Unit -3

Cracking:
Cracking, in petroleum refining, the process by which
heavy hydrocarbon molecules are broken up into
lighter molecules by means of heat and usually
pressure and sometimes catalysts and in the presence
of hydrogen. Process are known as thermal cracking,
catalytic cracking and hydro cracking.

Cracking is the most important process for the

commercial production of gasoline and diesel fuel and
also to balance the market demand from the fractions
obtained from distillation process of crude oil.

Cracking of petroleum yields light oils (corresponding

to gasoline), middle-range oils used in diesel fuel,
residual heavy oils, a solid carbonaceous product
known as coke, and such gases as methane, ethane,
ethylene, propane, propylene, and butylene.
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Depending on the end product, the oils can go directly
into fuel blending, or they can be routed through
further cracking reactions or other refining processes
until they have produced oils of the desired quality.
The gases can be used in the refinery’s fuel system, but
they are also important raw materials for
petrochemical plants, where they are made into a
large number of end products, ranging from synthetic
rubber and plastic to agricultural chemicals.

The first thermal cracking process for breaking up

large nonvolatile hydrocarbons into gasoline came into
use in 1913; it was invented by William Merriam
Burton, a chemist who worked for the Standard Oil
Company (Indiana), which later became the Amoco
Corporation. Various improvements to thermal
cracking were introduced into the 1920s. Also in the
1920s, French chemist Eugène Houdry improved the

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cracking process with catalysts to obtain a higher-
octane product. His process was introduced in 1936 by
the Socony-Vacuum Oil Company (later Mobil Oil
Corporation) and in 1937 by the Sun Oil Company
(later Sunoco, Inc.). Catalytic cracking was itself
improved in the 1940s with the use of fluidized or
moving beds of powdered catalyst. During the 1950s,
as demand for automobile and jet fuel increased,
hydrocracking was applied to petroleum refining. This
process employs hydrogen gas to improve the
hydrogen-carbon ratio in the cracked molecules and to
arrive at a broader range of end products, such as
gasoline, kerosene (used in jet fuel), and diesel fuel.
Modern low-temperature hydrocracking was put into
commercial production in 1963 by the Standard Oil
Company of California (later the Chevron
Corporation).

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Thermal Cracking:

Thermal cracking is defined as the thermal

decomposition under pressure and heat of large
hydrocarbon molecules to form smaller molecules.

In thermal cracking, high temperatures (typically in

the range of 450°C to 750°C) and pressures (up to
about 70 atmospheres) are used to break the large
hydrocarbons into smaller ones. Thermal cracking
gives mixtures of products containing high
proportions of hydrocarbons with double bonds –
alkenes.

The most important reaction is irreversible

endothermic cracking of paraffin molecule or side
chain yields lower molecular wt molecules.

Reactions : RCH2CH2R = RCH=CH2 + CH3R

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Additional olefinic hydrocarbon may be formed by
reversible dehydrogenation of paraffins.

RCH2CH3 ↔ RCH=CH2 + H2

this is a endothermic reaction proceeds through free

radical mechanism. Unsaturated olefins further
crack again

C 4H 8 → C2H6+ H2 or C2H4 + CH4 + C

C 4H 8 → CH4 + C3H4

C3H4 / C2H4 → C + H2

Olefins polymerizes also under the cracking conditions

2 C2H4 → C4 H8

C4 H8 + C2H4 → C6H12

2C3H4 → C6H6 (benzene)+ H2

hydrogenation also occurs to some extent

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C3H4 + H2 → C3H6

Aromatic saturates ring structure follow the different

pattern .

Chain detachment is frequent followed by

dehydrogenation.

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Saturates are converted to unsaturates

Isomerisation may also occur

CH3CH2CH=CH2 ↔ CH3CH=CHCH3

Single ring naphthenes are more stable than paraffins

or olefins although high temperature will produce
ring splitting . In addition dehydrogenation may
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occur leading to unsaturated naphthenic ring or
aromatics. For the substituted naphthenes , the
relative stability of attached side chain , not the ring
structure is the determining factor. for example,
stability of naphthenes with paraffin side chain
decreases as the molecular wt of attached
paraffinic chain increases.

The aromatics are most refractory( least crackable)

hydrocarbon class Again the stability of substituted
aromatic depends on the stability of side chain.

It is therefore evident that relative crakability of

hydrocarbon types decreases a their hydrogen to
carbon ratio decreases.

Coke formation is an additional reaction which plays

important role in thermal cracking.

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Reaction/Process Parameters :

Temperature , pressure and time are main parameter

along with feed material.

Temperature: The rate of cracking strongly depends

on temperature. Cracking reaction begins about 315 -
370C, depending on the nature of feed. for a given
reaction time , extent of decomposition rapidly with
temperature . Rate of primary decomposing doubles at
every increment of 15 C at 440C and every 40C at
600C

Pressure : Pressure determine the phase of reaction

and also product distribution. Low pressure ( atm -
100 psig) and high temperature ( more that 540C) lead
to vapor phase reaction. these condition favour high
volume production of low M W wt hydrocarbon. At
high pressure (200- 1000 psig) and lower temp (400-
510C) leads to liquid or mixed phase cracking
reacrion. These condition favours more yield of
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gasoline and middle distillate along with formation of
heavy tars and polymers. Increase in pressure retards
cracking reaction but higher pressure retards coke
production .

At a given pressure and temperature the yield of light

fraction is a function of time. time of cracking at a set
condition of temp and press increases with increase
in API gravity of feed. It explain that heavier fraction
cracks easily .

The properties of cracked products will also change in

reference to the feed as per following

 Characterization factor decreases

 BP, Pour Point , viscosity decreases.
 unstauration and aromatization increase.
 octane number increases
 sulphur in cracked heavier products increases and
in light product decreases.
 oxidation stability decreases.
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 Depending on the temperature employed in
cracking , nomenclature of cracking operation is
done and product will also change. Following are
the various thermal cracking process

Cracking Process name Products

Temperature
(C)
425-460 Vis-breaking Fuel oil
460-520 Thermal cracking Gas. gasoline, tar oil
, circulating oil
520-600 Low temp coking Gas. gasoline, soft
coke
600-800 Gas production Gas and unsaturated
800-100 High temp coking Gas , heavy
aromatics, coke ,
pitch
Above 1000 Decomposition Hydrogen gas,
carbon black

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Cracking Operation :

Visbreaking:

It is a mild thermal cracking process applied to reduce the

viscosity of straight run residue such as pitch. These heavy
residues are sometimes blended with lighter heating oil to
produce of fuel oils of acceptable viscosity. This procedure
uses a high value product , light heating oil to produce low
value product, fuel oil. By reducing the viscosity of pitch
fraction , visbrealing reduces the amount of light heating oil
required for blending a fuel oil od desired specification.
This process is also used to reduce the pour point of waxy
residue.

Visbreaking conditions ranges from 455 - 510C and from 50

- 300 psig at the heating coil outlet. Liquid phase cracking
takes place in these condition. In addition to main product
fuel oil, gas oil and gasoline range products are also
produced. Gas oil may be used as heating oil or as a feed to
catalytic cracking unit.

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In the Following flows sheet residue is passed
through furnace at 480C at 100 psig. In the coil,
visbreaking reaction completed, such coil are known
as coil with soaking section , alternatively short coil
with separate soaking section may be provided.

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(Temp 470 C and pressure 150 - 225 psig)

Dubbs two coil Cracking process:

It is a conventional thermal cracking process. In this

process wide boiling reduced crude are used as feed.
in this process intermediate boiling range products
boiling above gasoline range are recycled to the
heating coil for further cracking and heavy residual
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tar or coke are rejected . This process is used for the
production of gasoline heating oil and gases.

Two Coil Thermal cracking ( Dubbs Process)

Due to invention of catalytic cracking , this is a

obsolete process

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Coking :

Coking processes arereltively severe cracking

operation designed to convert residual products such
as pitch and tar into gas , naptha, heating oil, gas oil

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and coke. the gas oil is a major fraction obtained and
used for feed for catalytic cracking.. naphtha fraction
(Octane number 65-80) may be used in gasoline
blending. Coke obtained may be used as fuel ,
electrode , production of chemicals, and metallurgical
coke.

Several Process are available for coking operation.

Delayed Coking:

It is a semi continuous process in which heated fed

stock is charged in coking drums . Long residence
time is provided for completion of reaction . feed
stock which are normally not suited for thermal and
catalytic cracking are used in coking.

Feed Material : Atmospheric residue, cracked tar,

heavy catalytic cycle oil.

Charging time of drum 4 - 5 hrs

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Coking time in drum 10-16 hrs

Decoking time 24 hrs

Operating Conditions

Charge Temp 470 - 520 C

Coking Temp 450 - 470C

Pressure in coke drums 5- 6 atm

Drum Dia 4- 5M

Drum Height 14 - 20 M

Coke yield estimation

Delayed Coker Fluid coker

Coke yield 2 + 1.66 K 1.15 K

Gas yield 5.5 + 1.76 K 5 + 1.3 K

K = conradson number of feed stock

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Fluid Coking :

Fluid coking is a fluid-bed process developed from the

basic principles of FCC, with close integration of
endothermic (cracking, coking, or gasification) and
exothermic (coke burning) reactions. In fluid coking ,
part of the coke product is burned to provide the heat
necessary for coking reactions to convert vacuum
residua into gasses, distillate liquids, and coke.

It is a continuous process , Feed is sprayed on

fluidized bed of hot and fine coke particles. Reaction
time is less and also yield of coke is less and more
valuable liquid fraction yield is more .

The preheated vacuum residue is sprayed onto the hot

coke particles heated in the burner by partial
combustion of coke produced in the previous cycle.
Using fluid beds in the reactor and burner provides
efficient heat transfer and fast coking on a collectively
large surface area of the small coke particles
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circulating between the reactor and burner. The
products of coking are sent to a fractionators (similar
to that used in delayed coking after recovery of fine
coke particles). Steam is also added at the bottom of
the reactor in a scrubber to strip heavy liquids
sticking to the surface of coke particles before they are
sent to the burner. This steam also provides
fluidization of coke particles in the reactor. The
reactor and the burner operate at temperatures of
510–570°C and 595–675°C, respectively.

Higher temperatures and short residence times in the

reactor lead to higher liquid and lower coke yields
compared with those of delayed coking. Coke is
deposited layer by layer on the fluidized coke particles
in the reactor. Air is injected into the burner to burn
15–30 % of the coke produced in the reactor, part of
the particles are returned to the reactor, and the

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remainder is drawn out as the fluid coke product.
Fluid coking can process heavier VDR and gives a
higher distillate yield (and lower coke yield) than
delayed coking.

Operating Condition

Reactor temp 480 - 560C,

Reactor Pressure 1 atm

Burner Temp 590 - 650C,

Burner Pressure appx 2 atm,

Feed temperature 260 - 370 C

Coke contains 88 - 92 % carbon and 1.6 - 1.9 % Hydrogen

depending on feed quality.

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( fluid cocking Process sheet)

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Flexi Coking:

Flexi-coking is also a fluid-bed processes developed

from the basic principles of FCC, with close
integration of endothermic (cracking, coking, or
gasification) and exothermic (coke burning) reactions.
In flexi-coking processes, part of the coke product is
burned to provide the heat necessary for coking
reactions to convert vacuum residua into gasses,
distillate liquids, and coke. Flexi-coking, as a variation
of fluid coking, provides the options of partial or
complete gasification of the coke product to produce a
fuel gas with some or no coke as the product. Different
from the bulk liquid-phase coking in delayed coking,
coking takes place on the surface of circulating coke
particles of coke heated by burning the surface layers
of accumulated coke in a separate burner.

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Figure shows a schematic diagram of flexi-coking. A
gasifier is added for conversion of some or all coke
produced in the coker in reaction with air and steam
to produce a synthesis gas. The hot coke particles from
the combustor are circulated back to the coking
reactor to provide the heat necessary for coking. The
distillate products from the Coker are sent to the
fractionators, as is done in the fluid coking process.
On the gasifier outlet, after removing the fine particles
from the gas by cyclones, the gas is cooled in a direct-
contact cooler to condense the sour water and recover
the flexi-gas. The product gas can be used as fuel gas
in the refinery. Depending on the demand, the flexi-
coking process can produce both fluid coke and fuel
gas, or gasify all the coke to produce only fuel gas.

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 (Flexi coking)

Catalytic Cracking:

At present catalytic cracking is the most widely used

process to convert heady fraction into gasoline
fraction. Initially the process was developed from the
discovery of Houdry in 1927 that silica alumina clays
would catalyze the cracking of heavy oils to give god
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yield of gasoline. In the process catalyst quickly
covered with carbon which block the active sites of
catalyst leading to reduction of its activity. this could
be restored by carefully burning off the carbon on the
catalyst surface. Initially batch rectors were developed
however overall operation was made continuous by
using several reactors in series.

Real advancement in catalytic cracking was achieved

in with the development of continuous reactors of
moving bed and fluidized bed in1942. currently in
catalytic cracking, fluidized bed reactors are
predominantly used worldwide.

Use of a catalyst in the cracking reaction increases the

yield of high-quality products under much less severe
operating conditions than in thermal cracking. Several
complex reactions are involved, but the principal
mechanism by which long-chain hydrocarbons are
cracked into lighter products can be explained by the

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carbonium ion theory. According to this theory, a
catalyst promotes the removal of a negatively charged
hydride ion from a paraffin compound or the addition
of a positively charged proton (H+) to an olefin
compound. This results in the formation of a
carbonium ion, a positively charged molecule that has
only a very short life as an intermediate compound
which transfers the positive charge through the
hydrocarbon. Carbonium transfer continues as
hydrocarbon compounds come into contact with active
sites on the surface of the catalyst that promote the
continued addition of protons or removal of hydride
ions. The result is a weakening of carbon-carbon
bonds in many of the hydrocarbon molecules and a
consequent cracking into smaller compounds.

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Catalytic Cracking reactions:

The reactions that occurs during catalytic cracking

are complex , however following order of decreasing
activity has been observed in catalytic cracking

Olefins, alkyl benzene ( with side chains greater than

3 ), Naphthenes, Polymethyal aromatics, Paraffins,
Unsubstituted aromatics.

The major catalytic reaction is of paraffins leading to

lighter paraffins and olefins formation. Paraffins
tends to crack towards the center of molecule , with
long chain cracking in several places simultaneously.
Catalytic cracking tends to yields products containing
three to four carbon atoms rather than one or two
carbon atoms as in thermal cracking.

RCH2CH2CH2CH3 → RCH3 + CH2=CHCH3

As in thermal cracking large molecules crack readily

than small molecules. However in catalytic cracking

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normal paraffins crack from 5 to 60 times faster than
in thermal cracking.. Isoparaffins cracks even more
faster in catalytic cracking than normal paraffins of
same molecular wt.

Paraffins having more than 6 carbon atoms may go

for non equilibrium rearrangement of structure
proir to cracking, thus increasing the yield of light
isomeric molecule.

A minor amount of dehydrocyclisation also occur

yielding aromatics and hydrogen.

Olefins are the most reactive hydrocarbons in

catalytic cracking and cracking rate is 1000 to 10000

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times faster than in thermal cracking. Severe
cracking condition almost completely eliminates
olefins, except n low boiling gasoline and gasses.
Rate of cracking of olefins is also more than normal
olefines as in case of paraffins. The branched chain
olefines can undergo hydrogen transfer reaction with
naphthenes and other hydrocarbons. Tertiary olefines
are selectively saturated to corresponding
isoparaffins. This contributes to large isoparaffins to
nomal paraffins ratio in catalytic cracked products.

Olefins undergo polymerization and condensation

reactions leading to aromatic and coke ( with 8 - 10%
hydrogen) production.

Naphthenes catalytically crack more readily than

paraffins . Naphthene craking occurs by both ring
and chain rupture and yields olefins and paraffins.
Formation of C1 and C2 hydrocarbons are relatively
minor.

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Aromatic hydrocarbons has very wide variation in
cracking. Benzene ring is nearly inert and condensed
ring such as naphthelene, antharance and
phenanthrene crack very slowly. When these
aromatics crack , a substantial part of their
conversion represent coke deposition on catalyst
surface.

Alkylbenzenes with attached group of C2 or larger

crack primarily to form benzene and corresponding
olefins. They crack more easily as size of alkyl gp
increases.

The hydrogen formed in catalytic cracking comes

from direct dehydrogenation of various molecules
and also materials converted into coke or higher
molecular wt compounds by condensation reaction.

The product distribution in catalytic cracking is very

different from thermal cracking.

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Fed Stock:

Gas oil, thermally cracked oils, residuum, solvent

extracts etc. Feed stock generally contains sulphur ,
nitrogen, oxygen and metals. All these affect the
catalyst activity and needs purification as per
requirement.

Catalyst :

Both the moving bed and fluidized bed catalyst uses

similar catalyst but produced in different forms, In
the shape of beads for moving bed and a fine powder
for fluidized bed.

Initially catalyst was acid treated clays ground to

powder.

Synthetic silica alumina catalyst of higher activity

was produced in the shape of beads or micro -
spheroidal particles with better fluidizing properties.
Many variation in composition have been used but

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standard catalyst contains 13 % by wt alumina, 87%
silica . Increasing the alumina content to 27% gives
more active and also more expensive catalyst.
Magnesia has also been used in addition orto replace
alumina but not used extensively. Variation in mg
techniques have produced catalyst with more pour
volume , which increases the activity and also
increases resistance to deactivation by heat and
steam.

Most recently natural or synthetic aluminum

silicate zeolite catalyst are in use , which has better
activity because of their stronger acidity.

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Catalytic cracking Process :

Batch type : now obsolete

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Houdry fixed bed Process:

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There are 3 reactors in parallel , At the bottom of
each reactor there are four connection provided
through rotary valve. only one line to connected at a
time. when first reactor in process , second will be on
steam and air purge and 3rd reactor will be on
regeneration. Usual cycle of operation as under

 on stream 10 min
 downward purging with steam to recover
hydrocarbon 5 min
 regeneration by hot air from bottom 10 min
 air purge followed by downward steam purge 5
min.

Operating Condition:

 Reactor temp 450 - 520C

 operating velocity 1 - 2 kg/ cm2
 space velocity ( liquid) 1 - 1.75 L /hr
 regeneration temp up to 520C
 catalyst shape pallets/ beads
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  Catalyst type silica- alumina
 cat processing capacity 20 - 40 bbl/kg
 feed temperature 430C
 air pressure during regeneration up to 4 kg/ cm2

Moving bed reactors : Appx 20% of total reactors

Thermofor Moving bed Reactor:

Catalyst shape in beads (appx 1/8 inch dia). Hot

catalyst and preheated feed meet at the top of reactor
and move downward by gravity. Hydrocarbon vapor
are separated from catalyst at the bottom of reactor
and sent to fractionating column. Spent catalyst
contains 02 - 04 % coke by wt, which after
regeneration contains less than 0.5% coke by wt.
Catalyst is transferred from bottom to surge
separator by air ( air velocity 85 - 90 ft/sec) and the
catalyst average velocity 35 - 40 ft/sec. In general
product yield and qualities of product are very similar
a obtained from fluidized bed cracker.
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43
Operating parameters:

 Regenration temperature : 600C

 Recycle ratio : 0-0.5 vol/vol
 Cat/ oil ratio :2-7
 Space velocity : 0.7 v/hr v
 Vapour inlet temp : 500 C
 Catalyst temp : 515C
 Reactor pressure : 3 atm

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45
Fluidized bed cracking : most widely used now .

In this process catalyst remains in fluidized state by

controlling the vapour velocity in the reactor. Catalyst
will be in intense agitation and form isothermal bed.
Heat transfer is very fast and catalyst requirement
will be less as powder has large surface area in
comparison of beads or pallets shape catalyst.

The hot oil feed is contacted with hot catalyst in the

feed riser or in reactor. As the cracking reaction
progressed , catalyst is progressively deactivated by
the deposition of coke on catalyst surface. Catalyst and
hydrocarbon vapor separated by cyclone separator.
hydrocarbons sent to fractionating column for product
separation and catalyst is steam stripped to remove
traces of hydrocarbon before the catalyst enters in
regenerator.

Spent catalyst flows into regenerator and is

reactivated by burning off the coke deposits with air.
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regenerator temperature is carefully controlled to
prevent catalyst deactivation by overheating and to
provide desired amount of carbon burn off. This is
done by controlling air flow to get desired CO2/CO
ratio in flue gas or the desired temperature in
regenerator. Flue gas and catalyst is separated by
cyclone separator and electrostatic precipitators.
Catalyst in some units is steam stripped to remove
oxygen before catalyst comes in contact with oil feed

FCC units can be classified as either bed or riser (

Transfer line) cracking units, depending upon where
major fraction of cracking occurs.. Today almost all
the FCC units have been reconfigured to operate
with riser cracking.

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ESSO FCC unit Model III

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Procees Parameter:

• Reactor temperature 470 - 510 C

• Reactor pressure 8 - 30 psig
• Regenrator temp 650 - 815C
• Regenrator pressure 15 - 30 psig
• Cat / feed ratio
• Recyle / fresh feed ratio 0.05
• Reactor space velocity lb/ hr/lb 1.1 -13.4
• cat requirment lb/bbl feed 0.15 -- 0.25
• cat circulation rate , ton cat/ bbl feed 0.9 - 1.5
• Gasoline octane number, RON 92 - 99
• Gasoline octane number , MON 80 - 85

Few Definitions :
• Catalst selectivity : ratio of desirable product to
undesirable product
• Conversion : 100*( vol of feed - vol of cycle oil)/ vol
of feed
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 • Efficiency : % gasoline * conversion
• Cycle stock : portion of catalytic reactor product
not converted to naptha and lighter products (
generally material boiling above 220C)

Process Variables in catalytic cracking:

Folowing are process variables in catalytic cracking.

1. feed stock quality:

Composition of the feed ie boiling range and
hydrocarbon type present. It fas been observed
that lowe bioling range feed cracks to give more
gases and C4 at a given conversion than does
higher boiling feed.
Aromatic are refracory in nature and it is difficut
to get high conversion on some high aromatic
feed, and the recycle stream containg high
aromatic passes through thr reactor virtually
unchanged Remova of aromatic by furfural
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 extraction has been used to make recycle sream
lessrefractory.
2. Cracking temperature:
Reactor temperature can be used to some extent
to vary product quality and yield, higher
temperature increases conversion. Increase in
tempersature not necessarily increases gasoline
yield as increase in temperature beyond a certain
range increases converion, coke , gas yield and
octane number of gasoline but decreases the
gasoline yield. Higher temperature gives more
unsaturatd product and this can also be used to
increases quantity of butenes in product and thus
total quantity of gasoline when butenes ae fed im
alkylation unit.
3. Reactor Pressure: Reactor pressure is not an
indepedent variable as it is fixed within a very
narrow range in a perticular system. However
increases in pressure increases coke yield and
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 degree of saturation of gasoline but decreases the
octane number. it has little effect on conversion.
4. Cat / oil ratio: Increase in this ratio incresae the
conversion.
5. Space velocity ( wt of oil feed/ wt of catralyst)
In the older types of reactor space velocity was an
important varible to contral the conversion.
increase in space velocity decresae the conversion
but it has less significance in transfer line craking
unit.
6. Catalyst type and activity ( activity : ability to
crack gas oil to lower boiling fraction):
Commercial catalyst can be diveded in three
class. (1) Acid treated natura aluminosilicate (2)
Amorphus synthetic Silica alumina combination
(3) Crystaline synthetic silic alumina cataalyst
calle zeolites . Most of the commercail catalyst
used cureenty are either of class 3 or mixtures of

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class 2 and class three. Catalyst type has a very
important effect on a detailed below

Advantage of zeolite catalyt over natural and

amorphus catalst are : higher activity , higher
gasoline yield at a given conversion . production of
gasoline containg larger % of paraffins and

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 aromatic hydrocarbon, lower coke yield, more
isobutene production, higher conversion per pass
without over cracking.

7. Recycle ratio ; ( vol of recycle / vol of fresh feed)

Recyle increses the conversion and yield of
gasoline will also be be maximum at a prticlar
recyle ratio . Furter inrease in recyle ratio will
increase the conversion but decrease the gasoline
yield through secondary cracking. High recycle
rate can be used only when there is no build up
of refaratory aromatic mterial , which tends to
form coke by condensation and polymerisation
reaction .

Catalyst activity and processing:

During the cracking process the catalyst becomes
slowly deactivated and it is necessary to add fresh
catalyst to maintain the activity at satisfactory
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level. Loss of catalyst to atmosphere via cyclone
in regenrator amounts to 0.5 - 1% by wt of the
catalyst inventory/ day and this must be replaced
continously. In some cases this replacement/
addition is sufficient to maitain catalyst activity
however where rate of deactivation is higher , in
such case withdrawl of some catalyst is practiced
along with the equivalent addition of fresh catalyst
in addition to the replacemt of cartlyst for loss of
catalust in proces. One measure of actalstactivity
is surface area and satisfactoy activity cn be
expected with a surfacearea of 120 m2/g.
Deactivation can occure by exposure of catalyst at
high temperature in the presence of steam which
quickly reduces the surface area. Thus use of
spray water to cool the regerator must therefore
be kept to minimum to reduce the deactivation
rate.

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Contamination of the feed with Na, Fe, Ni,V or Cu
will cause severe loss of activity. Sodium will
reduce the fusion temperature of catalyst and thus
may cause a rapid loss of surface area. Other
metals increase te dehydrogenation activity of
catalyst so that more hydrogen and coke are
produced at the expense of gasoline. Nitrogen
compounds will alsoreduce catalystactivity
because of therebasic nature, which neutralises
the acidic cracking sites on the catalyst.

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Hydrocracking:
Hydrocracking is a process by which the
hydrocarbon molecules of petroleum are broken
into simpler molecules, as of gasoline or kerosene,
by the addition of hydrogen under high pressure
and in the presence of a catalyst. This process
employs hydrogen gas to improve the hydrogen-
carbon ratio in the cracked molecules and to
arrive at a broader range of end products.

Hydrocracking is a catalytic chemical process

used in petroleum refineries for converting the
high-boiling hydrocarbons in petroleum to low-
boiling products such as gasoline, kerosene, jet
fuel and diesel oil. The process takes place in a
hydrogen-rich atmosphere at elevated
temperatures ( 260–425 °C) and pressures (35–200
bars).

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Any sulfur and nitrogen present in the
hydrocracking feedstock are, to a large extent,
also hydrogenated and form gaseous hydrogen
sulfide (H2S) and ammonia (NH3), which are
subsequently removed. The result is that the
hydrocracking products are essentially free of
sulfur and nitrogen impurities and consist mostly
of paraffinic hydrocarbons.
Catalytic hydrocracking involves three primary
chemical processes:

Cracking of high-boiling hydrocarbons found in

crude oil into lower-boiling hydrocarbons
Hydrogenating unsaturated hydrocarbons to
obtain saturated hydrocarbons, usually referred
to as paraffins or alkanes
Hydrogenating any sulfur, nitrogen or oxygen
compounds in the original feedstock into gaseous
hydrogen sulfide, ammonia and water
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 Some of the advantges of hydrocracking are:
 Octane number of hydrocracked gasolive is
better than obtained from catalytic cracker.
 better balance of gasoline and distillate
production
 production of relatively higher amount of
isobutane and butane fraction.
 It suppliments catalytic cracking to upgrade
heavy cracking stock, aromatics, cycle oils
and coker oil to gasoline, jet fuel and diesel.

Hydrocracking Reactions :

The Mechanism of hydrocracking is basically is

similar to that of catalytic cracking with
hydrogenation superimposed. The olefins produced by
catalytic cracking are readily hydrogenated to
saturaed compounds . This rapid hydrogenation
67
prevents the adorption of olefinic molecules on the
catsalyst surface and subsequent dehydrogenation
leading to coke formation. as in catalytic cracking , so
that long stream time can be obtained without
regeration.

The two different reaction systems in hydrocracking,

hydrogenation and cracking, are supported by bi-
functional catalyst formulations, as illustrated in
below Figure

68
Hydrogenation reactions are promoted by the metal
component of the catalysts (e.g., Ni, Co, Mo), and the

69
cracking takes place on catalyst support consisting of
silica/alumina. Highly active noble metals (e.g., Pt, and
Pd) can be used for hydrogenation of hydrocarbons
with extremely low sulfur contents as the noble metals
are susceptible to sulfur poisoning.

Hydrocracking processes most commonly include two

reaction stages: Hydrotreating to remove (S, N, O)
compounds and Hydrocracking to increase the H/C
ratio of the hydrocarbons in the feeds by
hydrogenation and to decrease their molecular weight
by cracking.

In most cases, the hydrotreating reactor (HT) packed

with cobalt-molybdenum catalysts precedes the
hydrocracking (HC) reactor typically packed with
nickel-tungsten catalysts (for hydrogenation)
supported on alumina/silica (for cracking).

On catalyst such as Ni or tungusten sulphide on

silica alumina , isomerisation does not takes place , as
70
uncracked normal paraffins from the feed stock
tends to retain their nrmal structure. Extensive
splitting produce large amount of low molecular wt (
C3 - C6) paraffins with high iso / normal ratio
indicating that primary reaction of of paraffins is
catalytic cracking followed by hydrogenation to form
isoparafins directly.

With catalyst of higher hydrogenation activity ie Pt

on silica alumina, durect isomerisation occurs. The
product distribution is also different and the ratio of
low to intermediate molecular wt paraffins in the
brealdown product reduced . This indicates less
secondary splitting due to higher hydrogenation
activity of the catalyst in converting cracked product
into stable paraffins more rapidly . The variotio with
iso / normal ratio with different catalyst shown as
under

71
The degree of cracking in the product is also depend
on feed stock. Decalin , which is multiring naphthene ,
cracks more redily than the corrosponding normal
paraffins to give more isi/ normal products ratio than
those obtaibed from paraffins. A large yield of single
ring naphthenes are produced and these are
resistant to further hydrocracking and contain a
higher eqlibrium ratio of methyal cyclopentane to
cyclohexane.

72
One of the most important reactions of hydrocracking
is partial hydrogenation of polycyclic aromatics
followed by splitting of saturated ring to form
substituted monocyclic aromatic. the side chains are
then split off to give isoparaffins . It is desirable to
avoid excessive hydrogenation activity of the catalyst
so that monocyclic aromatics becomes hydrogenated
to naphthenes. over hydrogenation leads to loss in
73
octane number and increased hydrogen absorption ,
and increases the catalytic reforming requirement to
process highly naphthenic hydrocracked naphtha.

Side chains of three to four carbon atoms are easily

removed from an aromatic ring in hydrocracking.
The reaction of aromatic rings with shorter side
chains appears quite different. . It has been found that
hydrocracking single ring aromatic with four or
more methyl gps, the products are largely isobutane
and benzene.

The sequence of hydrogenation and cracking

reaction in the hydrocracking of light cycle oil has
been studied and rate contestant of various reaction
are as under. The results given in the fig shows that

74
75
  Polycyclic aromatics are partially hydrogenated
rapidly
 Naphthenic rings in polycyclic compounds are
readily removed by ring opening followed by
cracking .
 single ring naphthenes and paraffins are more
resistant to cracking.
 Single ring aromatic are difficult to hydrogenate.

It was also found that saturated compounds ,

particularly paraffin's and single ring naphthenes
appear to react more slowly at low feed conversions
than at high conversion levels .

76
Catlayst :
Hydrocracking catalysts consist of active metals
on solid, acidic supports and have a dual function,
specifically a cracking function and a
hydrogenation function. The cracking function is
provided by the acid catalyst support and the
hydrogenation function is provided by the metals.
The Acid function is is usually supply by the
catalyst base as HF treated montmorillonite
clay, alumina, alumina silica and zeolite.
Hydrogenation function are suplllied by metals
such as Ni, Tungsten, Pd, Pt etc.
These highly acidic catalyst are very sensitve to
nitrogen compounds in feed, which break down
under the reaction conditition to give ammonia
ant it neuralise the acidic site leading to loss of
cracking activity. Some heavy gas oils contain
substantial amountof nitrogen (up to appx 2500
ppm), a purifocation stage may frequenty
77
required. Denitogenation and desulphurisation
may be carried out using Co -Mo or Ni/Co/ Mo
on alumina or alumina silica.
Hydrocracking catalyst such as Ni (5 % Wt ) on
silica alumina works best on feed stock which
have been previiusy hydrotreated to low S and N
level. . The Ni catalyst then operate well at 350 -
370 C and pressure of about 100 atm to give good
conversion of feed to lower boiling fraction with
minimum saturation of single ring aromatics
and give high iso / normal ratio of lower
paraffins. The poisioning effect of N can be offset
to a certen degree by operation at
highertemperature , but it will increase the
production of C1 to C4 material and carbon
and decrease the operation stability of catalyst , so
that it requries more frequent regenration.
Catalyst containing Pt or Pd ( appx 0.5% wt) on
zeolite base appears to be somewhat less sensitive
78
to N than the Ni catalysts, and work well with
feed containg 40 ppm N . This caralyst is more
tolrent to S in feed which acts as temporary
poision. . The catalyst recovers its activity when S
content in feed is reduced.
It has been obesrved that severe hydrocracking
operation like poroduction of gasoline from
vacuum gas oil , it is necessary to operate the
zeolite based catalyst at low N and S levels and
that is only possible to tolerate these poision
under less severe condition i.e. at low
temperature.
As the cracking operation go o , to counter
theloss of activity of catalyst , the reactor
temperature is increase day by day by 0.5 - 1 C .

79
Hydrocracking Process:
A number of hydrocracking process are avalible.
These process are normally fixed batch type or
ebullating bed type. The most sucessful process
are Isomax by UOP and Chevorn, Unicracking -
JHC by Union oil Co., Hydrocracking by Esso
and Houndary Gulf and Hydrocarbon research
Inc. also offered hudrocracking processes.
These Process may be single stage or 2 stage
depending upon thr severity requird and feed
quality. First stage reactor gve 40- 50% gasoline
conversion while the heavy portion (effuluent
from reactor I forms the feed stock for 2nd stage
reactor where 60% conversion is expected.

Isomax Process :
These are configured as single stange and double
stage fixed bed reactors.

80
In Single stage reactors , charge stock, recycle
hydrogen and makeup hydrogen are mixed and
passed through a heater The mixture enters to
reactor from top while cold hydrogen is admitted
into reactor at different points to maintain the
temperature. Effulents from the rteactors are are
immedately heat exchanged with the feed , cooled
and fed into high pressure seperator, where
hydrogen is seperatrd , Seperated hydrogen is
treated for the removal of H2S andNH3. The
recoverd and treated hydrogen is compressed to
required pressure and recycle back. Product
from high pressure seperator goes to low pressure
seperator where fuel gas upto C3 and remaining
H2S removed . Liquid fraction from the bottom is
sent to fractionater , where distillate are seperated
into diffrent fraction and unconverted heavy
fraction from the fractionator is recycled back to
reactor stock.
81
Two stage isomax process are also in use . It is
used when feed contains excessive amount of
sulphur and extent of eonversion requirmnet is
high. In this case bottom product from high
pressure seperator is mixed with fresh and
recyled hydrogen and after heating to required
temperature is fed to second stage reactor .
Product from second stage reactor is send to
seperator to remove light gases and bottom
product from seperator is sent to distillation
column to seperate into different fraction.
Unconverted heavy fraction is recylced back to
second stage reactor.

82
Isomax Hydrocraking single stage Process

83
 Isomax Hydrocraking two stage Process

Operating conditions :

Pressure : 30 - 100 atm

Temp reactor : 250 - 370 °C

Consumption of Hydrogen : 35 - 50 M3 / barrel

space velocity 0.2- 1.0 V/V/hr

84
Hydrogen recycle rate : 8000- 15000 scf / barrel

H. G. Hydrocracking Process :

H.G. Hydrocraking single stage Process

85
 H.G. Hydrocraking two stage Process

Gulf research & development Co and Houndary had

jointly deloped this process. In this orocess ,
86
conversion of light and heavy gas oil into more
valuable lower boiling products obtained. The
process is designed for single as well as double stage
operation as in Isomax process.

When two stage operation is employed , mild hydro

treating operation is carried out in first reactor and
hydro cracking in second reactor. Heavy fraction
from the distillation column may be recycled back to
the second reactor in case of two stage or into the
reactor in case of singe stage operation.

Ultra cracking of standrd oil operates on similar

lines as above. Catalyst used is multifunctional , these
function include denitrogenation, desulphurisation ,
olefins and aromatic saturation. Long life of the
catalyst is specialty of the process. In this process
water is directly injected into reactor effluent , which
absorb NH3 and partially H2S too.100% conversion

87
with feed of 70/30 mixture of Coker and heavy
catalytic oil is most usual.

Hydrocraking two stage Process

All the fixed bed operation resemble one another ,

they differ only in catalyst composition, feed stock
and product pattern.

88
( different types of fixed bed Hydrocracker design)

Fixed bed catalyst reactor tends to plug owing to

solids in the feed or carbon lay-down , when
processing residual feed. At high conversion problem
of temperature control due to excessive exothermic
reactions is also there.

Moving Bed ( Ebulient Bed) reactors.

89
Ebulient bed process had been developed by Citi
Services & Development Co, Hydrocarbon Research
Inc etc to overcome the process difficulty, especially in
the hydrocracking of residues in fixed bed reactor.

The advantages claimed in Ebulient bed are :

 Because bed are in moving or semi fluidized

state so behaves as isothermal system and
elaborate quenching system not required.
 addition and withdrawal of catalyst is possible
from reactor so catalyst activity can be
maintained at steady level
 accumulation of solid on catalyst bed is
minimized.

To achieve the moving bed condition feed and

hydrogen is fed to reactor from bottom. to maintain
the catalyst bed in fluidized bed , liquid from top of
the reactor may be recalculated from the bottom of
the reactor to maintain the bed in fluidized state. Two
90
reactor work in series in the process. Feed having BP
of 650C can be taken in this process .

Pressure of appx 200 atm ant temperature of 400 - 460

C is employed in these process.

Moving bed Hydro cracking Process

91
Moving bed Hydro cracking Process (H-Oil Unit)

92
93
Process variables in Hydrocracking:
The severity of hydrocracking operation / reactions is
measured by the degree of conversion of feed to
lighter products . conversion is defined as volume
percentage of feed that disappear to form products
boiling blow the desired product end boiling point.
In order to compare operation severity, it is necessary
to compare conversions to the same product end
point. A given % conversion at low product end point
represents more severe operation than does the same
% conversion at higher product end point.

The primary reaction variables are reactor

temperature and pressure, space velocity, hydrogen
consumption, hydrogen circulation rate, nitrogen and
sulphur content of the feed and hydrogen sulphide
content of gases.

Reactor Temperature :

94
Reactor temperature is the most important parameter.
t normal rector temperature 10C in temperature
almost doubles the reaction rate but does not affect
the conversion level much. High temperature favors
removal of nitrogen and thiophenic sulfur , but excess
temperature retards the reaction rate due to coke
formation.

Reactor Pressure: The primary effect of reactor

preesur is its effect on prtial pressure of hydrogen
andammonia. An increase in in total pressure
increases the partial pressure of hydrogen and
ammonia. Conversion increases with increasing of
hydrogen partial pressure and decreases with
increasing ammonia partial pressure.. Hydrogen effect
is more therefore net effect of raising total pressure is
to increase conversion.

Space Velocity: space velocity varies directly with

feed rate . More space velocity means less contact time

95
with catalyst. Increase in space velocity decreases
conversion rate. Temperature of the reactor should be
increased to maintain the conversion in case of
increased feed rate.

Nitrogen Content:

Organic nitrogen : It deactivated the catalyst .

Increase in organic nitrogen in feed decreases the
conversion.

Hydrogen circulation rate:

More is the hydrogen circulation rate higher will be

catalyst life. Higher rate will carry more impurities
from catalyst and rate of deposition of coke will be
less. However cost of circulation will be more so
circulation rate of hydrogen are optimized. Normally
circulation rate is 8 10 times more than hydrogen
consumption rate.

96
Deep Catalytic cracking:

Objective:

light olefins ( Ethylene and propylene) are the most

fundamental petrochemical raw materials. These are
produced by steam cracking of naphtha , LPG and
from off gases from FCC. To meet the ever increasing
demand of olefins, DCC is one such process which
uses VGO, VTB ( vacuum tower residue) or VGO
blended with DAO (De-asphalted oil) to produce light
olefins ( ethylene, propylene and butylenes).

Process Description :

The deep catalytic cracking (DCC) process is a

fluidized bed catalytic cracking (FCC) process
modified to increase the production of light olefins
from heavy oil feedstock. One commercial version,
DCC Type I, maximizes selectivity to propylene and
substantially increases the yield of ethylene. In a
97
second commercial version, DCC Type II, Iso-olefins
(isobutylene plus isoamylene) selectivity is maximized.
The two versions use different, novel zeolitic catalysts
and their reaction conditions differ. The Type I
operation produces a high-octane, aromatic naphtha
rich in toluene and xylenes. Operating conditions are
more severe than those in conventional catalytic
cracking. The Process scheme of DCC is similar to
FCC consisting of reactor, regenerator, distillation
and gas concentration sections. Feedstock dispersed
with steam is fed to reactor which contacted with hot
catalyst either in riser plus fluidized bed dense
reactor (for DCC I) or in a riser reactor ( for DCC II)
for cracking. Reactor product sent to fractionation
and gas concentration section for product separation.
Coke deposited catalyst is steam stripped and
transferred to regenerator for coke removal. Hot
regenerated catalyst transferred to reactor.

98
Reaction temperature is one of the most important
factor in cracking reaction. The optimum reaction
temperature in DCC is normally within 520 C - 580 C
varying with crackability of feed stocks and required
product. DDC I ( Maximum propylene mode) employ
higher temperature than DCC II ( Maximum iso
olefins) .

The crackablity of feedstock can have great effect on

operation parameters and product distribution.
Higher UOP K value and hydrogen content of
feedstock results in higher carakability and hence
higher olefins yield.

99
(DCC II configuration )

100
101
102
Hydro treatment:
Hydro treating, hydro processing, hydro cracking and
hydro desulphurization are various terms used in
industry.

In hydro cracking and hydro desulfurization,

cracking and desulphurization occur simultaneously,
but intentions are different. In hydro cracking
primary aim is to lower down the boiling range of the
products and in hydro desulphurization primary aim
is to remove S, N, and oxygen and cracking are
minimized by process variation and selection of
catalyst

Hydro treating is relatively mild process used to

stabilize the product by saturation of olefins or it may
be used for treatment of lubricating oil for
improving VI, color removal, oxidation stability etc.

103
Catalyst for hydro treatment: cobalt and
molybdenum sulphide on alumina is the most widely
used catalyst.

Most economic catalyst for sulphur removal

contain cobalt and molybdenum sulphide on alumina
support . for nitrogen removal Ni Co Mo or Ni Mo
compounds supported on alumina are more efficient.
Ni tungsten is most efficient for nitrogen removal and
saturation of aromatic ring to reduce aromatic
content but much more expensive than Ni Mo and not
used widely.

Hydro treatment of lubes oil

1. Hyrofining Process: :

this process stabilizes the undesirable compounds by

mild catalytic hydrogenation. Oxygen containing
compounds are converted in low boiling compounds
hydrocarbon and water. This process removes almost

104
al of the oxygen, 50% S but very little nitrogen.
Conditions are such not to affect hydrocarbon but
unsaturated bonds will be saturated. Reactor temp 200
- 425 C and pressure from 7 to 80 atm, Space
velocity 2 v/hr/v. Operating conditions to be optimized
for the process depending on feedstock and product
required.

105
Mild hydro treating process:

Naphthenic oil are widely used as process oil and

general industrial lubricant. Good color and color
stability are the major requirement of lubricating oil.
Nitrogen compounds are largely responsible for poor
color and color stability . In this process most of the
nitrogen compounds are removed. Process is similar
to hydrofinning but vacuum distillation Coolum is
additional.

106
Severe hydro treating Process:

This process is used for improving VI of lubricants oil.

In this process extensive hydro cracking in addition of
saturation of aromatics and destructive
107
hydrogenation of non hydrocarbon occurs. The
process is similar to mild hydro treating but designed
to achieve greater severity. Higher temperature is
used, catalyst used is such that promotes ring scission.

Severe hydro treating can produce a wide range of

high VI oil from low quality feedstock's. Product
quality and yield are comparable as from solvent
extraction. However oil with VI from 120 - 130 can be
produced by this method which normally cannot be
produced by solvent extraction. Apart from high VI
oil , other products as diesel, gasoline and high
quality light lube oils are produced as by product.

108
109