Petrochemical & Petroleum

Refining Technology
Conversion Process
Conversion
 Change the size and/or 2. Unification (combining)
structure of hydrocarbon
molecules - alkylation & polymerization

1. Decomposition (dividing) 3. Alteration (rearranging)

- hydro, thermal & catalytic - isomerization & catalytic

cracking, coking and reforming
visbreaking
Catalytic Cracking Process
Catalytic Cracking Process
 Catalytic cracking breaks up  This process rearranges the
complex hydrocarbons into molecular structure, converting
simpler molecules in order to heavy hydrocarbon feedstocks into
increase the quality and quantity lighter fractions such as kerosene,
of lighter, more desirable products gasoline, LPG, heating oil and
and decrease the amount of petrochemical feedstocks
residuals.
 Selection of a catalyst depends
 Heavy hydrocarbons are exposed upon a combination of the
at high temperature and low greatest possible reactivity and
pressure to catalysts which the best resistance to attrition.
promote chemical reactions..
Catalytic Cracking Process
 The catalysts used in refinery
cracking units are typically solid
materials (zeolite, aluminium
hydrosilicate, treated bentonite
clay, Fuller’s earth, bauxite and
silica-alumina) which are in the
form of powders, beads, pellets or
shaped materials called extrudites
Catalytic Cracking Process
Catalytic Cracking Process
 There are three basic functions in all catalytic cracking processes:
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.
Catalytic Cracking Process
 Catalytic cracking processes are very flexible and operating
parameters can be adjusted to meet changing product demand. The
three basic types of catalytic cracking processes are:
1. fluid catalytic cracking (FCC)
2. moving bed catalytic cracking
3. thermofor catalytic cracking (TCC).
Fluid Catalytic Cracking
 Fluid-bed catalytic crackers have  The FCC process mixes a
a catalyst section (riser, reactor preheated hydrocarbon charge
and regenerator) and a with hot, regenerated catalyst as it
fractionating section, both enters the riser leading to the
operating together as an reactor.
integrated processing unit.
 The charge combines with
 The FCC uses finely powdered recycle oil within the riser, is
catalyst, suspended in oil vapour vaporized and is raised to reactor
or gas, which acts as a fluid. temperature by the hot catalyst.
 Cracking takes place in the feed  As the mixture travels up the
pipe (riser) in which the mixture of reactor, the charge is cracked at
catalyst and hydrocarbons flow low pressure.
through the reactor.
Fluid Catalytic Cracking
 This cracking continues until the  Spent catalyst flows through the
oil vapours are separated from the catalyst stripper to the
catalyst in the reactor cyclones. regenerator where it mixes with
preheated air, burning off most of
 The resultant product stream the coke deposits.
enters a column where it is
separated into fractions, with  Fresh catalyst is added and
some of the heavy oil directed worn-out catalyst removed to
back into the riser as recycle oil. optimize the cracking process.
 Spent catalyst is regenerated to
remove coke which collects on the
catalyst during the process.
Fluid Catalytic Cracking
Moving Bed Catalytic Cracking
 Moving-bed catalytic cracking is  The cracked product is separated
similar to fluid catalytic cracking; into recycle gas, oil, clarified oil,
however, the catalyst is in the form distillate, naphtha and wet gas.
of pellets instead of fine powder.
 The pellets move continuously
by conveyor or pneumatic lift
tubes to a storage hopper at the
top of the unit, and then flow
downward by gravity through the
reactor to a regenerator.
 The regenerator and hopper are
isolated from the reactor by steam
seals.
Thermofor Catalytic Cracking
 In thermofor catalytic cracking,
the preheated feedstock flows by
gravity through the catalytic
reactor bed.
 Vapours are separated from the
catalyst and sent to a fractionating
tower.
 The spent catalyst is
regenerated, cooled and recycled,
and the flue gas from regeneration
is sent to a carbon monoxide
boiler for heat recovery.
Catalytic Cracking Reaction
Products in catalytic cracking are the results of
1. Primary reaction
2. Secondary reaction

Primary reaction:
Carbon-carbon bond scission & neutralization of the carbonium ion
Paraffin paraffin + olefin
Alkyl naphtene naphtene + olefin
Alkyl aromatic aromatic + olefin
Catalytic Cracking Reaction
Catalytic Cracking Reaction
Secondary reaction:
Isomerization, polymerization, saturation, aromatization, carbon
formation
Pre-treatment
1. Reduced sulfur & nitrogen
2. Increased production of naphtha & LCO yield

Types of pretreatment:
Deasphalting : to prevent excessive coking on catalyst surfaces
 Demetallation (Ni, V): prevent catalyst deactivation
 Hydrocracking: to prevent excessive coking
Catalyst
 A substance added to a chemical
reaction that facilitates or causes
the reaction but when the reaction
is complete the catalyst comes out
just like it went in.
 In other words, the catalyst does
not change chemically. It causes
reactions between other
chemicals
Catalyst
1. Zeolite
2. Aluminium hydrosilicate
3. Treated bentonite clay
4. Fuller’s earth
5. Bauxite
6. Silica-alumina

Zeolite
Catalyst
 Higher activity
 Higher gasoline yields
 Gasoline production contained
larger % of paraffinic and aromatic
content
 Lower coke yield
 Increased isobutane production
 Higher conversions
Fluidized Catalytic Cracker (FCC)
FCC Cyclone FCC Regenerator
(located in the reactor)
Catalytic Cracker at ExxonMobil's Oil Refinery
Hydrocracking Process
Hydrocracking Process
 Hydrocracking is a two-stage  In the process, heavy aromatic
process combining catalytic feedstock is converted into lighter
cracking and hydrogenation, products under very high
wherein distillate fractions are pressures and fairly high
cracked in the presence of temperatures.
hydrogen and special catalysts to
produce more desirable products.  When the feedstock has a high
paraffinic content, the hydrogen
 Hydrocracking has an advantage prevents the formation of PAHs,
over catalytic cracking in that high- reduces tar formation and
sulphur feedstocks can be prevents build-up of coke on the
processed without previous catalyst.
desulphurization.

Hydrocracking Process
 Hydrocracking produces  Sulphur and nitrogen
relatively large amounts of compounds are converted by a
isobutane for alkylation feedstocks catalyst in the primary stage
and also causes isomerization for reactor to hydrogen sulphide and
pour point control and smoke ammonia.
point control, both of which are
important in high-quality jet fuel.  The residual is heated and sent
to a high-pressure separator,
 In the first stage, feedstock is where hydrogen-rich gases are
mixed with recycled hydrogen, removed and recycled.
heated and sent to the primary
reactor, where a large amount of
the feedstock is converted to
middle distillates.
Hydrocracking Process
 The remaining hydrocarbons are  These products go through a
stripped or purified to remove the series of high- and low-pressure
hydrogen sulphide, ammonia and separators to remove gases, which
light gases, which are collected in are recycled.
an accumulator, where gasoline is
separated from sour gas.  The liquid hydrocarbons are
stabilized, split and stripped, with
 The stripped liquid hydrocarbons the light naphtha products from
from the primary reactor are the hydrocracker used to blend
mixed with hydrogen and sent to gasoline while the heavier
the second-stage reactor, where naphthas are recycled or sent to a
they are cracked into high-quality catalytic reformer unit.
gasoline, jet fuel and distillate
blending stocks.
Hydrocracking Process
Reasons of Hydrocracking
Process
1. Demand for petroleum
products has shifted to high
ratios of gasoline and jet fuel
compared usage of diesel fuel
and home heating oils
2. By product hydrogen at low
cost and large amounts
3. Limiting sulfur & aromatic
compound in motor fuels have
increased
Advantages of Hydrocracking
Process
1. Better balance of gasoline &
distillate production
2. Greater gasoline yield
3. Improved gasoline octane
quality & sensitivity
4. Production of relatively high
amounts of isobutane in the
butane fraction
Hydrocracking Reaction
 Mechanism of hydrocracking is superimposed of catalytic cracking &
hydrogenation
 Catalytic cracking is the scission of a carbon-carbon single bond
 Hydrogenation is the addition of hydrogen to a carbon-carbon double
bond
Hydrocracking Reaction

 Cracking & Hydrogenation are complementary

 Cracking provides olefins for hydrogenation

Hydrogenation provides heat for cracking

 Overall reaction provides excess heat  quenching unit

Hydrocracking Reaction
Thank You