MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY, JAIPUR

JAIPUR, RAJASTHAN 302017

DEPARTMENT OF CHEMICAL ENGINEERING
PETROLEUM REFINING REPORT:
DCC-DEVLOPMENT OF CATALYTIC CRACKING AND
HYDROCRACKING

______________________________________________________________________________

SUBMITTED TO:
Mr. Shiv Om Meena
Assistant Professor
Department OF Chemical Engineering

SUBMITTED BY:
Himanshu Sharma
2013UCH1091
CH1

INDEX
1. INTRODUCTION
2. CATALYTIC REACTIONS
3. CRACKING OF PARAFFINS
4. CRACKING OF OLEFINS
5. CRACKING OF NAPTHENIC HYDROCARBONS
6. HYDROCRACKING
7. HYDROCRACKING PROCESS

catalytic cracking
INTRODUCTION
Main incentive for catalytic cracking is the need to increase gasoline
production.
Feedstocks are typically vacuum gas oil.
Besides C - C cleavage many other reactions occur:
- isomerisation
- protonation and deprotonation
- alkylation
- polymerization
- cyclization and condensation
The catalytic cracking process is very flexible, and operating parameters can
be adjusted to meet changing product demand.
Catalytic cracking breaks complex hydrocarbons into simpler molecules in
order to increase the quality and decrease the amount of residuals.
This process rearranges the molecular structure of hydrocarbon compounds to
convert heavy hydrocarbon feedstock into lighter fractions such as kerosene,
gasoline, liquified petroleum gas (LPG), heating oil, and petrochemical
feedstock.
Catalytic cracking is similar to thermal cracking except:
1. catalysts facilitate the conversion of the heavier molecules into lighter
products.
2. Use of a catalyst acts under much less severe operating conditions than in
thermal cracking.
Typical temperatures are from 850-950 F at much lower pressures of 10-20
psi.

4 Cracking is catalyzed by solid acids which promote the rupture of C-C

bonds. The crucial intermediates are carbocations (+ve charged HC ions)
formed by the action of the acid sites on the catalyst.
The catalysts used in refinery cracking units are:
Zeolite
aluminum hydrosilicate
treated bentonite clay
fuller's earth
Bauxite
silica-alumina
catalysts form:
powders
beads
Pellets
shaped materials called extrudites
5 There are three basic functions in the catalytic cracking process:
1. Reaction: Feedstock reacts with catalyst and cracks into different
hydrocarbons
2. Regeneration: Catalyst is reactivated by burning off coke
3. Fractionation: Cracked hydrocarbon stream is separated into various
products.
The three types of catalytic cracking processes are
1. fluid catalytic cracking (FCC)
2. moving-bed catalytic cracking
3. Thermofor catalytic cracking
CRACKING REACTIONS

 primary reactionsPrimary reactions are designed as those involving the initial

carboncarbon bond scission and the immediate neutralization of the carbonium
Paraffin paraffin + olefin
Alkyl naphthene naphthene naphthene naphthene + olefin
Alkyl aromatic aromatic + olefin
secondary reactions
1. carbonium ions are formed initially by a small amount of thermal cracking of
n-paraffins to form olefins.
2. These olefins add a proton from the catalyst to form large carbonium ions
which to form small carbonium ions and olefins.
3. The small carbonium ions propagate the chain reaction by transferring a
hydrogen ion from a n-paraffin to form a small paraffin molecule
Step 1: Mild thermal cracking initiation reaction.
nC8H18 CH4 + RECHCCH2
Step 2: Proton shift.

Step 3: Beta scission.

Step 4: Rearrangement toward more stable structure. The order of

carbonium ion stability is tertiary> secondary> primary.

 Step 5: Hydrogen ion transfer.

CRACKING OF PARAFFINS
The catalytic cracking of paraffins is characterized by
1. high production of C3 and C4 hydrocarbons in the cracked gases
2. reaction rates and products determined by size and structure of paraffins
3. isomerization to branched structures
4. aromatic hydrocarbons formation resulting from secondary reactions
involving olefins.
OLEFIN CRACKING
The catalytic cracking rates of olefinic hydrocarbons are much higher than
those of the corresponding paraffins.
The main reactions are :
1. Carboncarbon bond scissions
2. Isomerization
3. Polymerization
4. Saturation, aromatization, and carbon formation
Olefin isomerization followed by saturation and aromatization are responsible
for the high octane number and lead susceptibility of catalytically cracked
gasolines.
The higher velocity of hydrogen transfer reactions for branched olefins results
in ratios of iso- to normal paraffins higher than the equilibrium ratios of the
parent olefins.
naphthenes act as hydrogen donors in transfer reactions with olefins to yield
isoparaffins and aromatics.

CRACKING OF NAPHTHENIC HYDROCARBONS

dehydrogenation to aromatics
There is also carboncarbon bond scission in both the ring and attached side
chains but at temperatures below 1000F (540 C) the dehydrogenation
dehydrogenation reaction reaction is considerably considerably greater.
Dehydrogenation is very extensive for C9 and larger naphthenes and a highoctane gasoline results.
The non-ring liquid products and cracked gases resulting from naphthenic
hydrocarbon cracking are more saturated than those resulting from cracking
paraffins.
AROMATIC HYDROCARBON CRACKING
Aromatic hydrocarbons with alkyl groups containing less than three carbon
atoms are not very reactive.
The predominant reaction for aromatics with long alkyl chains is the clean
splitting off of side chains without breaking the ring. 20 CRACKING
CATALYSTS
Commercial cracking catalysts can be divided into three classes:
(1) acid-treated natural aluminosilicates
(2) amorphous synthetic silica-alumina combinations
(3) crystalline synthetic silica-alumina catalysts called zeolites or molecular
sieves.
Most catalysts used in commercial units today are either class 3 or mixtures
mixtures of classes of classes 2 and 3 catalysts. catalysts.
The advantages of the zeolite catalysts
1. Higher activity
2. Higher gasoline yields at a given conversion
3. Production of gasolines containing a larger percentage of paraffinic and
aromatic hydrocarbons

4. Lower coke yield (and therefore usually a larger throughput at a given

conversion level)
5. Increased isobutene production .
6. Ability to go to higher conversions per pass without overcracking.
The catalytic effects of zeolitic catalysts can be achieved with only 10 to 25%
of the circulating catalyst as zeolites and the remainder amorphous silicaalumina cracking catalyst.
Amorphous catalysts have higher attrition resistance and are less costly than
zeolitic catalysts.
thus obtain the benefits of the higher activity and gasoline selectivity of the
zeolites and the lower costs and make-up rates of the amorphous catalysts.
Poisons of cracking catalysts
basic nitrogen compounds, iron, nickel, vanadium, and copper
The nitrogen reacts with the acid centers on the catalyst and lowers the catalyst
activity.
The metals deposit and accumulate on the catalyst and cause a reduction in
throughput by increasing coke formation and decreasing decreasing the amount
of coke burn -off per unit of air by catalyzing coke combustion to CO2 rather
than to CO.
nickel has about four times as great an effect on catalyst activity and selectivity
as vanadium deposition of nickel and vanadium reduces catalyst activity by
occupying active catalytic sites, promote the formation of gas and coke and
reduce the gasoline yield at a given conversion level.

Hydrocracking
Hydrocracking is a two-stage process combining catalytic cracking and
hydrogenation, wherein heavier feedstocks are cracked in the presence of
hydrogen to produce more desirable products.
The process employs high pressure, high temperature, a catalyst, and
hydrogen.

 The hydrocracking process largely depends on the nature of the feedstock and
the relative rates of the two competing reactions, C. Hydrocracking
hydrogenation and cracking.
Heavy aromatic feedstock is converted into lighter products under a wide
range of very high pressures (1,000-2,000 psi) and fairly high temperatures
(750-1,500 F), in the presence of hydrogen and special catalysts.
Hydrocracking produces relatively large amounts of isobutane for alkylation
feedstock. Hydrocracking also performs isomerization for pour-point control
and smoke-point control, both of which are important in high-quality jet fuel.
Hydrocracking is used for feed stocks that are difficult to process by either
catalytic cracking or reforming, since these feed stocks are Hydro cracking feed
stocks.
1. high polycyclic aromatic content
2. high concentrations of the two principal catalyst poisons, sulfur and nitrogen
compounds.

. Important role of hydrogen

1. When the feedstock has a high paraffinic content, the primary function of
hydrogen is to prevent the formation of polycyclic aromatic compounds
2. to reduce tar formation and prevent buildup of coke on the catalyst.
3. Hydrogenation also serves to convert sulfur and nitrogen compounds present
in the feedstock to hydrogen sulfide and ammonia.

Hydrocracking process
Preheated feedstock is mixed with recycled hydrogen and sent to the firststage reactor, where catalysts convert sulfur and nitrogen compounds to H 2S
and NH 3. Limited hydrocracking also occurs.
After the hydrocarbon leaves the first stage, it is cooled and liquefied and run
through a separator. The hydrogen is recycled to the feedstock.
The liquid is charged to a fractionator.

 The fractionator bottoms are again mixed with a hydrogen stream and
Hydrocracking Process
The fractionator bottoms are again mixed with a hydrogen stream and charged
to the second stage. Since this material has already been subjected to some
hydrogenation, cracking, and reforming in the first stage, the operations of the
second stage are more severe (higher temperatures and pressures). Again, the
second stage product is separated from the hydrogen and charged to the
fractionator.
Depending on the products desired (gasoline components, jet fuel, and gas
oil), the fractionator is run to cut out some portion of the first stage reactor
outturn.
Kerosene-range material can be taken as a separate side-draw product or
included in the fractionator bottoms with the gas oil.
The fractionator bottoms are again mixed with a hydrogen stream and charged
to the second stage.
Since this material has already been subjected to some hydrogenation,
cracking, and reforming in the first stage, the operations of the second stage are
more severe (higher temperatures and pressures).
Like the outturn of the first stage, the second stage product is separated from
the hydrogen and charged to the fractionator.