LU3: OIL

DISTILLATION,
THERMAL CRACKING,
CATALYTIC CRACKING
ASSOC PROF DR SIM SIONG FONG
 Introduction to refinery

• Petroleum refining is the separation of petroleum into fractions and

the subsequent treating of these fractions to yield marketable
products.

• Refinery processes must be selected in which petroleum is

converted into products according to the demand.

• The development of new petroleum refining processes are due to:

 The demand for products such as gasoline, diesel, fuel oil, and jet fuel,
 Feedstock supply
 Environmental regulations that include more stringent regulations in relation to sulfur in gasoline
and diesel
 Technology development such as new catalysts and processes.
 Refinery processes

(1) Separation processes- distillation

(2) Conversion processes – thermal and catalytic cracking
(3) Treatment processes – hydrotreating
Crude oil distillation 4
 Desalting

• Before the separation of petroleum into its various constituents,

there is the need to clean the petroleum – desalting and
dewatering.

• Desalting is a water-washing operation performed at the

production field and at the refinery site - to remove water-soluble
minerals and entrained solids.

• If these crude oil contaminants are not removed, they can cause
equipment plugging, corrosion and catalyst deactivation.
Figure 1 : A Desalting Unit
 ATMOSPHERIC DISTILLATION

• Distillation unit – heating unit and fractional distillation tower.

• The feed to a distillation tower is heated by flow-through pipes
arranged within a large furnace.
• The pipe heats the feed to a predetermined temperature - a
predetermined portion of the feed will change into vapor.
• The vapor is held under pressure until it discharges as a foaming
stream into the fractional distillation tower.
• The unvaporized descends to the bottom of the tower to be
pumped away as a bottom non-volatile products.
An atmospheric distillation unit
 Vacuum distillation

• Operating conditions - 50 to 100 mm of mercury (atmospheric pressure =

760 mm of mercury).

• The vacuum tower has a larger diameter than the atmospheric units.

• Heavy gas oil may be obtained as an overhead product at temperatures of

150 C.

• Lubricating oil (light, intermediate, heavy) cuts may be obtained at

temperatures of 250 C to 350 C.

• Feed and residue (asphalt) are kept below the temperature of 350C,
above which cracking will occur.
A vacuum distillation unit
Crude oil distillation
Crude oil distillation
Thermal Cracking
 Thermal cracking

• It is one of the earliest conversion processes - decomposition of

higher-boiling materials into lower-boiling products.
• The majority of the thermal cracking processes use
temperatures of 455C to 540C and pressures of 100 to 1000
psi.
• Visbreaking,
• Steam cracking,
• Coking: delayed and continuous
 VISBREAKING

• It was initially introduced to reduce the viscosity of residue to

allow the products to meet fuel oil specifications or to be blended
with lighter product oil.

• In a typical visbreaking operation, a crude oil residuum is passed

through a furnace where it is heated to a temperature of 480C
under an outlet pressure of about 100 psi.

• The overhead material from this chamber is fractionated to

produce a low-quality gasoline as an overhead product and light
gas oil as bottom.
A visbreaker
 Steam cracking

• This process break ethane, butane and naptha into ethylene and
benzene - chemicals.

• The operating facilities are similar to gas oil cracking units,

operating at temperatures of 840C and at low pressures.

• Steam is added to the vaporized feed to achieve a 50–50

mixture, and furnace residence times are only 0.2 to 0.5 sec.
 Steam cracking

• Ethane extracted from natural gas is the predominant

feedstock for ethylene cracking units.
• Propylene and butylene are largely derived from catalytic
cracking units and from cracking a naphtha or light gas oil
fraction to produce a full range of olefin products.
Steam cracking process

CH 3 CH 3 CH 3 + CH 3 I n it ia t io n

CH 3 CH 3 + CH 3 CH 4 + CH 3 CH 2

P r o p a g a t io n
CH 3 CH 2 CH 2 CH 2 + H

H + CH 3 CH 3 H 2 + CH 3 CH 2

2 CH CH 3 CH 2 CH 2 CH 3
3 CH 2 T e r m in a t io n
CH
CH 3 CH 2 + H CH 3 3
 Steam cracking process

 n-octane for example:

 Thermal cracking is initiated by homolysis of a C-C bond to form two
free radicals.

CH 3(CH 2)6CH 3 CH 3CH 2CH 2CH 2CH 2

+ CH 2CH 2CH 3

Abstraction of secondary hydrogen is favored over primary hydrogen due to

the lower C-H bond energy, with an equal probability for removal of each
secondary hydrogen.
 Steam cracking process

 Any of these radicals can also undergo -cleavage to form

ethylene or propene and a shorter alkyl radical.

CH 3CH 2CH 2CH 2CH 2 CH 3CH 2CH 2 + CH 2 CH 2

CH 3(CH 2)3CH 2CH 2CH 2CHCH 3 CH 3(CH 2)3CH 2 + CH 2=CHCH 3

 Coking

• Coking is a thermal process for the continuous conversion of

heavy, low-grade oils into lighter products.

• Unlike visbreaking, coking involves complete thermal conversion

of the feedstock (residuum) into volatile products and coke.

• The products are gases, naphtha, fuel oil, gas oil and coke.
 Coking

• Gas oil is the major product of a coking operation and serves as a

feedstock for catalytic cracking units.

• The coke obtained is used as fuel but specialty uses - electrode

manufacture, production of chemicals and metallurgical coke.

• The coke may require treatment to remove sulfur and metal

impurities.
A delayed coker
Catalytic Cracking
 Historical development

• In the 1930s, thermal cracking units produced approximately

50% of the total gasoline.

• The octane number of this gasoline was about 70 compared

with 60 for straight-run (distilled) gasoline.

• The thermal reforming and polymerization processes that were

developed during the 1930s could be expected to further
increase the octane number of gasoline to some extent.
 Overview of Catalytic Cracking

 Catalytic cracking breaks complex hydrocarbons into simpler molecules with

the aims:
 To increase the quality and quantity of lighter fraction
 To increase more desirable products
 To decrease the amount of residuals

 This process rearranges the molecular structure of hydrocarbon compounds to

convert heavy hydrocarbon feedstock into lighter fractions.
 Catalytic cracking is similar to thermal cracking, except that catalysts
facilitate the conversion of the heavier molecules into lighter products (the
operating conditions is less severe than in thermal cracking).
 Overview of Catalytic Cracking

 Typical temperatures are from 440°-510 °C at much lower pressures of

10-20 psi.

 The catalysts used are typically solid materials (zeolite, aluminum

hydrosilicate, treated bentonite clay, fuller's earth, bauxite, and silica-
alumina) that come in the form of powders, beads, pellets or shaped
materials.
 Overview of catalytic cracking

• Catalytic cracking process involves contacting a gas oil faction

with an active catalyst under suitable conditions of temperature,
pressure, and residence time.
• A substantial part (>50%) of the gas oil is converted into gasoline
and lower-boiling products.
• During the cracking reaction, carbonaceous material is deposited
on the catalyst reduces its activity.
• Removal of the deposit is necessary- by burning the catalyst in the
presence of air, until catalyst activity is re-established.
 Historical development

• In 1936, a new cracking process opened the way to higher-

octane gasoline—this process was catalytic cracking.

• This process is basically the same as thermal cracking, but

differs by the use of a catalyst, which is not (in theory)
consumed in the process, and directs the course of the cracking
reactions to produce more of the desired higher-octane
hydrocarbon products.
 Advantages of catalytic cracking
over thermal cracking
 The gasoline produced has a higher octane number.
 The catalytically cracked gasoline consists largely of iso-paraffins
and aromatics, which have high octane numbers and greater
chemical stability than monoolefins and diolefins which are
present in much greater quantities in thermally cracked gasoline.
 Substantialquantities of olefinic gases suitable for polymer
gasoline manufacture and smaller quantities of methane, ethane,
and ethylene are produced.
 Advantages of catalytic cracking over thermal
cracking

 Sulfurcompounds are changed in such a way that the sulfur

content of catalytically cracked gasoline is lower than in
thermally cracked gasoline.
 Produces less heavy residual or tar and more of the useful gas
oils than does thermal cracking.
 The process has considerable flexibility, permitting the
manufacture of both motor and aviation gasoline and a variation
in the gas oil yield to meet changes in the fuel oil market.
 Comparisons Catalytic Vs Thermal
Cracking
 Catalytic Cracking is different from Thermal Cracking
 Uses a catalyst
 Lower temperature
 Lower pressure
 More flexible
 Different reaction mechanisms
 Ionic vs. free radical
 High thermal efficiency
 Good integration of cracking and
regeneration
 High yields of gasoline and other
distillates
 Low gas yields
 High product selectivity
 Low n-alkane yields
 High octane number
 Chain-branching and high yield of
C4 olefins
 High yields of aromatics
 Catalytic Cracking

 Reaction - Feedstock reacts with catalyst and cracks into

different hydrocarbons;

 Regeneration - Catalyst is reactivated by burning off coke;

 Fractionation - Cracked hydrocarbon stream is separated into

various products.
Schematic of catalytic cracking process
Cracking Processes
 Fluid catalytic cracking (FCC)

• Fluid catalytic cracking was introduced in 1942 involving continuous

feedstock flow with fluidized-bed catalysts.

• Fluid catalytic cracking units are currently in place in approximately

400 refineries around the world and the units are considered to be one
of the most important achievements of the twentieth century.

• Most fluid catalytic cracking units are operated to maximize

conversion to gasoline and LPG.
 Fluid catalytic cracking (FCC)

• In the unit, the catalyst and the feed

and product hydrocarbons are lifted up
the riser pipe to the reactor.
• As the reactions are endothermic,
reaction temperature declines from
bottom to top.
• Cracked gases are separated and
fractionated; the catalyst and residue,
together with recycle oil from a
second-stage fractionator, pass to the
main reactor for further cracking.
• The products of this second-stage
reaction are gas, gasoline and gas oil
streams, and recycle oil.
 Fluid Catalytic Cracking (FCC)

 Fluid-bed catalytic crackers have a

catalyst section (riser, reactor and
regenerator) and a fractionating section,
both operating together as an integrated
processing unit.
 The FCC uses finely powdered catalyst,
suspended in oil vapor or gas, which
acts as a fluid.
 Cracking takes place in the feed pipe
(riser) - mixture of catalyst and
hydrocarbons flow through the reactor.
Moving Bed Catalytic Cracking (MBCC)

 Moving-bed catalytic cracking is similar to fluid catalytic

cracking;

 however, the catalyst is in the form of pellets instead of fine

powder.

 The cracked product is separated into recycle gas, oil,

clarified oil, distillate, naphtha and wet gas.
 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.
 Hydrocracking

• Hydrocracking is a thermal process in which hydrogenation

accompanies cracking.

• Two stage processes combining catalytic cracking reactions

with hydrogenation where heavier feedstock are cracked in the
presence of hydrogen to produce more desirable products.

• The process employs high pressure, high temperature, a catalyst,

and hydrogen.
 Hydrocracking

• The feedstocks are characterized by

a high polycyclic aromatic content
 and/or high concentrations of the two principal catalyst poisons,
sulfur and nitrogen compounds, difficult to process by catalytic
and reforming process.
 Hydrocracking

• Hydrogen is also used:

 To reduce tar formation;
 To prevent build up of coke on the catalyst.
 Serves to convert sulfur and nitrogen compounds present in the
feedstock to hydrogen sulfide and ammonia.
 Hydrocracking

• The overall result is usually a change in the character or quality

of the products.

• 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

 In the first stage, preheated feedstock is

mixed with recycled hydrogen and sent to
the first-stage reactor, where catalysts
convert sulfur and nitrogen compounds to
hydrogen sulfide and ammonia.

 After the hydrocarbon leaves the first stage,

it is cooled and liquefied and run through a
hydrocarbon separator.

 The hydrogen is recycled to the feedstock.

The liquid is charged to a fractionator.

HP High pressure (hydrogen is separated & recycled back to the reactor)

LP Low pressure (stabilizes the liquid products)
 Hydrocracking

 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).
 The second stage product is separated
from the hydrogen and charged to the
fractionator.
 Partial saturation
H13
C6 2H2 H13
C6 CH
2

C2H5 CH
2 C2H5

4H2 Ringseparation &

Typical opening

hydrocracking H13
C6 CH C2H5
+ H

reactions CH C2H5

Sidechain hydrocracking&
Isomerization

CH
3
C2H5
C C3H7
H
+
CH
3
 Hydrocracking

 Hydrocracking – is a combination of catalytic cracking and

hydrogenation carried out over dual function catalysts (generally
alumina-silicates doped with metals) at 400°C and 65-135 atm of H 2.
 Most olefins are reduced to their corresponding alkanes and as a
consequence the product does not have as high an octane number.
 Its advantage is that it eliminates the formation of coke in the reactor.
 In practice it is more expensive than normal catalytic cracking and is
used as a complement rather than as a replacement – for cracking the
higher boiling residues left after catalytic cracking.
 This is a method of
producing high octane
gasoline products from
the gaseous byproducts
of catalytic cracking,
which contain
substantial amounts of
isobutane, butene and
propene. Catalytic Cracking of a Vacuum Distillate (350-
550°C) from Middle East Crude
 Hydrocracking

• Better balance of gasoline and distillate production.

• Greater gasoline yield.
• Improved gasoline pool octane quality and sensitivity.
• Production of relatively high amounts of isobutane in the
butane fraction.
• Supplementing of fluid catalytic cracking to upgrade heavy
cracking stocks, aromatics, cycle oils and coker oils to
gasoline, jet fuels and light fuel oils.
 Alkylation

• In alkylation, low molecular weight compounds, such as

propylene and butylene are mixed in the presence of a catalyst
such as hydrofluoric acid or sulfuric acid and isobutane to form
larger branched chain molecules (isoparaffins) that make high
octane petrol.

• In practice, only isobutane is used because isopentane has a

sufficiently high octane number and low vapor pressure to allow
it to be effectively blended into finished gasolines.
 Alkylation

• Isobutane + butylene  isooctane

• C4H10 + C4H8  C8H18

CH 3 CH 3 CH 3 CH 3

CH 3 C + CH 3 C CH 3
CH 2 CH 3 C CH 2 CH CH 3

H CH 3

Isobu tylen e Isobu tan e 2,2,4 - trimeth ylpen tan e (isooctan e)

 Alkylation

 It involves the reaction of isobutane with the alkenes, in the presence of

an acid catalyst like 98% sulfuric acid or anhydrous HF to give
branched chain C7 and C8 alkanes.
 With sulfuric acid the process has to be refrigerated to 0-10°C while HF
allows temperatures of up to 50°C to be used – an advantage which
may be outweighed by the cost of HF and the difficulties in handling it.
 Although of minor importance as a refinery operation it adds a few %
to the total gasoline production of a refinery.
 In the US alkylation is worth about a million barrels/day to the
petroleum industry.
 Alkylation

 Catalytic alkylation gives a

fairly complex mixture of
products.
The main products formed by reaction of CH(CH 3)3 and
 The mixture derived from CH2=CHCH3 under HF catalysis at 38°C

isobutane and propene in an

experimental laboratory
reaction is shown in the table,
many more products might be
expected in a refinery
operation.
 Polymerisation

• Polymerization is a process in which a substance of low

molecular weight is transformed into one of the same composition
but of higher molecular weight.
• In the petroleum industry, polymerization is the controlled
process by which olefin gases are converted to liquid
condensation products that may be suitable for gasoline.
• The feedstock usually consists of propylene, propene and
butylenes from cracking processes.
 Polymerisation

• The treated olefin-rich feed stream is contacted with a catalyst

(sulfuric acid, copper pyrophosphate, or phosphoric acid) at
150C to 220C and 150 to 1200 psi depending on feedstock
and product requirement.
 Catalytic reformation

• Catalytic reformation uses heat, pressure and catalyst

(platinum, platinum-rhenium mix) to process primarily low
octane heavy straight-run (from the crude distillation unit)
gasoline and naphtha into high octane aromatics (including
benzene).

• Catalytic reforming processes result in the formation of a liquid

product of higher octane number, but also produce substantial
quantity of gases.
 Catalytic reformation

• Heptane  toluene + hydrogen

• C7H16  C7H8 + 4H2
• Cyclohexane  benzene + hydrogen
• C6H12  C6H6 + 3H2

• Catalytic reforming processes require substantial recycling of a

hydrogen stream.
• A significant by-product of this reaction is hydrogen gas, which
is then either used for hydrocracking or sold.
 Isomerisation

• Isomerisation refers to chemical rearrangement of straight-chain

hydrocarbons (paraffins), so that they contain branches attached
to the main chain (isoparaffins).

• This is done for 2 reasons:

 To create extra isobutane feed for alkylation
 To improve the octane of straight run pentanes and hexanes and
hence making them into better petrol blending components.
 Isomerisation

• Isomerisation is achieved by mixing normal butane with a little

hydrogen and chloride and allowed to react in the presence of
catalyst to form isobutanes and a small amount of normal butane
and some lighter gases.
• Products are separated in fractionator. The lighter gases (pentanes
and hexanes) are used as refinery fuel and the butane cycled as
feed.
• Isomerisation can be used to improve petrol quality by converting
these hydrocarbons to higher octane isomers.
Catalytic Cracking

 Fluid Catalytic Cracking

 Moving Bed Catalytic Cracking
 Thermofor Catalytic Cracking
 Hydrocracking – what are the catalyst used?
Conditions? Example equation.
 Alkylation
 Catalytic Reformation
 Polymerisation
 Isomerisation