CRUDE OIL REFINING PROCESSES

FINAL YEAR B. TECH

Various unit operations in refining process
- Crude distillation unit (CDU)
- Vacuum distillation unit (VDU)
- Thermal cracker
- Hydrotreaters
- Fluidized catalytic cracker
- Separators
- Naphtha splitter
- Reformer
- Alkylation and isomerisation
- Gas treating
- Blending pools
- Stream splitters
ATMOSPHERIC RECTIFICATION
The petroleum crude prepared at the oil well comes to the petroleum refinery and
the first step is atmospheric rectification (distillation). The methods of fractional
distillation, differential distillation, or rectification are utilized for the primary
separation of crude oil into fractions with regard to their boiling temperatures.
The petroleum rectification units operate continuously. For rectification, after
drying and desalting, crude is drawn from storage tanks at ambient temperature
and pumped at a constant rate through a series of heat exchangers in order to
reach a temperature of approximately 120°C. The preheated petroleum passes
through an oven ( or called furnace). At this position it is heated to a temperature
between 315 and 400°C, depending on the type of petroleum and the quality of
the end products desired. A mixture of vapor and non-vaporized oil passes from the
oven into the rectification tower. The pressure maintained is about 1 bar.
CRUDE DISTLLATION UNIT
The unit comprising of an atmospheric distillation column, side strippers,
heat exchanger network, feed de-salter and furnace as main process
technologies enables the separation of the crude into its various products.
Usually, five products are generated from the CDU namely gas + naphtha,
kerosene, light gas oil, heavy gas oil and atmospheric residue. In some
refinery configurations, terminologies such as gasoline, jet fuel and diesel are
used to represent the CDU products which are usually fractions emanating as
portions of naphtha, kerosene and gas oil. Amongst the crude distillation
products, naphtha, kerosene have higher product values than gas oil and
residue. On the other hand, modern refineries tend to produce lighter
components from the heavy products. Therefore, reactive transformations
(chemical processes) are inevitable to convert the heavy intermediate
refinery streams into lighter streams.
• The size of the rectification tower is about 45 meters tall with 20 to 40
fractionating trays. The most common trays used are sieve or valve trays.
Petroleum vapor rises up through the trays to the top of the tower. It is
condensed to a liquid in a water- or air-cooled condenser at the top of the tower.
A small amount of gas remains uncondensed and is piped to Gas Separation
tower or into the refinery fuel- gas system. A pressure control valve on the fuel-
gas line maintains rectification tower pressure at the desired value, usually near
atmospheric pressure. Part of the condensed liquid, reflux, is pumped back into
the top of the column and descends from tray to tray, contacting rising vapours as
they pass through the slots in the trays. The liquid progressively absorbs heavier
constituents from the vapor and, in turn, releases lighter constituents to the
vapor phase.
• The intermediate products, or side-streams are drawn at several points from the
tower dependent on the fractions desired. Usually these fractions are Naphtha
gasoline and diesel fractions. Dependent on the production type in the refineries,
jet fraction can be drawn as well. In addition, modern petroleum rectification
units employ intermediate reflux streams
PRODUCT STREAMS

• Typical boiling ranges for various streams are as follows:

• Light straight-run naphtha (head), 20-95°C;
• Heavy naphtha (side-stream), 90-165°C;
(Naphtha fractions are a blend of alkanes, naphthenes, and aromatic hydrocarbons. All these
hydrocarbons contain 5-10 carbon atoms.)
• Crude kerosene or jet (side-stream), 150-245°C;
• Middle Distillate (side-stream) 180-280°C; Varies depending on crude
• Light gas oil or diesel (side-stream), 215-315°C.
• Non-vaporized oil entering the tower flows downward over the trays (below the feed tray) called
stripping trays. These act to remove any light constituents remaining in the liquid. In any case,
steam is injected into the bottom of the tower in order to reduce the partial pressure of the
hydrocarbons; this plays a similar role as a vacuum during vacuum rectification. The residue that
is obtained from the bottom of the tower is suitable for blending into residual fuels. Alternatively,
it may be further distilled under vacuum conditions to yield quantities of distilled oils for
manufacture into lubricating oils or for use as feed- stock in gas oil cracking processes.
Fractions
• Kerosene fraction – oil cut with the boiling temperature from 150-180 oC to 270-
280 oC. This fraction contains C10-C15 hydrocarbons.
It is used for motor fuel (power kerosene, diesel fuel component), for daily living
needs (lamp oil), etc.
• Gas-oil fraction - the boiling temperature is from 270-280 oC to 320-350oC. This
fraction contains C14-C20 hydrocarbons. It is used for diesel fuel.
• Residue – the remainder after distillation of the above-listed fractions with the
boiling temperature above 320-350 oC.
Residue can be used as fuel oil or being refined or rectified under reduced
pressure (in vacuum) with extraction of oil fractions or vacuum gas-oil wide
fraction (that is used as feed for catalytic cracking in order to get high-octane
gasoline component), or being exposed to cracking.
• Tar – almost solid remainder after stripping oil fractions from the residue.
Residual oils and bitumen are produced from it. By bitumen oxidation one can get
asphalt used for roads construction, etc. Coke used in metallurgy industry can be
produced out of tar or other secondary
CRUDE DISTILLATION WITH DOUBLE EVAPORATION
• In this case double oil evaporation and two rectification columns scheme is used.
In the first column light gasoline and gas are produced. It decreases general
pressure in the system and pressure in the main rectification column. It results in
more complete separation of light oil products and more precise fractionation in
the column.
• Crude oil is collected by the pump 1 and brought for dehydration and desalting to
the electric dehydrators 3 via the heat-exchangers 2. Dehydrated and desalted oil
goes through the second group of heat-exchangers 4, is heated up to 210-220 oC
and enters the first rectification column C-1, where light naphtha and gas fraction
are produced. The rest of oil from column C-1 is collected by the hot pump 5, is
heated up to 340-360 oC in the tube furnace and enters the second rectification
column C-2, where the rest of needed fractions are produced. In case oil is not
hot enough before it enters the column C-1 there is an opportunity to bring a part
of reduced oil heated in the furnace 6 to the bottom of column C-1 in a hot jet
form. This scheme requires higher heating temperature in a furnace in
comparison with the single evaporation scheme due to separate evaporation of
low-boiling and high-boiling fractions. All the modern CDU units basically work
according to the double evaporation scheme.
 MODERN CRUDE DISTILLATION UNITS

1-Crude pump, 2-Heat Exchanger, 3-Condenser-refrigerators, 4-Hot pump, 5-Refrigerators, 6-Furnace

VACUUM DISTILLATION
VACUUM DISTILLATION UNIT

• The atmospheric residue when processed at lower pressures does not allow
decomposition of the atmospheric residue and therefore yields LVGO, HVGO and
vacuum residue. The LVGO and HVGO are eventually subjected to cracking to
yield even lighter products. The VDU consists of a main vacuum distillation
column supported with side strippers to produce the desired products. Therefore,
VDU is also a physical process to obtain the desired products.
• Operating Conditions : The pressure maintained is about 25 – 40 mm Hg. The
temperature is The temperature is kept at around 380 – 425oC.
VACUUM RECTIFICATION
• The principles and main units for vacuum rectification resemble those for atmospheric
rectification. The major exceptions are that larger-diameter towers are used to maintain
comparable vapor velocities at reduced operating pressures. A vacuum of 50 to 100 mm of Hg
absolute is produced by a vacuum pump or steam ejector. The capacity of modern vacuum
rectification units is about 3.5 million tons per annum.
• The primary advantage of vacuum rectification is that it allows the distilling of heavier materials
at lower temperatures than would be required at atmospheric pressure, thus avoiding thermal
cracking of the components. The input temperature of the atmospheric residue in the vacuum
tower usually does not exceed 425°C. The residue from atmospheric rectification is preheated
against distillates and vacuum residue before heating up in the fired heater. From the heater
outlet the stream is fed to the vacuum tower. The high specific volume of vapour at low pressure
demands large tower diameters, particularly in the upper part. The lower part of the tower
(below the feed inlet) is used as a stripping section using steam to reduce the partial pressure of
hydrocarbons in the vapor phase.
• An example of the one-step vacuum rectification is shown in the following figure . The feed
(atmospheric residue) passes through oven O1 to the vacuum tower Tl. In this tower, the feed is
typically separated into the following fractions: vacuum residue 8, middle oil distillate 4, and light
oil distillate 3. The middle oil fraction is fractionated in tower T2 into fraction with narrower
boiling temperature ranges. Steam 2 is used to reduce the partial pressure of the oil fraction
which, finally, helps in the separation of the light fractions from the oil.
• O-1 and O-2-Oven
• Tl and T2- Rectification towers
• 1. Residue from the rectification under the atmosphere pressure,
• 2. Light oil,
• 3-6. Distillate,
• 7-9. Vacuum residue
Vacuum Distillation Cont..
The residue remaining after vacuum rectification is called "Goudron". This
may be used for blending to produce road asphalt or residual fuel oil, or it
may be used as a feedstock for thermal cracking or coking units. Vacuum
rectification units are an essential part of the many processing units required
for the production of lubricants.
In modern refineries, atmospheric and vacuum rectification processes are
rarely carried out in separate units. Usually, combined atmospheric-vacuum
rectification units are used for these processes.
Petroleum 1 for rectification is fed from storage tanks at ambient
temperature through a series of heat exchangers in order to attain the
temperature of approximately 120. A controlled amount of fresh water is
introduced, and the mixture is pumped into an electrical desalting and drying
unit (EDDU), where it passes through an electrical field and a salt water
phase is separated. If the salt is not removed at this stage, it will be
deposited later on the tubes of the ovens or heat exchangers. This can cause
plugging and corrosion.
Refining Processes
1. Light fraction processing
1.1 Catalytic Naphtha reforming
1.2 Isomerization
1.3 Alkylation
1.4 Etherification
1.5 Polymerization and Dimerization

2. Heavy Distillate processing

2.1 Catalytic Hydrotreating
2.2 Fluid Catalytic cracking (FCC)
2.3 Hydrocracking

3. Residual Oil processing

3.1 Solvent De-asphalting
3.2 Visbreaking
3.4 Residual Hydrocracking & residue FCC
Thermal Cracking
• With the advent of the mass production of large numbers of gasoline- powered vehicles,
the demand for gasoline has grown dramatically. On the other hand, distillation
processes produce only a specific amount of gasoline from a given quantity of crude oil
of specific characteristics. In 1913, the thermal cracking process was developed. In this
process, heavy fuels containing large molecules are broken into smaller ones to produce
additional gasoline and distillate fuels by application of both pressure and intense heat.
• Thermal cracking is a radical chain process. The chain process contains three main stages:
chain start, chain growth and chain termination. In the "chain start", cracking of the
hydrocarbons in the heavy feed proceeds at the weakest bonds of the hydrocarbons.
Also, cracking of C-C bonds proceeds first, because the energy requirement for C-C bond
breakage in hydrocarbons is lower than that for C-H bond scission. In a long chain, the
weakest C-C bond (C-C bond with the lowest energy requirement for breakage) is at the
centre of the molecule. Furthermore, the difference in energy of the C-C bond at
different locations in a molecule is lower at a higher temperature than at lower
temperatures. This means that at moderate temperature (about 400-450°C), cracking of
the hydrocarbon chains proceeds symmetrically. At a higher temperature, cracking can
proceed almost with the same probability at every C-C bond in the hydrocar- bon
molecule.
Thermal Cracking Cont…
• It should be noted that paraffins and olefins are formed during paraffin cracking
• The olefins formed during thermal cracking are characterized by the fact that the
bond in the beta-position (the second bond from the double bond) is weaker
than the C-C bond in the paraffin chain. The energy of the bond in the paraffin
chain is approximately 320 kJ/mol, whereas the energy of the bond in the beta-
position is 259 kJ/mol and the energy of the C-C bond in the alpha-position is 371
kJ/mol. This means that the olefins formed during cracking can be cracked more
extensively than the initial paraffins.
• The side chains of aromatic rings can be cracked very extensively. The energy of
the bond in the beta-position for these compounds is 273 kJ/mol.
• The next step after "chain start" is "chain growth". The same reactions as
occurred during "chain start" also occur in this stage of thermal cracking.
However, the most important reaction of "chain growth" is the reaction for
formation of light stable molecules (HR), from the radical (-R) formed during
chain start as well as from the heavier radical from the feed molecule.
Reactions during thermal cracking
Important reaction of "chain growth" is the reaction for formation of light stable molecules (HR), from the
radical (-R) formed during chain start as well as from the heavier radical from the feed molecule.
•R + CH3-CH2-CH2-CH2-CH3 -> HR + •CH2-CH2-CH2-CH2-CH3
Another reaction that can also occur in this stage is the cracking of radicals at the beta-bond
•CH2-CH2-CH2-CH2-CH3 -> -CH2-H2C + •CH2-CH2-CH3
⏚
• CH2=CH2
Another reaction type that occurs during the "chain growth" step of thermal cracking is the addition reaction
involving a radical and a double bond
•CH3 + CH2=CH-CH3 -> CH3-CH2-CH-CH3

Chain termination is the last stage of every chain reaction. There are two types of reactions that typically occur
in thermal cracking chain termination. One type is radical recombination is as follows;
•CH2-CH3 + -CH2-CH2-CH3 -» CH3-CH2-CH2-CH2-CH3

The second type is radical disproportionation

•CH2-CH3 + -CH2-CH2-CH3 -» CH3-CH3 + CH2=CH-CH3

 Reactions during thermal cracking
The greatest problem during thermal cracking arises from reactions involving aromatic feed. Aromatic
compounds in the feed have a very high tendency to undergo polycondensation reactions that lead to coke
formation. Coke formation decreases the yields of the desired gasoline and diesel fractions. One example of a
polycondensation reaction is shown in reaction

This reaction is an illustration that molecules of some products from thermal cracking reactions
can sometimes be larger than the feed molecules.
Two stage Thermal Cracking
Thermal cracking units provide a severe treatment to the feed and, often, convert up to 50% of the incoming
feed to naphtha and light diesel oils. To obtain a more severe treatment of the feed during thermal cracking, a
two-stage cracking unit is employed. A schematic of such a unit is shown in following figure.
Two stage Thermal Cracking
• In the scheme, the feed (heavy residue from atmospheric rectification) passes to the bottom part
of tower T3 and to the upper part of the low- pressure evaporator T4. The feed in T4 mixes with
the heavy gas oil vapours and then passes to T3. The feed from the bottom of T3 passes to oven
O1 for the heavy feed.
• Tower T3 has a blind tray in its middle section. The vapor from the bottom part of the tower can
pass through this tray to the upper section of the tower, but the liquid from the upper section
cannot pass to the bottom section. The liquid from the upper section of tower T3 passes to the
deep cracking oven O2.
• The cracked products from both the ovens are directed to the reaction tower Tl. The mixture of
vapor and liquid from Tl passes to the high-pressure evaporator T2. In T2 the cracking residue is
separated from the vapor. This residue passes to the low-pressure evaporator T4, and is partly
evaporated. The evaporator T4 has a blind tray in the middle section similar to that of tower T3.
The vapor product (heavy gas oil) is partly condensed in the upper section of T4 and mixed with
the fresh feed. The non-condensed part leaves the cracking unit as kerosene - gas oil fraction 2.
• The volatile product from T2 passes to the rectification tower T3. The gas 1 and gasoline fractions
leave the upper section of tower T3. The gasoline fraction passes to the rectification tower T5 for
further fractionation into fractions of light gasoline 3 and gasoline fraction 4. feed
• The last product of the thermal cracking unit is the cracking residue 5, the bottom product of the
low-pressure evaporator T4.
• Thermal cracking processes can only convert up to 50% of the feed. Hence it may subjected to
catalytic cracking in order to improve the conversion level of the heavy feed.
Catalytic Cracking
• The use of thermal cracking units to convert gas oils into naphtha began in 1913. These
units produced small quantities of unstable naphtha and large amounts of by-product
coke. While they succeeded in providing a small increase in gasoline yields, it was the
commercialization of the fluid catalytic cracking process in 1942 that really established
the foundation for modern petroleum refining. The process not only provided a highly
efficient means of converting high boiling gas oils into naphtha to meet the rising
demand for high-octane gasoline, but it also represented a breakthrough in catalyst
technology.
• The 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 carbonium ion theory.
According to this theory, the catalysts can be classified into two groups as follows:
a) Catalysis on metals
b) Catalysis on acid catalysts
Catalytic Cracking
The main stages of the catalytic reaction can be represented as follows:
• Diffusion of reactants through the liquid or gas film on the surface of the catalyst
particle,
• Diffusion of reactants into the pores of the catalyst,
• Adsorption of the reactants on the inner surface of the catalyst pores,
• Chemical reaction on the inner catalyst surface,
• Desorption of products from the inner catalyst surface,
• Diffusion from the inner catalyst surface through the pores to the external catalyst
surface,
• Diffusion of products through the liquid or gas film on the external surface of catalyst
The aromatic hydrocarbons only have a negative influence in catalytic cracking as a result
of polycondensation and coke formation on catalyst surface. The destruction of aromatic
ring without previously saturating the unsaturated bonds is impossible even in catalytic
cracking. However, aromatic compounds are not absolutely non-reactive during catalytic
cracking. The most important reactions of aromatic compounds during catalytic cracking
are isomerization reactions
Catalytic Cracking
There are three basic functions in the catalytic cracking process:
• Reaction: Feedstock reacts with the catalyst and cracks into different hydrocarbons.
• Regeneration: The catalyst is reactivated by burning off the coke.
• Fractionation: The cracked hydrocarbon stream is separated into various products.
A modern catalytic cracking unit employs a finely divided solid catalyst that has properties
analogous to a fluid when it is agitated by air or oil vapours. The oil feed is vaporized when
it meets the hot catalyst at the feed-injection point, and the vapor flows up- ward through
the riser reactor at a high velocity, providing a fluidizing effect for the catalyst particles.
Catalytic reaction occurs exclusively in the riser reactor.
Coke, a by-product of cracking, is deposited on the catalyst particles. Since these deposits
impair reaction efficiency, the catalyst must be continuously put through the regenerator,
where the carbon is burned with a current of air. The high temperature of the regeneration
process (675-785°C) heats the catalyst to the de- sired reaction temperature for re-
contacting fresh feed in the unit.
In order to regenerate the activity of the catalyst completely, a small amount of fresh
catalyst is added to the system from time to time. Following figure depicts typical reactor-
regenerator sections of a catalytic cracking unit used in petroleum refineries.
Catalytic Cracking
Catalytic Cracking
The catalytic cracking process is very flexible, and operating parameters can be adjusted to meet changing
product demand. In addition to cracking, catalytic activities include dehydrogenation, hydrogenation, and
isomerization.
The three types of catalytic cracking processes in operation in modern refineries are:
• Fluid catalytic cracking (FCC)
• Moving-bed catalytic cracking
• Thermofor catalytic cracking (TCC)
The most common process is fluid catalytic cracking (FCC) in which the oil is cracked in the presence of a finely
divided catalyst maintained in a fluidized state by the oil vapours. The fluid cracker consists of a catalyst section
and a fractionating section that operate together as an integrated processing unit. The catalyst section contains
the reactor and regenerator. The fluid catalyst is continuously circulated between the reactor and the
regenerator using air, oil vapours, and steam as the conveying media
A typical FCC process involves mixing a preheated hydrocarbon charge with hot, re-generated catalyst as it
enters the riser leading to the reactor. The charge is combined with a recycle stream within the riser, vaporized,
and raised to reactor temperature (500-550°C) by the hot catalyst.
The moving-bed catalytic cracking process is similar to the FCC process. The catalyst is in the form of pellets
that are moved continuously to the top of the unit by conveyor or pneumatic lift tubes to a storage hopper,
then flow downward by gravity through the reactor, and finally to a regenerator. The regenerator and hopper
are isolated from the reactor by steam seals. The cracked product is separated into recycled gas, oil, clarified
oil, distillate, naphtha, and wet gas.
In a typical thermofor catalytic cracking unit, the preheated feedstock flows by gravity through the catalytic
reactor bed. The vapours are separated from the catalyst and sent to a fractionating tower. The spent catalyst is
regenerated, cooled, and recycled. The flue gas from regeneration is sent to a carbon monoxide boiler for heat
recovery.
Catalytic Naphtha Reforming
It is part of Light Oil processing.
Catalytic naphtha reforming produces high-octane reformate for gasoline blending or Benzene,
Toluene & Xylene aromatics for petrochemical feedstocks.
Reforming reactions comprise cracking, polymerization, dehydrogenation, and isomerization, which
take place simultaneously.
Reforming processes differ in the mode of operation semi-regenerative or continuous catalyst
regenerative (CCR), catalyst type, and process engineering design. It is important to remove
permanent reforming catalyst poisons and to reduce the temporary catalyst poisons to low levels.
There are more than 700 reformers worldwide, with a total capacity of approximately 14.5 million
barrels/day. Approximately 40% of this capacity is located in North America, followed by 20% each
in Western Europe and Asia-Pacific regions.
CATALYTIC REFORMING
• There are many chemical reactions that occur in the catalytic
reforming process, all of which occur in the presence of a catalyst and
a high partial pressure of hydrogen. Depending upon the type or
version of catalytic reforming used as well as the desired reaction
severity, the reaction conditions range from temperatures of about
495 to 525 °C and from pressures of about 5 to 45 atm.
• The commonly used catalytic reforming catalysts contain noble
metals such as platinum and/or rhenium, which are very susceptible
to poisoning by sulfur and nitrogen compounds. Therefore, the
naphtha feedstock to a catalytic reformer is always pre-processed in
a hydrodesulfurization unit which removes both the sulfur and the
nitrogen compounds. Most catalysts require both sulphur and
nitrogen content to be lower than 1 ppm.
Four major catalytic reforming reactions:
1: The dehydrogenation of naphthenes to convert them into aromatics as exemplified in the
conversion methylcyclohexane (a naphthene) to toluene(an aromatic), as shown below:

2: The isomerization of normal paraffins to isoparaffins as exemplified in the conversion of normal

octane to 2,5-Dimethylhexane (an isoparaffin), as shown below:

3: The dehydrogenation and aromatization of paraffins to aromatics (commonly called

dehydrocyclization) as exemplified in the conversion of normal heptane to toluene, as shown below:
4: The hydrocracking of paraffins into smaller molecules as exemplified by the cracking of
normal heptane into isopentane and ethane, as shown below:
Isomerization
Isomerization is an intermediate process.
There are mainly two types of units exist: C4 isomerization and C5/C6 isomerization.
• C4 unit converts normal butane into isobutane, to provide additional feedstock for alkylation
units,
• C5/C6 unit isomerizes mixtures of C5/C6 paraffins,
Isomerization is similar to catalytic reforming in that the hydrocarbon molecules are rearranged, but
unlike catalytic reforming, isomerization just converts normal paraffins to isoparaffins. The greater
value of branched paraffins over straight paraffins is a result of their higher octane contribution.
The formation of isobutane is a necessary step to produce alkylate gasoline or methyl tertiary butyl
ether (MTBE). The extent of paraffin isomerization is limited by a temperature-dependent
thermodynamic equilibrium. For these reactions, a more active catalyst permits a lower reaction
temperature and that leads to higher equilibrium levels.
Isomerization of paraffins takes place under medium pressure (typically 30 bar) in a hydrogen
atmosphere. C4 isomerization produces isobutane feedstock for alkylation. Platinum or another
metal catalyst, alumina chloride, is used for the higher temperature processes. In a typical low-
temperature process where only aluminum chloride is used, the feed to the isomerization unit is
n-butane or mixed butanes combined with hydrogen (to inhibit olefin formation).
C5/C6 isomerization increases the octane number of the light gasoline components n-pentane and
n-hexane, which are found in abundance in straight run gasoline. The basic C5/C6 isomerization
process is essentially the same as butane isomerization.
Alkylation
Alkylation is the process that produces gasoline range compounds from the combination of light
C3–C5 olefins (mainly a mixture of propylene and butylene) with isobutene.

The highly exothermic reaction is carried out in the presence of a strong acid catalyst, either sulfuric
acid (H2SO4) or hydrofluoric acid (HF).

The world alkylation capacity stands at 2.5 million barrels/day and new grassroots units have been
constructed in many refineries worldwide, especially those with FCC units.

The alkylate product is composed of a mixture of high-octane, branched-chain paraffinic

hydrocarbons.

Alkylate is a premium clean gasoline blend, with octane number depending on the type of
feedstocks and operating conditions. Research efforts are being directed toward the development
of environmentally acceptable solid super acids capable of replacing HF and H2SO4. Much of the
work is concentrated on sulfonated zirconia catalysts
Polymerization and Dimerization
Catalytic polymerization and dimerization in petroleum refining refers to the conversion of FCC light
olefins, such as ethylene, propylene, and butenes, into higher octane hydrocarbons for gasoline
blending.

Polymerization combines two or more identical olefin molecules to form a single molecule, with the
same elements being present in the same proportions as in the original molecules. Light olefin
feedstock is pre-treated to remove sulfur and other undesirable compounds. In the catalytic
process, the feedstock either is passed over a solid phosphoric acid catalyst on silica or comes into
contact with liquid phosphoric acid, where an exothermic polymeric reaction occurs.

Another process uses a homogenous catalyst system of aluminum-alkyl and a nickel coordination
complex. The hydrocarbon phase is separated, stabilized, and fractionated into LPG and oligomers
or dimers.
Hydroprocessing
it is impossible to convert a hundred percent of the crude oil residue to light fractions by using
both thermal and catalytic cracking processes alone. The main reason for this is that cracking
reactions need to be accompanied by hydrogen transfer reactions in order to stabilize the
product. It is obvious that light fractions such as gasoline or diesel fractions are more hydrogen
rich than coke and residue by-products of thermal or catalytic cracking processes. This means
that hydrogen transfer proceeds from heavy fractions to light cracking products during the
cracking processes. However, the complete conversion of cracking feed to light fractions is
impossible because of the shortage of hydrogen in the feed. Also, heteroatom compounds
present in the feed tend to form coke on the catalysts. The elimination of heteroatom
compounds requires hydrogen, which thereby limits hydrogen transfer to the light fractions.
Catalytic hydro-processing is a hydrogenation process used to remove heteroatom compounds
(i.e., compounds containing nitrogen, sulphur, oxygen, and/or metals) from liquid petroleum
fractions. These compounds adversely influence equipment and catalysts in the refinery and
the quality of the finished product, especially on the ecological properties of the product.
Hydroprocessing units are installed prior to units for processes such as catalytic reforming so
that the expensive platinum catalyst is not contaminated by untreated feedstock.
Hydroprocessing is also used prior to catalytic cracking to reduce sulphur and improve product
yields, and to upgrade middle-distillate petroleum fractions into finished kerosene, diesel fuel,
and heating fuel oils. In addition, hydrotreating converts olefins and aromatics to saturated
compounds.
Reactions that take place during hydroprocessing

All the reactions that take place during hydroprocessing can be classified into four large groups:
• Reactions of sulphur containing compounds
• Reactions of nitrogen containing compounds
• Reactions of oxygen containing compounds
• Reactions of hydrocarbons
Depending on the feed used, hydroprocessing can be used for the treatment of
middle fractions, for example, to improve the burning characteristics of distillates,
such as kerosene. Hydrotreatment of a kerosene fraction can convert aromatics
into naphthenes.
The hydroprocessing of heavy oil fractions, for example, lubricating oil
hydroprocessing, uses a catalytic treatment of the oil with hydrogen to improve
product quality. The objectives in mild hydroprocessing include saturation of olefins
and reduction of the acid nature of the oil. Mild oil hydrotreating also may be used
following solvent processing.
Hydrotreating also can be employed to improve the quality of pyrolysis gasoline, a
by-product from the manufacture of ethylene. Traditionally, the outlet for this
gasoline has been motor gasoline blending, a suitable route in view of its high
octane number. However, only small portions of untreated pyrolysis gasoline can be
used for blending owing to its unacceptable odour, colour, and gum-forming
tendencies. The quality of pyrolysis gasoline, which is high in diolefin content, can
be satisfactorily improved by hydroprocessing, whereby conversion of diolefins into
mono-olefins provides an acceptable product for motor gasoline blending.
Hydroprocessing
• The hydroprocessing of sulphur containing compounds proceeds with the formation of hydrogen
sulphide. An example of this reaction is shown in the following reaction equation.
2R-SH + 3H2 -» 2R-H + 2H2S
• Sulphides and disulphides are hydrogenated in two steps. The reactions for the hydrogenation of
sulphides and disulphides are shown in the reaction equations.
2RSR + 2H2 -»2R-SH + 2RH + 3H2 -> 2R-H + 2RH + 2H2S RSSR + H2 -> 2R-SH + 3H2 -> 2R-H + 2H2S
• The hydrogenation of the cyclic sulphide proceeds with ring destruction + H2 -> CH3-CH2-
• The next important class of heteroatom containing compounds are those that contain nitrogen.
The hydrogenation of these compounds proceeds with the formation of ammonia
C6H5NH2 + H2 -> C6H6 + NH3
• The hydrogenation of cyclic nitrogen containing compounds proceeds very slowly and with a very
low conversion. This reaction proceeds in four steps shown in the reaction equation
• 2H2 H2 -» CH3-CH2-CHrCH2-NH2 NX " + H2 -T CH3-CH2-CH2-CH3 + NH3
• During the hydrogenation of oxygen containing compounds, hydrocarbons and water are formed.
An example of this reaction is shown in the reaction equation .
R-COOH + 2H2 -> R-CH3 + 2H2O
• The hydrogenation of hydrocarbons involves the saturation of the non- saturated bonds (6.51),
which are formed during all the cracking processes shown in the previous sections.
CH3-CH=CH-R + H2 -» CH3-CH2-CH2-R
• The majority of hydroprocessing reactions are exothermic reactions.
However, the hydroprocessing of light fractions from the catalytic
cracking unit can have a relatively small exothermic heat effect,
approximately 80 kJ/kg. On the other hand, the hydroprocessing of
more unsaturated and heteroatom rich feed can have an exothermic
heat effect of up to 500 kJ/kg. It has therefore become essential that
most modern hydroprocessing plants have heat exchangers to take
out the heat during the process.
• Modern hydroprocessing is carried out with the use of catalysts. The
typical catalysts for this process are oxides and sulphides of nickel,
cobalt, molybdenum, and vanadium.
• In a typical catalytic hydroprocessing unit, the feedstock is deaerated and mixed with hydrogen.
This is preheated in a fired heater to the temperature of 350-400°C and then charged through a
fixed-bed catalytic reactor. In the reactor, the sulphur and nitrogen compounds in the feedstock
are converted into H2S and NH3. The reaction products leave the reactor and, after separation in
the hot separator and cooling to a low temperature, enter the liquid/gas separators in which
wash water is used to remove the ammonia and hydrogen sulphide. The sour water leaves the
separator in the bottom section of the equipment. The overhead gas from the cold separator is
charged to the high-pressure scrubber to remove hydrogen sulphide from the recycled gas. It is
chemically absorbed in an amine solution. The purified recycle gas is mixed with fresh hydrogen
to compensate for the losses in the hydrogenation reactions. The recycled gas compressor routes
the gas back to the reactor loop. The liquid product streams are sent to a rectification tower
where the volatile product is hydro- treated naphtha.
• The bottom product from the rectification tower is sent to the vacuum rectification tower for
further rectification. The bottom product from vacuum tower is the middle distillate.
Just like any catalytic process in the crude oil industry, the big problem in hydroprocessing
is the deactivation of the catalyst during the process. There two main mechanisms of
catalyst deactivation during hydroprocessing:
• Deactivation by coke formation on catalyst surface
• Deactivation by heavy metals deposition on catalyst active centres
Deactivation by coke formation can take place by many mechanisms. For example, coke or
similar compounds such as polyaromatic compounds can be adsorbed on the surface of
the catalyst.
Catalyst can also be deactivated by adsorption of asphaltenes during the hydroprocessing
of heavy crude oil residues.
All heavy crude oil residues have heavy metals such as Ni, V or Fe in their structure. These
metals are bonded as organometallic compounds. At high temperatures and for
hydrogenation reactions, these compounds are cracked and heavy metals are deposited on
the catalyst surface. These metals can also react with hydrogen sulphur from the gas phase
to form metal sulphides. The deposition of sulphides of iron, vanadium or nickel leads to
irreversible poisoning of the catalyst. This is the difference between catalyst deactivation
by metals and deactivation by coke; the former leads to an irreversible loss of the catalyst
activity.
Coking
Coking converts heavy feedstocks into solid coke and low boiling hydrocarbon intermediate
products — suitable for conversion into higher value transportation fuels.
Coking is a severe thermal cracking process resulting in carbon (coke) as an end-product.
For reasons of safety, the volatile matter from the coke is removed by calcining at about
1200 C. Petroleum coke is usually one of three types in appearance: sponge-like, needle-
like and spherical.
Petroleum coke is mainly used for manufacture of:
• Anodes for electrolytic cells;
• Electrodes for electric furnaces to produce phosphorous, titanium dioxide and various
carbides;
• Graphite.

Three processes for Coking

• Delayed Coker
• Flexi Coker
• Fluid Coker
Delayed coker
A typical delayed coking unit involves furnaces, coke-drums, fractionating unit, hydraulic
decoking equipment, coke storage, cooling and water purification facilities.
Per ton of coke, about 300 kgs of steam and 30 units of power are required. Effluent of
coke drums on fractionation gives streams varying from gas to gas-oil. The most crucial
part of the operation is the switching of the coke drums. When the coke drum in service is
‘full’ to the pre-specified level, the preheater effluent is switched to the ‘empty’ coke
drum, while isolating the ‘full’ drum. The ‘full’ drum is then steamed to remove
hydrocarbon vapours, cooled by filling with water, opened, drained and the coke removed.
So, minimum two coke drums are required. Filling a drum takes about a day and switching,
steaming out, cooling, draining, decoking etc. of the other drum takes as much time. When
the time period of either one is improved, the other has to be matched.
The main operating independent variables are:
• Carbon content of feedstock
• Preheater outlet temperature;
• Fractionator pressure, and
• Gasoil draw-off temperature
Conceptual layout of Delayed cocker unit
Delayed Coker output
As a thumb-rule, coker gas consists of about 15% H2, 50% methane, 15% ethane,
10 % propane, the balance being olefins.

The naphtha is drawn usually in two cuts, for example:

• Light naphtha (1/3rd by vol. of 65 oAPI) after hydrotreating for sulphur removal
and olefin saturation and hence is either isomerized to improve octane or blended
directly into finished gasoline.
• Heavy naphtha (2/3rd by vol of 50 oAPI) which is reformed after hydrotreating.

Similarly, the gas oil is drawn usually in two cuts, for example:
• Light gas oil (2/3rd by vol. of 30 oAPI), which is fed to FCC after hydrotreating; and
• Heavy gas oil (1/3rd by vol. of 13 oAPI), which is used as fuel or sent for vacuum
distillation.
Other Coking processes
Flexicoker
A flexicoker is equipped with a fluidized bed of hot coke and is designed to gasify majority
of the coke produced in its reactor. The coke gas from flexicoker after cleaning has about
15-20% H2, 0.5- 2% CH4, 20-25% CO and the balance 57-63% as N2+CO2. Such a gas has a
molecular weight of about 24 and the low heating value (LHV)

Fluid coker
Fluid coking is a thermal conversion (coking)process. It uses a two vessel fluid bed system
much the same as in an FCCU, except that instead of catalyst, coke particles flow from one
vessel to another. Further, a fluid coker is similar to flexicoker except that gasification of
coke is done only partially. For a given feedstock, fluid coker costs roughly about as much
as delayed coker; but flexicoker somewhat more.
Utility requirements of a fluid coker are significantly higher than for a delayed coker.
Combined yield of gasoline and gas oil (C5+liquid) from fluid and flexicoking is nearly the
same and somewhat better than delayed coker. However, the net yield of coke from fluid
coker is about 2/3rd and from Flexicoker just about 7% of that from delayed coker.
Visbreaking
Visbreaking is a mild thermal cracking process applied to reduce the viscosity of VDR to
produce fuel oil and some light products to increase the distillate yield in a refinery

The demand for light fractions grows all the time, at the same time the requirement for
heavy residual fuel oils declines. Furthermore, many of the new sources of crude
petroleum have yielded heavier crude oils with higher natural yields of residual fuels. As a
result, refiners have become even more dependent on the conversion of residue
components into lighter products.

Visbreaking units typically convert about 15% of the feedstock to naphtha and diesel oils
and produce a lower-viscosity residual fuel.
Visbreaking is achieved in two different ways:
• Furnace cracking, it requires about 1 to 3 minutes as reaction time
and about 470 to 500 C temperature. In this case, the furnace effluents
are quenched with gas oil to stop cracking before entering fractionator.
Fuel consumption accounts for about 80% of operating cost.
• Soaker cracking, the furnace effluents at about 430 to 440 C pass
through a soaker drum to have higher reaction time before it is
quenched and sent for fractionation. The fuel requirement is about
35% lower than furnace cracking.
Density and viscosity of middle distillates obtained from a visbreaker
are largely independent of their feedstock characteristics. However,
diesel index and octane number are closely related to feed
characteristics.
Conceptual plant layout for Soaker Visbreaker
Processes for Lube base oils manufacturing
The manufacture of lube base oils can be done using any of the following processes
below,
• Extraction Process
• Conversion Process
The extraction process is achieved in a sequence of processes namely: Distillation,
De- asphalting, Extraction, Dewaxing, Finishing.
The conversion process is achieved by Distillation, Hydrocracking, Hydrodewaxing,
& Hydrotreating
Extraction process for base oils
Extraction process involves following steps;

Distillation process: This process separates the atmospheric residue mixture into a series of
fractions representing different viscosity, ranges from 90 - 500 neutrals. The residue contains
the heavier base oils such as the bright stocks. (150 - 250 SUS at 100 C). The latter is separated
from resins and asphaltenes prior to introduction into the extraction process.

De-asphalting: It takes the residuum from the bottom of the distillation column and separates
them into de-asphalted oil and tar. De-asphalted oil is similar to the lube distillates but
possesses higher boiling points.

Extraction Process: This process involves the removal of impurities such as aromatics, sulfur
and nitrogen compounds. Aromatics make poor quality base oils because they are among the
most reactive components in the natural lube oil boiling range. Oxidation of aromatics can start
a chain reaction that can dramatically shorten the useful life of base oil. Conventionally, solvent
extraction is adopted as the purification process, in which aromatics are removed by feeding
the raw lube distillate into a solvent extractor where it is counter-currently contacted with a
solvent. The resulting product is usually referred to as raffinate.
Extraction process for base oils (Cont)..
Dewaxing Process: It utilizes dewaxing solvents like methyl-ethyl-ketone (MEK), toluene or phenol to be mixed
with the waxy oil. The mixture is then cooled to a temperature 10 to 20 degrees below the desired pour point .
The wax crystals are then removed from the oil by filtration. More desirable alternatives to solvent dewaxing
are;
1. Catalytic dewaxing - It removes long n-paraffins and waxy side chains from other molecules by catalytically
cracking them into smaller molecules
2. Wax hydro-isomerization - The more advanced form of the catalytic dewaxing process. This process
isomerizes n-paraffin and other molecules with waxy side chains into branched molecules with very desirable
quality as base oils rather than cracking them away.

Finishing Process: It is the final process in the manufacturing of base oils. Its aim is to improve colour and
thermal/oxidative stability of base oil. Here hydrogen is added to base oil at an elevated temperature in the
presence of catalyst. By reaction of hydrogen with some remained sulfur and/or nitrogen containing molecules,
these sulfur/nitrogen containing compounds are decomposed into smaller molecules. A great majority of
sulfur, nitrogen and aromatics are thus removed. The reforming process produces molecules that have
improved isometrics, oxidative stability and product colour
Conversion process for Base oils
The Conversion process involves following steps;

Distillation process: This process separates the atmospheric residue mixture into a series of fractions with
different molecular weight and viscosity ranges.

Hydrocracking: The distillates are subjected to a chemical reaction with hydrogen in the presence of a catalyst
at high pressures and temperatures. The naphthenic and aromatic carbon rings are broken, and re-joined
using hydrogen to form an iso-paraffin structure (S-Oil Corporation, 2011). In this process water, ammonia,
hydrogen-sulfide is also removed.

Hydrodewaxing: This process employs a hydrogenation unit and a catalyst that is specific to conveying waxy
normal paraffin to more desirable isoparaffin structures.

Hydrotreating: The process helps to introduce saturation of any unsaturated molecules as the two previous
processes involved the breaking of chemical bonds between carbon atoms. This is easily done by introducing
more hydrogen.
Several different reactions occur in this process, the principal ones being:
• Polar compounds containing oxygen, sulphur and nitrogen removal.
• Aromatic hydrocarbons conversion to saturated cyclic hydrocarbons.
• The breaking up of heavy poly-cycloparaffin to lighter saturated hydrocarbons, etc.
These reactions take place at very high temperatures (380 - 420°C) and pressures (216 – 217 Bars) in the
presence of a catalyst. The hydrocarbons that are formed in the process are very stable
Advantages of Conversion process
Generally, both solvent extracted/refined and hydro-treated base oils are manufactured in
the same way, but differ in the methods employed. The following are the characteristics
and significant differences:

• Colour - Hydro-treated base oils are clear and colourless.

• Viscosity Index – Hydro-treated base oils generally have higher VI's than Solvent Refined
oils. As a result, viscosity drops off less at high temperatures than with Solvent Refined
oils.
• Carbon Residue - Lower for Hydro-treated base oils.
• Total Acid Number (TAN) - Lower for Hydro-treated base oils.
• Demulsibility – Hydro-treated oils will shed water better than Solvent Refined oils.
• Oxidation Resistance – Hydro-treated base oils, at equal levels of anti-oxidant treatment,
give superior resistance to oxidation.
• High Temperature Stability - Better high temperature stability for Hydro-treated oils.