CRUDE OIL DISTILLATION

Pre-treatment of crude oil

• Oil and gas when they come out of oil field are separated
(Phase separator).
• The natural gas is compressed to liquid (LPG) which is
used for heating domestic and industrial ovens.
• Crude oil is made free from:
– water (up to25%), requires extra heat for distillation.
– salts (MgCl2, CaCl2, NaCl etc. up to 2 – 5 g/lit) scaling,
corrosion and reduces heat transfer coefficient.
– sediments (1 – 1.5%) cause erosion and scaling.
 DESALTING CRUDE OILS
 If the salt content of the crude oil is greater than 10 lb/1000 bbl
(expressed as NaCl), the crude requires desalting to minimize
fouling and corrosion caused by salt deposition on heat
transfer surfaces and acids formed by decomposition of the
chloride salts.
 In addition, some metals in inorganic compounds dissolved in
water emulsified with the crude oil, which can cause catalyst
deactivation in catalytic processing units, are partially rejected
in the desalting process.
 Currently, all crude is desalted in order to reduce the
equipment fouling and corrosion and longer catalyst life.
 Two step desalting is used if the crude oil salt content is more
than 20 lb/1000 bbl and, there are some crudes for which
three-stage desalting also used.
 DESALTING CRUDE OILS
 The salt in the crude is in the form of dissolved or
suspended salt crystals in water emulsified with the
crude oil.
 The basic principle is to wash the salt from the crude oil
with water.
 Problems occur in obtaining efficient and economical
water/oil mixing, water-wetting of suspended solids, and
separation of the wash water from the oil.
 Factors influence the desalting of crude oil: pH, gravity,
and viscosity of the crude oil, as well as the volume of
wash water used per volume of crude.
 DESALTING CRUDE OILS
• Desalting is carried out by mixing the crude oil with 3 to 10 vol%
water at temperatures from 200 to 300°F (90 to 150°C).

 Desalting involves mixing heated crude oil with washing water, using
a mixing valve or static mixers to ensure a proper contact between the
crude oil and the water, and then passing it to a separating vessel,
where a proper separation between the aqueous and organic phases is
achieved.

 DC fields may be used with the potentials from 12,000 to 35,000 volts
to promote coalescence.

 For single-stage desalting units 90 to 95% efficiencies are obtained

and two-stage processes achieve 99% or better efficiency.
Single- and two-stage electrostatic desalting
systems
 Basic terminologies
• The liquid mixture that is to be processed is known as the feed.
• Feed is introduced usually somewhere near the middle of the
column to a tray known as the feed tray.
• The feed tray divides the column into a top enriching or
rectification section and a bottom stripping section.
• The feed with high boiling point flows down the column where it is
collected at the bottom in the reboiler where it is heated again to
produced the vapours and re-introduced into the column.
• The liquid product obtained from reboiler is called residue or
bottom product.
• The vapour moves up the column, and as it exits the top of the unit,
it is cooled by a condenser.
• The condensed liquid is stored in a holding vessel known as the
reflux drum.
• Some of this liquid is recycled back to the top of the column and this
is called the reflux.
• The condensed liquid that is removed from the system is known as
ATMOSPHERIC UNIT
• After desalting, the crude oil is pumped through a
series of heat exchangers and its temperature raised to
about 550°F (288°C) by heat exchange with product
and reflux streams.
• It is then further heated to about 399 °C in a furnace
(i.e., direct-fired heater or ‘‘pipe-still’’)
• Charged to the flash zone of the atmospheric
fractionators (340 to 399 oC).
• The furnace discharge temperature is sufficiently high
[650 to 750°F (343 to 399°C)] to cause vaporization of
all products withdrawn above the flash zone plus about
10 to 20% of the bottoms product.
 ATMOSPHERIC UNIT
• Reflux is provided by condensing the tower overhead
vapors and returning a portion of the liquid to the top
of the tower.
• Although crude towers do not normally use reboilers,
several trays are generally incorporated below the
flash zone and steam is introduced below the bottom
tray to strip any remaining gas oil from the liquid in
the flash zone and to produce a high-flash-point
bottoms.
• The atmospheric fractionator normally contains 30 to
50 fractionation trays.
 ATMOSPHERIC UNIT
• Generally five to eight trays are needed for each side
stream product.
• Crude oil atmospheric fractionation tower with four
liquid side stream draw offs will require from 30 to 42
trays.
ATMOSPHERIC DISTILLATION
 VACUUM DISTILLATION

• Materials are therefore distilled under vacuum

because the boiling temperature decreases with
a lowering of the pressure.
• Distillation is carried out with absolute
pressures in the tower flash zone area of 25 to
40 mmHg.
• To improve vaporization, the effective pressure
is lowered even further (to 10 mmHg or less)
by the addition of steam to the furnace inlet
and at the bottom of the vacuum tower.
 VACUUM DISTILLATION
• Addition of steam to the furnace inlet increases the furnace
tube velocity and minimizes coke formation in the furnace as
well as decreasing the total hydrocarbon partial pressure in
the vacuum tower.
• Furnace outlet temperature 388 to 454°C are generally used.
• A few millimeters decrease in pressure drop will save many
dollars in operating costs.
• The lower operating pressures cause significant increases in
the volume of vapor per barrel vaporized and, as a result, the
vacuum distillation columns are much larger in diameter than
atmospheric towers.
• It is not unusual to have vacuum towers up to 40 feet in
diameter.
 VACUUM DISTILLATION
• The size and number of ejectors and condensers
used is determined by the vacuum needed and
the quality of vapors handled.
• For a flash zone pressure of 25 mmHg, three
ejector stages are usually required.
• The first stage condenses the steam and
compresses the non condensable gases, while
the second and third stages remove the non
condensable gases from the condensers.
VACUUM DISTILLATION
 Hydrocarbon cracking
Cracking: It is the process of breaking long chained
hydrocarbon into shorter one i.e. high boiling point
petroleum fraction into low boiling point lighter fractions.
Necessity: Increasing demand of gasoline exceed its
availability by distillation alone, hence cracking of heavier
fraction of petroleum is done mainly to produced gasoline.
Types: There are two types of cracking processes:
– Thermal cracking (450 – 750 C, 1 – 70 atm)
– Catalytic cracking (350 – 650 C, 1 – 15 atm)
The yield of process and quality of product depend on type
of feed, temperature and pressure.
Higher temperature gives higher yield of gasoline
Higher pressure reduces the octane number of gasoline
 Thermal Cracking
• Thermal reactions involves two reactions: primary reaction resulting in the
decomposition of large molecules into small molecules and secondary
reactions where the some of the primary products interact to form higher
molecular weight materials.
• Thermal cracking reaction is a free radical chain reaction.
• Free radical is formed by carbon-carbon scission.
• Breaking of the bonds results predominantly in an increase in small
molecules.
• Breaking of the bonds also leads to free radical formation, that can also result
in subsequent polymerization or condensation.
Initiation: C6H14  C2H5 O + C4H9 O
Propagation
• C2H5 O + C6H14  C2H6 + C6H13 O
• C4H9 O + C6H14  C4H10 + C6H13 O
• C4H9 O  C3H6 + CH3 O
• C6H13 O  C4H8 + C2H5 O (MANY OTHER PRODUCTS)
• Termination: During the cracking operation,
some coke is usually formed. Coke is the end
product of thermalization reaction in which two
large olefin molecules combine to form an even
larger olefinic molecule
C10H21-CH=CH2 + CH2=CH-C10H21  C10H21-
CH=CH-CH2-CH2-C10H21

Free radical + Hydrocarbon  Stable End

Product
Thermal cracking mechanism
 Catalytic Cracking
• Cracking of heavy hydrocarbon in presence of catalyst.
• It gives higher yield and higher octane number of gasoline than
thermal cracking.
• Moreover the process requirement for temperature and pressure
are 450 – 550 C and 1.5 to 2.5 atm respectively which is lower than
thermal cracking.
• Feed mainly is light gas oil
• The more naphthenic the feed, the higher is the yield of gasoline.
• High boiling point feed sometime contain appreciable amount of
Conradson carbon which gets deposited on the catalyst which are
discarded and replaced by fresh one.
• Primary catalyst used were natural or artificial clay e.g bentonite,
metallic catalyst being used presently are platinum, chromium, iron
and nickel.
• Synthetic catalyst being used include silica-alumina and silica-
magnesia.
• The size of catalyst in moving bed catalytic process is 3 – 5
mm. while in fluidized bed catalytic process is about 20 – 40
micron.
• The cracking process produces carbon (coke) which remains
on the catalyst particle and rapidly lowers its activity.
• To maintain the catalyst activity at a useful level, it is
necessary to regenerate the catalyst by burning off this coke
with air.
• The cracking reaction is endothermic and the regeneration
reaction exothermic.
Properties of catalyst Type of processes
• High reactivity • Fixed bed
• Good selectivity • Moving bed
• Sufficient strength • Fluidized bed
• Easy regenerability
• High surface area
• High porosity
• Primary cracking occurs by the carbenium ion
intermediates in the following steps:
(a) Olefin is formed first by the mild thermal cracking
of paraffin:

(b) Proton shift:

• Beta scission: Carbon–carbon scission takes place at the
carbon in the position beta to the carbenium ions and olefins

• The newly formed carbenium ion reacts with another paraffin

molecule and further propagates the reaction.
• The chain reaction is terminated when (a) the carbenium ion
losses a proton to the catalyst and is converted to an olefin; or
(b) the carbenium ion picks up a hydride ion from a donor (e.g.
coke) and is converted to paraffin.
• Beside paraffins, other hydrocarbons which are formed by
primary cracking.
 Secondary Reactions
• Gasoline formed from primary cracking can undergo further
secondary cracking, which is generally caused by hydrogen
transfer mechanisms such as isomerisation, cyclisation and
coke formation.
 Fluidized bed catalytic cracking
• Fluidized bed catalytic cracking is the most widely used process in
oil refineries.
• The plant consisting of three main column:
– Reactor
– Regenerator
– Fractionator
• The catalyst is in powdered form and is circulated between rector
and regenerator.
• Fluidized bed of catalyst is obtained by forcing the vapors through
bed until minimum fluidized velocity is reached at which the particles
of catalyst arranged a loose packing in vapours.
• A slight increase in the velocity cause the vapours to flow through a
zone of low solid concentration in which high mass transfer rates
between catalyst surface and vapours enables high reaction rates.
•
Fluid catalytic cracking process flow sheet

316–427 C

649–760 C

482–538 C
• Steam and VGO heated up to 316–427 C are fed to the bottom of the
riser.
• The regenerated hot catalyst at 649–760 C is also fed to the bottom of
the riser.
• The riser is the main reactor in which the endothermic reactions take
place (RT- 2-10 S).
• At the top of the riser, the gaseous products flow into the fractionator.
• While the catalyst and some heavy liquid hydrocarbon flow back in the
disengaging zone.
• Steam is injected into the stripper section, and the oil is removed from
the catalyst.
• Spent catalyst is sent to the regenerator at a temperature of 482–538 C.
• The coke in the spent catalyst, produced in the cracking reaction, is
burned off in the regenerator by introducing excess air.
• The hot flue gas contains carbon dioxide, carbon monoxide water and
excess air at the regenerator temperature.
• The product gases from the reactor are sent to the fractionator
which produces light gases, heavy gasoline (main product), light
cycle gas oil (LCO), heavy cycle gas oil (HCO) and decant slurry.
• The light gases are sent to the gas concentration unit where flue
gas, propane, butane, LPG and light gasoline are produced.
• The operating conditions are usually adjusted to produce the
maximum amount of gasoline from the VGO.
• The decant slurry from the bottom of the fractionator is a mixture
of heavy aromatics and fine catalyst particles.
• The catalyst oil ratio is 5 – 15 and the reactor space velocity is 1 –
3 kg oil/hr/kg catalyst.
Gasoline yield = 53 – 59 %
Heavy gas oil = 2 – 3 %.
light gas oil = 18 – 25 %.
coke = 5 – 8 %.
Octane number of gasoline = 92 – 94.
 FCC Catalyst
Schematic representation of shape-
Structure of Y-faujasite selective cracking with ZSM-5
 Factors effecting on catalytic cracking
• Temperature:
– Rate of reaction increases with increase in temperature.
– For every 40oC the decomposition rate doubles.
– For a given conversion gasoline yield is reduced at higher temperature.
• Pressure:
– For high pressure more residence time is required which result in formation more
unsaturated hydrocarbon as a consequence less octane number gasoline is achieved.
– At given conversion, increase in pressure increases the production of coke.
• Catalyst to oil ratio:
– Conversion increases with increase in catalyst to oil ratio as it shorten the time
required to pass through reactor and hence reduces the extent of its deactivation from
coke production.
• Coke concentration on catalyst:
– Lesser the concentration of coke on catalyst, better be the effective activity of
catalyst.
– Lower coke concentration is obtained by increasing catalyst to oil ratio.
• Catalyst activity:
– With decrease in catalyst activity, the conversion declines making less product yield.
– Fresh catalyst are being replaced by old catalyst to increase catalytic activity.
 Hydroconversion
• Hydrocarbon reacts with hydrogen is called
as Hydro conversion.
• Hydrotreating: Removal of sulphur,
nitrogen and metal impurities in the
feedstock by hydrogen in the presence of a
catalyst.
• Hydrocracking: Catalytic cracking of
feedstock to products with lower boiling
points by reacting them with hydrogen.
 Hydrotreating
I. Meeting finished product specification
• Kerosene, gas oil and lube oil desulphurization.
• Olefin saturation for stability improvement.
• Nitrogen removal.
• De-aromatization for kerosene to improve cetane
number, which is the percentage of pure cetane in
a blend of cetane and alpha-methyl-naphthalene.
The later matches the ignition quality of kerosene
sample.
 MAJOR PRODUCTS DEMAND, QUALITY SCENARIO
AND NEW TECHNOLOGIES
Changing Scenario in Gasoline Specifications
Period Specifications
Prior to Lead phase out
1994 Lower RVP
1995-2000 Reformulated gasoline
Zero lead
Benzene: 1% max, lower aromatics: 25 vol % max
Oxygen: 25 wt% min
RVP 7.2/8.1 psi max
Beyond Reformulated gasoline Phase II
2000 Lower sulfur content; 30%
Benzene: 0.8 % max, Aromatics: 22.0% max
RVP: 7.0 %
Olefins: 4 %
Oxygen: 2 %
 Changing Scenario in Diesel Specifications
Period Specifications
Prior to Sulphur: 1.0% 0.2% (Sweden 0.001-0.05% from
1993 1991)
Cetane: No limit
(Sweden: 47-50 from 1991)

1993-2000 Aromatics : No limits (Sweden: 5-25% from

1991)
Sulphur : 0.2-0.05%
Cetane : 40-46 min.
Beyond Aromatics : 35% max (California 10% max)
2000 Sulphur : Further reduction to Sweden levels
Cetane : Further increase 40-46 min.
Aromatics : Further reduction
Volatility : increase over present level
 Hydrotreating
II. Feed preparation for downstream units
Naphtha is hydrotreated for removal of metal and
sulphur.
Sulphur, metal, polyaromatics and Conradson carbon
removal from vacuum gas oil (VGO) to be used as
FCC feed.
Pretreatment of hydrocracking feed to reduce sulphur,
nitrogen and aromatics.
Hydrotreating
 Hydrotreating Reactions
I. Desulphurization
 Hydrotreating Reactions
II. Denitrogenation

III. Deoxidation
 Hydrotreating Reactions
IV. Hydrogenation of chlorides

V. Hydrogenation of olefins

VI. Hydrogenation of aromatics

 Hydrotreating Catalysts
• It is a porous alumina matrix impregnated with combinations of
cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W).
• Catalysts mainly have pores with a surface area of (200–300 m2/g).
• Co–Mo catalysts are the most popular for desulphurization of
straight run petroleum fractions.
• Ni–Mo catalysts are chosen when higher activity is required for the
saturation of polynuclear aromatic compounds or for the removal of
nitrogen and refractory sulphur compounds.
• Ni–W catalysts are chosen only when very high activity aromatic
saturation is reqired.
 Hydrotreating Catalysts
• It is a porous alumina matrix impregnated with combinations of
cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W).
• Catalysts mainly have pores with a surface area of (200–300 m2/g).
• Co–Mo catalysts are the most popular for desulphurization of
straight run petroleum fractions.
• Ni–Mo catalysts are chosen when higher activity is required for the
saturation of polynuclear aromatic compounds or for the removal of
nitrogen and refractory sulphur compounds.
• Ni–W catalysts are chosen only when very high activity aromatic
saturation is required.
 Naphtha Hydrotreating
• It is usually used to remove the impurities so that
the hydrotreated naphtha can be introduced to the
catalytic reformer.
• The expensive platinum based catalyst used in the
reformer is sensitive to poisoning by such
impurities.
• It Consist of feed heater, reactor, high and low
pressure separators, recycle compressor and
treated naphtha fractionator.
• A hydrogen sulphide scrubber might be placed
between the high and low pressure separators.
• A catalyst of Co–Mo on alumina is used.
 Naphtha Hydrotreating

Reactor conditions for naphtha hydrotreating unit are around 400-500˚F (205-260˚C) and pressure of 350-650 psi (25-
45 bar). As coke deposits on the catalyst, reactor temperature must be raised. Once the reactor temperature reaches
~750˚F (400˚C), the unit is scheduled for shutdown and catalyst replacement.
 Hydrocracking
• It is a catalytic hydrogenation process in which high molecular
weight feedstocks are converted and hydrogenated to lower
molecular weight products.
• The catalyst used in hydrocracking is a bifunctional one.
• It is composed of a metallic part, which promotes
hydrogenation, and an acid part, which promotes cracking.
• Hydrogenation removes impurities in the feed such as
sulphur, nitrogen and metals.
• Cracking will break bonds, and the resulting unsaturated
products are consequently hydrogenated into stable
compounds.
 Role of Hydrocracking in the Refinery
• Hydrocracking plays an important role as one of the
main conversion processes in the refinery.
• It is mainly used to produce middle distillates of low
sulphur content such as kerosene and diesel.
• More recently, it has been used to remove wax by
catalytic dewaxing and for aromatic removal by
hydrogen saturation.
• This has been applied to the lube oil plants and is
gradually replacing the old solvent dewaxing and
aromatic solvent extraction.
Typical feedstocks and products
Hydrocracking Chemistry
Hydrocracking Chemistry
 Hydrocracking Catalysts
• Hydrocracking catalysts have a cracking function and
a hydrogenation function.
•
 Bifunctional catalyst strength for
hydrogenation and cracking
• Cracking and isomerization reactions take place on
the acidic support.
• These metals catalyze the hydrogenation of the
feedstock, making it more reactive for cracking and
heteroatom removal and reducing the coking rate.
• They also initiate the cracking by forming a reactive
olefin intermediate via dehydrogenation.
 TWO-STAGE HYDROCRACKER
• The effluent from the first stage reactor is sent to a
separator and fractionator.
• The fractionator bottoms are sent to the second reactor.
• In both configurations, the hydrogen is separated in the
high pressure separator and recycled back to the reactor.
• A hydrotreatment reactor may be added before the first
hydrocracker to help in removing sulphur and nitrogen
compounds from the feed.
• Since H2S and NH3 are separated before entering the
second hydrocracker, this allows the selection of special
catalysts in the second reactor without the poisoning
effect of sour gases.
first stage: high
hydrogenation/acidity
ratio -- causing sulphur
and nitrogen removal.
second reactor: low
hydrogenation/acidity
ratio to maximize the
naphtha production
high
hydrogenation/acidity
ratio to maximize the
middle distillate,
kerosene, diesel and jet
fuel
 Reforming

• Reforming means rearrangement of molecules without much

affecting the average molecular weight of feed which is generally
naphtha of gasoline boiling range.
• Reforming carried out to produce high quality octane number gasoline.
• Like cracking reforming can also be done either thermally or
by using catalyst.
• Low octane thermally cracked gasoline is also subjected to reforming
to improve its octane number.
• Gasoline produced by reforming is called reformed gasoline or
reformate.
• Thermal reforming has been almost completely replaced by catalytic
reforming.
• Besides the main product i.e. reformate or reformed gasoline,
reforming also produces lighter hydrocarbons, hydrogen and traces
of high boiling materials.
 Catalytic Reforming
• Catalytic reforming of heavy naphtha and isomerization of
light naphtha constitute a very important source of products
having high octane numbers which are key components in
the production of gasoline.
• Catalytic reforming is the process of transforming C7–C10
hydrocarbons with low octane numbers to aromatics and iso-
paraffins which have high octane numbers.
• It is a highly endothermic process requiring large amounts of
energy.
• The process can be operated in two modes: a high severity
mode to produce mainly aromatics (80–90 vol%) and a
middle severity mode to produce high octane gasoline (70%
aromatics content).
• Environmental regulations limit on the benzene content in
gasoline. Elimination of benzene forming hydrocarbons, such
as, hexane will prevent the formation of benzene, and this
can be achieved by increasing the initial point of heavy
 Reaction Kinetics and Catalysts
• The catalyst used for reforming is a bifunctional catalyst
composed of platinum metal on chlorinated alumina.
• Platinum acts as the centre for the dehydrogenation reaction
• Chlorinated alumina acts as an acidic site to promote structure
changes, such as cyclization of paraffin's and isomerization of the
naphthenes.
• Recently additional elements have been added to platinum to
promote additional properties for the catalyst.
• Iridium (Ir) is added to boost activity.
• Rhenium (Re) is added to operate at lower pressures
• Tin (Sn) is added to improve yield at low pressures.
Catalytic Reforming
Reforming Reactions

All the above reactions are

highly endothermic.
Role of reformer in the refinery
• The hydrotreated naphtha (HTN) is fractionated
into light naphtha (LN), which is mainly C5–C6,
and heavy naphtha (HN) which is mainly C7–C10
hydrocarbons.
• It is important to remove C6 from the reformer
feed because it will form benzene which is
considered carcinogenic upon combustion.
• Light naphtha (LN) is isomerized in the
isomerization unit (I).
• Light naphtha can be cracked if introduced to the
reformer.
 Isomerization of Light Naphtha
• Isomerization is the process in which light straight
chain paraffins of low RON (C6, C5 and C4) are
transformed with proper catalyst into branched chains
with the same carbon number and high octane numbers.
• Light naphtha C5 -80 oC is used as a feed to the
isomerization unit.
• The isomerization reactions are slightly exothermic and
the reactor works in the equilibrium mode.
• There is no change in the number of moles and thus the
reaction is not affected by pressure change.
• Better conversions are achieved at lower temperature
reactor at 130 oC will give good results.
 Isomerization Reactions
• Isomerization is a reversible and slightly
exothermic reaction:
• The conversion to iso-paraffin is not complete
since the reaction is equilibrium conversion
limited.
• It does not depend on pressure, but it can be
increased by lowering the temperature.
• However operating at low temperatures will
decrease the reaction rate.
• For this reason a very active catalyst must be
used.
Isomerization Reactions
 Isomerization of Light Naphtha
• Isomerization is the process in which light straight
chain paraffins of low RON (C6, C5 and C4) are
transformed with proper catalyst into branched chains
with the same carbon number and high octane numbers.
• Light naphtha C5 is used as a feed to the isomerization
unit.
• The isomerization reactions are slightly exothermic and
the reactor works in the equilibrium mode.
• There is no change in the number of moles and thus the
reaction is not affected by pressure change.
• Better conversions are achieved at lower temperature
reactor at 130 oC will give good results.
 Isomerization Catalysts
• This bi-functional nature catalyst consists of highly chlorinated
alumina (8–15 w% Cl2) responsible for the acidic function of the
catalyst.
• Platinum is deposited (0.3–0.5 wt%) on the alumina matrix.
• Platinum in the presence of hydrogen will prevent coke deposition,
thus ensuring high catalyst activity.
• The reaction is performed at low temperature at about 130 oC to
improve the equilibrium yield and to lower chlorine elution.
• The standard isomerization catalyst is sensitive to impurities such as
water and sulphur traces which will poison the catalyst and lower its
activity.
• For this reason, the feed must be hydrotreated before isomerization.
• Furthermore, carbon tetrachloride must be injected into the feed to
activate the catalyst.
• The pressure of the hydrogen in the reactor will result in the elution of
chlorine from the catalyst as hydrogen chloride.
• For all these reasons, the zeolite catalyst, which is resistant to
impurities, was developed.
 Alkylation and Polymerization

• The need for high-octane aviation fuels during World War II acted
as a stimulus to the development of the alkylation process for
production of isoparaffinic gasoline of high octane number.
• The addition of an alkyl group to any compound is an alkylation
reaction
• Alkylation can take place at high temperatures and pressures
without catalysts, the only processes of commercial importance
involve low temperature alkylation conducted in the presence of
either sulfuric or hydrofluoric acid.
• The reactions occurring in both processes are complex and the
product has a rather wide boiling range.
• By proper choice of operating conditions, most of the product
can be made to fall within the gasoline boiling range with motor
octane numbers from 88 to 94.
ALKYLATION FEEDSTOCKS
• Olefins and isobutane are used as alkylation unit feedstocks.
• The chief sources of olefins are catalytic cracking and coking
operations.
• Butenes and propene are the most common olefins used, but
pentenes (amylenes) are included in some cases.
• Hydrocrackers and catalytic crackers produce a isobutane used
in alkylation but it is also obtained from catalytic reformers,
crude distillation, and natural gas processing.
• In some cases, normal butane is isomerized to produce
additional isobutane for alkylation unit feed.
 ALKYLATION REACTIONS
• In alkylation processes using hydrofluoric or sulfuric acids as
catalysts, only isoparaffins with tertiary carbon atoms, such as
isobutane or isopentane, react with the olefins.
• 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 directly into finished gasolines.
• The process using sulfuric acid as a catalyst is much more
sensitive to temperature than the hydrofluoric acid process.
• With sulfuric acid it is necessary to carry out the reactions at 40 to
70°F (5 to 21°C) or lower, to minimize oxidation
reduction reactions which result in the formation of tars and the
evolution of sulfur dioxide.
• When anhydrous hydrofluoric acid is the catalyst, the temperature
is usually limited to 100°F (38°C) or below
• In both Process Acid employed is about equal to that of the liquid
hydrocarbon charge and sufficient pressure is maintained on the
system to keep the hydrocarbons and acid in the liquid state.
• High isoparaffin/olefin ratios (4:1 to 15:1) are used to minimize
polymerization and to increase product octane.
• Efficient agitation to promote contact between the acid and
hydrocarbon phases is essential to high product quality and yields.
• Contact times from 10 to 40 minutes are in general use.
• The yield, volatility, and octane number of the product is regulated
by adjusting the temperature, acid/hydrocarbon ratio, and
isoparaffin/olefin ratio.
• At the same operating conditions, the products from the
hydrofluoric and sulfuric acid alkylation process are quite similar.
• In practice, however, the plants are operated at different conditions
and the products are somewhat different.
• The principal reactions which occur in alkylation are the
combinations of olefins with isoparaffins as follows:
Another significant reaction in propylene alkylation is the
combination of propylene with isobutane to form propane plus
isobutylene.
The isobutylene then reacts with more isobutane to form 2,2,4-
trimethylpentane.
 PROCESS VARIABLES
• Acid strength has varying effects on alkylate quality
depending on the effectiveness of reactor mixing and the water
content of the acid.
• In sulfuric acid alkylation, the best quality and highest yields
are obtained with acid strengths of 93 to 95% by weight of
acid, 1 to 2% water.
• The water concentration in the acid lowers its catalytic activity
about 3 to 5 times .
• Thus an 88% acid containing 5% water is a much less effective
catalyst than the same strength acid containing 2% water.
• Isobutane concentration is generally expressed in terms of
isobutane/olefin ratio.
• High isobutane/olefin ratios increase octane number and yield,
and reduce side reactions and acid consumption.
• In industrial practice the isobutane/olefin ratio on reactor
charge varies from 5:1 to 15:1.
HYDROFLUORIC ACID PROCESSES
 SULFURIC ACID ALKYLATION PROCESSES
• The major alkylation processes using sulfuric acid as a catalyst
are the auto refrigeration process, licensed by Exxon Research
and Engineering
• The major differences between the auto refrigeration and
effluent refrigeration processes are in the reactor designs and the
point in the process at which propane and isobutane are
evaporated to induce cooling and provide the process
refrigeration required.
• The auto refrigeration process uses a multistage cascade reactor
with mixers in each stage to emulsify the hydrocarbon–acid
mixture.
• Olefin feed or a mixture of olefin feed and isobutane feed is
introduced into the mixing compartments and enough mixing
energy is introduced to obtain sufficient contacting of the acid
catalyst with the hydrocarbon reactants to obtain good reaction
 SULFURIC ACID ALKYLATION PROCESSES
• The reaction is held at a pressure of approximately 10 psig (69 kPag) in order to
maintain the temperature at about 40°F (5°C).
• In the Exxon process, acid and isobutane enter the first stage of the reactor and
pass in series through the remaining stages.
• The olefin hydrocarbon feed is split and injected into each of the stages.
• Exxon mixes the olefin feed with the recycle isobutane and introduces the
mixture into the individual reactor sections to be contacted with the catalyst.
• The remainder of the liquefied hydrocarbon is sent to a depropanizer column for
removal of the excess propane which accumulates in the system.
• The liquid isobutane from the bottom of the depropanizer is pumped to the first
stage of the reactor.
• The acid–hydrocarbon emulsion from the last reactor stage is separated into
acid and hydrocarbon phases in a settler.
• The acid is removed from the system for reclamation, and the hydrocarbon
phase is pumped through a caustic wash followed by a water wash to eliminate
trace amounts of acid and then sent to a deisobutanizer.
• The deisobutanizer separates the hydrocarbon feed stream into isobutane (which
is returned to the reactor), n-butane, and alkylate product.
SULFURIC ACID ALKYLATION PROCESSES
 POLYMERIZATION
• Propene and butenes can be polymerized to form a high-
octane product boiling in the gasoline boiling range.
• The polymerization process was widely used in the 1930s
and 1940s to convert low-boiling olefins into gasoline
blending stocks but was supplanted by the alkylation
process after World War II.
• Polymerization produces about 0.7 barrels of polymer
gasoline per barrel of olefin feed as compared with about
1.5 barrels of alkylate by alkylation
• Product has a high octane sensitivity, but capital and
operating costs are much lower than for alkylation.
• As a result, polymerization processes are being added to
some refineries.
 POLYMERIZATION
• The most widely used catalyst is phosphoric acid on an inert
support.
• This can be in the form of phosphoric acid mixed with a natural
clay or a film of liquid phosphoric acid on crushed quartz.
• Sulfur in the feed poisons the catalyst and any basic materials
neutralize the acid and increase catalyst consumption.
• Oxygen dissolved in the feed adversely affects the reactions and
must be removed.
• Normal catalyst consumption rates are in the range of one pound
of catalyst per 100 to 200 gallons of polymer produced (830 to
1660 l/kg).
• The feed, consisting of propane and butane as well as propene
and butene, is contacted with an amine solution to remove
hydrogen sulfide and caustic washed to remove mercaptans.
 POLYMERIZATION
• It is then scrubbed with water to remove any caustic or amines and
then dried by passing through a silica gel or molecular sieve bed.
• Finally, a small amount of water (350–400 ppm) is added to
promote ionization of the acid before the olefin feed steam is
heated to about 400°F (204°C) and passed over the catalyst bed.
• Reactor pressures are about 500 psig (3450 kPa).
• The polymerization reaction is highly exothermic and temperature
is controlled either by injecting a cold propane quench or by
generating steam.
• The propane and butane in the feed act as diluents and a heat sink
to help control the rate of reaction and the rate of heat release.
• Propane is also recycled to help control the temperature.
• After leaving the reactor the product is fractionated to separate the
butane and lighter material from the polymer gasoline.
• Gasoline boiling range polymer production is normally 90–97 wt%
on olefin feed or about 0.7 barrel of polymer per barrel of olefin
feed.
POLYMERIZATION
Flow sheet of Modern Refinery
Dewaxing:
– Removal of wax from petroleum product, mainly lubricating oil.
– Petroleum waxes are solid hydrocarbons which are soluble in
petroleum and its products and cannot be separated by distillation as
their boiling points (35 – 95oC) overlap with other petroleum products.
– At low temperatures, waxes crystallize and precipitate out from
diesel and lubricating oil, hence to maintain their fluidity they must be
dewaxed.
Deasphalting:
– Removal of asphalts from heavy stocks.
– Asphalts are high molecular weight compounds present in petroleum
and have high boiling point in range of lube oil and heavy gas oil.
– Asphalts are undesirable in catalytic cracking because they form
coke.
– Asphalts are readily oxidize and form carbonaceous sludge and hence
must be removed.
– Deasphalting is done by distillation (atmospheric or vacuum), acid
treating and by solvent (propane) extraction.
Purification of petroleum products
• Alkyl and aromatic Mercaptans are among important sulphuric
compounds distributed in petroleum products.

• These Mercaptans cause foul odour and are corrosive towards metals.

• Mercaptans may cause oxidative deterioration as well as inhibit the

performance of various additives in finished products.

• It is necessary to remove them, either by extraction processes or by

converting them into harmless disulphides.

• Such processes are usually referred to as “sweetening’’

 Caustic Treatment
• Caustic treatment of petroleum products is as old as the
industry itself.
• Hydrogen sulphide in low concentration, napthenic
acids , aryl mercaptans , alkyl phenol are normally
removed by a non-regenerative caustic treatment.
• Naphthenic acids or alkyl phenols are removed by
simple one stage caustic wash in a mixer/settler unit,
because of their effects on some sweetening catalysts.
• Recovery of the acids for by product sale is a common
practice.
 Solutizer Process
• Caustic washing removes some of the lighter
mercaptans, to remove the heavier mercaptans
solutizer process is used.
• This process utilizes suitable organic solvents or
salt in the aqueous phase with improved solubility
of mercaptans.
• The solutizer process can treat most cracked or
straight-run napthas below 0.0003 percent
mercaptans.
• Slight improvement in Octane number.
 Doctor’s sweeting process
• This process was the first treating process to be employed
commercially for conversion of mercaptans.
• The operation can be either batch or continuous , regenerative
or non- regenerative.
• Sour naptha is mixed with the doctor solution (sodium
plumbite), this doctor solution reacts with mercaptans to form
lead mercaptides.
• A stream of lead mercaptides is mixed with the stream of the
naptha containing dissolved sulphur. On reacting it gives
disulphides and lead sulphides.
• As a disadvantage of this process is the formation of
polysulphide which increases the corrosion and reduce the
thermal stability.
• Regeneration of Doctor’s solution is carried out at 80 – 110oC
and 1 – 7 atmospheric pressure.
 Copper Chloride Sweetening
• This process is used for sweetening of gasoline's and
kerosene's by the direct oxidation of mercaptans to
disulphides, using cupric chloride as the oxidizing agent.
• There is a net production of water which must be
removed continuously to maintain reaction conditions.
• There are many advantages of this process:-
a. No loss in octane number.
b. Good thermal stabilities
 Merox Process
• This is an efficient and economical catalytic process
developed for the chemical treatment of petroleum
distillates to remove mercaptans.
• This process is based on the ability of a catalyst to
catalyse the oxidation of mercaptans to disulphides in
alkaline medium at ambient temperature using air as
the source of oxygen.
• It is used for liquid-phase treating of LPG, napthas ,
kerosene's, jet fuels , diesel fuels and heating oils.
 Merox Extraction & Sweetening
• The merox extraction process are used to extract low
molecular weight mercaptans from gases , LPG and
light napthas fractions.
• This reduces the total sulphur content in the finished
product.
• The merox sweetening process is achieved by blowing
caustic/hydrocarbon mixture with the air in the
presence of merox catalyst.
• Mercaptans are oxidized into disulphides which remain
dissolved in the product. There is no reduction in the
total sulphur content of the finished product.
 Sulphuric acid Treatment

One of the oldest process for the removal of sulphur , aromatics ,

olefins is the sulphuric acids treatment .
• This treatment is usually applied to light petroleum distillates.
• The process is applicable to the pretreatment of straight-run napthas
that are to be reformed and for the removal of thiophene from aromatic
streams.
• But two major drawbakcs of this process are appreciable material
loss resulting from the formation of acid sludge and the problem of
sludge disposal.
 Clay Treatment
• This treatment is generally applied for removal of
olefins and di-olefins from cracked gas/liquid streams.
• This process improves colour ,odour , and oxidation
stability of the lubricating oil base stocks and waxes.
• The feed enters at the top of the tower and the treated
product leaves from the bottom. While treating
lubricating oils and waxes ,the slurry of oil and clay is
heated at about 120-150 o C.
• The clay used in the process is generally activated.