good mass & heat transfer. Part of the reactor effluent is
recycled back through the reactors for temperature control & to maintain the requisite liquid
velocity. The entire bed is held within a narrow temperature range, which provides essentially an
isothermal operation with an exothermic process. Because of the movement of catalyst particles
in the liquid-gas medium, deposition of tar & coke is minimized, & fine solids entrained in the feed
will not lead to reactor plugging. They can also be added & withdrawn from the reactor without
interrupting the continuity of the process.

The reactor effluent is cooled by exchange & separates into vapor & liquid. After scrubbing in a
lean-oil absorber, hydrogen is recycled, and the liquid product is either stored directly or
fractionated prior to storage & blending.

Hydrogen
recycle

Hydrogen
Gas recycle

Lean oil
Reactor

Reactor

Separator

Absorber
Flasher

Rich oil

Distillate

Product
Feedstock stream

Hydrogen make-up

Flowsheet for H-Oil Process

Unicracking-JHC: This is a fixed-bed catalytic process that employs a high-activity catalyst with a
high tolerance for sulfur & nitrogen compounds & can be regenerated. The design is based upon
a single-stage or a two-stage system with provisions to recycle to extinction.

A two-stage reactor system receives untreated feed, make-up hydrogen, and a recycle gas at the
first stage in which gasoline conversion may be as high as 60% by volume. The reactor effluent is
separated to recycle gas, liquid product, and unconverted oil. The second-stage oil may be either
once through or recycle cracking; feed to the second stage is a mixture of unconverted first-stage
oil & second-stage recycle.

Page 20 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
Hydrogen
make-up Gas and light
gasoline
Feedstock

Hydrogen Gasoline
recycle

Fractionator
Flasher (s)

Reactor
Reactor

Diesel fuel

Feedstock recycle

Flowsheet for Unicracking-JHC process

Gulf HDS: This is a regenerative fixed-be process to upgrade petroleum residues by catalytic
hydrogenation to refined fuel oils or to high-quality catalytic charge stocks. Desulfurization &
quality improvement are the primary purposes of the process, but if the operating conditions &
catalysts are varied, light distillates can be produced & the viscosity of heavy material can be
lowered. Long on-stream cycles are maintained by reducing random hydrocracking reactions to a
minimum, and whole crudes, virgin, or cracked residua may serve as feedstock.

The catalyst is a metallic compound supported on pelleted alumina & may be regenerated in situ
with air & steam or flue gas through a temperature cycle of 400 to 650°C. On-stream cycles of 4
to 5 months can be obtained at desulfurization levels of 65 to 75% & catalyst life may be as long
as 2 years.
Hydrogen
make-up
Hydrogen recycle

Lean
Gas
Absorber

Feedstock Diethanolamine

Rich Light
Gas gasoline

Heavy
(high press.)

(low press.)

naphtha
Reactor

Reactor

Separator

Separator

Light
gas oil

Heavy
gas oil
“Light”
bottoms
“Heavy”
bottoms

Flowsheet for Gulf HDS process

Page 21 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
H-G Hydrocracking: This process may be designed with either a single- or a two-stage reactor
system for conversion of light & heavy gas oils to lower-boiling fractions. The feedstock is mixed
with recycle gas oil, make-up hydrogen, and hydrogen-rich recycle gas, and then heated &
charged to the reactor. The reactor effluent is cooled & sent to a high-pressure separator where
hydrogen-rich gas is flashed off, scrubbed, then recycled to the reactor. Separator liquid passes
to a stabilizer for removal of butanes & lighter products, & the bottoms are taken to a fractionator
for separation; any unconverted material is recycled to the reactor.
C2 gases

Hydrogen C 3, C4 gases
Feedstock recycle
(Heavy gas oil) Gasoline

(Recycle) Product
Stream

Fractionator
Hydrogen

Stabilizer
Separator
Reactor
(Make-up)

Feedstock
recycle

Flowsheet for H-G hydrocracking process

Ferrofining: The mild hydrogen-treating process was developed to treat distilled & solvent-refined
lubricating oils. The process eliminates the need for acid & clay treatment. The catalyst is a three-
component material on alumina base with low hydrogen consumption & life expectancy of 2 years
or more. Process operations include heating the hydrogen-oil mixture & charging to a downflow
catalyst-filled reactor. Separation of oil & gas is a two-stage operation whereby gas is removed to
the fuel system. The oil is then stripped to control the flash point, dried in vacuum, & a final
filtering step removes the catalyst fines.

Hydrogen
Feedstock Fuel
Gas Gas and
steam
Stripper/vacuum drier
(high press.)

(low press.)
Reactor

Separator
Separator

Filter

Product
Flowsheet for Ferrofining process

Page 22 of 23
 PETROLEUM TECHNOLOGY
THE PROCESS & TECHNOLOGY OF CRACKING
List of know-how suppliers for Cracking Processes: Most oil majors have developed &
modified technologies to suit their own particular requirements. There have been many
modifications to the older technologies & many of these processes are patented with the patents
owned by the world’s leading refining companies. Some of the major technology licensors are:

Universal Oil Products (UOP): They are one of the leading technology licensors & provide
integrated refinery solutions including catalytic cracking, hydroprocessing & reforming. “Reliance
Petroleum Ltd.”, the largest single-stream refinery in Asia has major processing units designed by
UOP.

Shell Development Company (Shell): Shell is a leading company providing technology for
visbreaking units & crackers.

ABB-Lummus Global/Chevron: They are among the top technology & engineering solutions
provider for FCC units, Hydrocrackers & Hydrotreaters.

Stone & Webster Engineering Corporation (S & W): They specialize in FCC units & have a major
share of the world market.

Institut Francais Petole (IFP): IFP is recognized the world over for its Hydrotreating technologies
for light distillates & majority of new installations are opting for IFP technology. One of their
specialties is a new selective hydrotreating technology named “Prime G” for ultra-low sulfur
gasoline.

Haldor Topsoe AS (Topsoe): They are leading contenders for supply of Hydrotreating technology.

Kellogg, Brown & Root Inc. (KBR): Most of the older FCC units in North America were designed
by KBR & they are doing a lot of revamp/ technology upgradation jobs on their older units.

BASF: BASF is a Germany based multinational & they have developed certain commercial
Hydroprocessing technologies.

ExxonMobil: They have developed new selective hydrotreating technologies for ultra-low sulfur
gasolines called “Scanfining”, “Octgain 125” & “Octgain 220” which shall become very relevant
when international norms for sulfur content in motor fuels are brought down to 50 ppm.

Some other companies offering Cracking & Hydroprocessing technologies include CD tech,
Petrobras (Brazil), Akzo, Criterion (mainly catalyst suppliers) etc.

It is important to note that of the various technologies available, the selection has to be made
based basically on three factors: a) feedstock to be processed b) end-product or its mix required
& c) economics of a particular process vis-à-vis its competitive technology.

List of reference books:

1. The Chemistry and Technology of Petroleum – James G. Speight

Publisher: Marcel Dekker, Inc.

2. Petroleum Refinery Engineering – W. L. Nelson

Publisher: McGraw-Hill Kogakusha, Ltd.

3. Chemical Process Industries – R. Norris Shreve & Joseph A. Brink, Jr.

Publisher: McGraw-Hill International Book Company

Prepared by: Ankur Srivastava

Chemical Engineer
ankurcheme@gmail.com
Page 23 of 23