Petroleum Refining &

Petrochemicals
Chemical Engineering Department
NIT Hamirpur (H.P) - 177005
Petroleum Refining, Operation &
Optimization
• Crude oil received from oil fields are stored in refinery storage tanks

• From tank to atmospheric distillation unit (ADU)

• Crude oil physically separated based on their boiling range by conventional process of distillation

• In order of rising boiling range the fractions are

• Methane, ethane and propane mixture

• Liquefied petroleum gas (LPG)

• Naphthas /Gasoline fractions

• Kerosine /Aviation Turbine Fuel (ATF)

• High Speed Diesel Oil (HSD) and Light Diesel Oil (LDO)

• Reduces crude oil (RCO)

Petroleum Refining, Operation &
Optimization
• Reduced Crude Oil further distilled under vacuum to recover lighter fractions – light vacuum gas
oil (LVGO), heavy vacuum gas oil (HVGO) and vacuum residue (VR)
• For viscosity specification of fuel oil, HVGO, RCO and VR are processed in visbreaking unit to
reduce viscosity
• Bitumen – vacuum residue air blown in bitumen blowing unit

• Middle distillates – HVGO processes in fluid catalytic cracking (FCC) unit, hydrocracking unit and
coking unit
• Straight-run naphtha of low octane number processed in catalytic reforming unit to enhance octane
number
• Reformate rich in benzene/toluene is used as feedstock for Udex unit to produce benzene and
toluene
• To improve smoke point, Edeleanu process is usually employed
Petroleum Refining, Operation &
Optimization
• Selection of processes for optimization
• Optimization is a process to determine the best possible way of selecting the processes scheme and fixing the
unit capacities etc. The influencing factors which decides the process scheme for a given refinery are as follows
• Type of crude oil

• Product slate

• Product specification

• Investment and operating costs

• Merits/demerits of alternative processes

• Type of crude oil – High sulfur crude requires installation of desulphurization or sweeting unit

• Product slate – The capacity of the refinery, type and size of the secondary processing units is governed by the
product slate which decides the demand of petroleum products
Petroleum Refining, Operation &
Optimization
• Selection of processes for optimization
• Product specification – Treatment process are governed by specification of the products.
Depending upon crude type processed and quality of streams, treatment has to be selected
from simple caustic wash, sweeting unit to hydro-desulphurization

• Investment and operating costs – refinery capacity, processing and sizing of unit
capacities

• Merits/demerits of alternative processes – extraction of aromatics from kerosene, apart

from conventional Edeleanu process one can choose sulfolane process.
Petroleum Refining, Operation &
Optimization
• Optimization in running refinery
• Factors beyond refinery control

• Crude mixture

• Type of processing units

• Demand pattern

• Movement constraints

• Product specifications

• External streams

• Industrial relations

• Factors within refinery control

• Improving over processing capacitates

• Adopt various effective measurements to control corrosion/erosion

• Plan shut down of various unit at optimum time

• Utilization of various stream to produce one finished product

• Profitability of refinery by reducing operating cost

Petroleum Refining, Operation &
Optimization
• Refinery Capacity in India

• IOC (company)

Guwahati (Refinery) – 1.0 MMTPA (Capacity as on 1.4.1997)

Barauni - 3.3 MMTPA

Gujarat – 9.5 MMTPA

Haldia – 3.75 MMTPA

Mathura – 7.5 MMTPA

Digboi – 0.65 MMTPA

• BPCL – Bombay – 6.0 MMTPA

• HPCL – Bombay – 5.5 MMTPA

Visakhapatnam – 4.5 MMTPA

• CRL – Cochin – 7.5 MMTPA

• MRL – Madras – 6.5 MMTPA

Narimanam – 0.5 MMTPA

• BRPL – Bongaigaon – 2.35 MMTPA

• MRPL – Mangalore – 3.0 MMTPA

• Total – 61.75 MMTPA

 Constituents of crude oil
• Main constituents are hydrocarbon
• C – 84 – 87%, H – 11 – 14%, S – 0.06 – 8%, N – 0.02 – 1.7, O – 0.08 – 1.82,
Metals – 0 – 0.14
• Alkanes (CnH2n+2)– Paraffins (straight chain and iso or neo)
• Cyclo alkanes (cycloparaffins) – naphthenes (saturated ring hydrocarbon)
• Alkenes, alkynes, cycloalkanoarenes,
• Non- hydrocarbon – Sulphur, nitrogen, oxygen, metallic compound, asphaltenes and
resins

• Classification of crude oil

• Paraffinic base
• Asphaltic base
• Intermediate base
• Hybrid base of naphthenic base
Hydrocarbon
 Non - Hydrocarbon

Complex Hydrocarbon

Crude oil also contains a large number of hydrocarbons that do not fall into the category of paraffi ns, olefi ns, naphthenes, or
aromatics, but may be the combined group of any two or more groups of paraffi ns, naphthenes, or aromatic hydrocarbons.
 Physical Properties of Crude Oil
• API Gravity - It measure the density of the stream, the API gravity is expressed as

o
API = 141.5 / specific gravity – 131.5

where specific gravity is measured at 60 oF. Higher values of API gravity indicate lower specific gravity and therefore lighter crude
oils or refinery products and vice-versa. As far as crude oil is concerned, lighter API gravity value is desired as more amount of gas
fraction, naphtha and gas oils can be produced from the lighter crude oil than with the heavier crude oil. Therefore, crude oil with
high values of API gravity are expensive to procure due to their quality.

• Watson Characterization factor - The Watson characterization factor is usually expressed as

K = (TB)1/3/specific gravity

where TB is the average boiling point in degrees R taken from five temperatures corresponding to 10, 30, 50, 70 and 90 volume %
vaporized. Typically Watson characterization factor varies between 10.5 and 13 for various crude streams. A highly paraffinic crude
typically possesses a K factor of 13. On the other hand, a highly naphthenic crude possesses a K factor of 10.5. Therefore, Watson
characterization factor can be used to judge upon the quality of the crude oil in terms of the dominance of the paraffinic or
naphthenic components.
 Typical Properties of Refinery
• TBP/ASTM distillation curves
• The most important characterization properties of the
crude/intermediate/product streams are the TBP/ASTM distillation curves.

• Both these distillation curves are measured at 1 atm pressure. In both these
cases, the boiling points of various volume fractions are being measured.

• However, the basic difference between TBP curve and ASTM distillation curve
is that while TBP curve is measured using batch distillation apparatus
consisting of no less than 100 trays and very high reflux ratio, the ASTM
distillation is measured in a single stage apparatus without any reflux.

• Therefore, the ASTM does not indicate a good separation of various

components and indicates the operation of the laboratory setup far away from
the equilibrium.
 TBP distillation curves
• The separation of hydrocarbons can be improved if the vapour and its

condensates (reflux) are in intimate contact for some time during distillation

and a reproducible distillation analysis is possible. Such a method of

distillation is known as true boiling point (TBP) distillation

• A reflux ratio of 5:1 is usually sought as the standard separation. Separation of

fraction by 1% volume can be obtained at a very close temperature difference

and such a close separation is comparable with a distillation tower of 10–12

plates. A routine crude distillation test is carried out in a standard TBP

distillation apparatus in a packed column of specific size and packing material

with a certain amount of reflux ratio (reflux/vapour ratio)

 Typical Properties of Refinery
• Sulphur content - Typically, crude oils with high sulphur content are termed as sour crude. On the other hand, crude oils with low sulphur
content are termed as sweet crude. Typically, crude oil sulphur content consists of 0.5 – 5 wt % of sulphur. Crudes with sulphur content
lower than 0.5 wt % are termed as sweet crudes.

It is estimated that about 80 % of world crude oil reserves are sour. The sulphur content in the crude oil is responsible for numerous
hydrotreating operations in the refinery process. Strict and tighter legislations enforce the production of various consumer petroleum products
with low quantities of sulphur (in the range of ppm). This indicates that large quantities of inorganic sulphur needs to be removed from the fuel.
Typically, inorganic sulphur from various intermediate product streams is removed using hydrogen as hydrogen sulphide.

• Viscosity - Viscosity is a measure of the flow properties of the refinery stream. Typically in the refining industry, viscosity is measured in
terms of centistokes (cst) or saybolt seconds or redwood seconds. Viscosity is a very important property for the heavy products obtained
from the crude oil. The viscosity acts as an important characterization property in the blending units associated to heavy products such as
bunker fuel. Typically, viscosity of these products is specified to be within a specified range and this is achieved by adjusting the viscosities
of the streams entering the blending unit.

• Flash point and fire point - Flash and fire point are important properties that are relevant to the safety and transmission of refinery
products. Flash point is the temperature above which the product flashes forming a mixture capable of inducing ignition with air. Fire point
is the temperature well above the flash point where the product could catch fire. These two important properties are always taken care in the
day to day operation of a refinery.
Visual presentation
 Typical Properties of Refinery
• Pour point - When a petroleum product is cooled, first a cloudy appearance of the product occurs at a certain temperature. This temperature is termed as the cloud
point. Upon further cooling, the product will ceases to flow at a temperature. This temperature is termed as the pour point. Both pour and cloud points are important
properties of the product streams as far as heavier products are concerned. For heavier products, they are specified in a desired range and this is achieved by blending
appropriate amounts of lighter intermediate products.

• Octane number - Octane number is an important property for many intermediate streams that undergo blending later on to produce automotive gasoline, diesel etc.
Typically gasoline tends to knock the engines. The knocking tendency of the gasoline is defined in terms of the maximum compression ratio of the engine at which
the knock occurs. Therefore, high quality gasoline will tend to knock at higher compression ratios and vice versa. However, for comparative purpose, still one needs
to have a pure component whose compression ratio is known for knocking. Iso-octane is eventually considered as the barometer for octane number comparison.
While iso-octane was given an octane number of 100, n-heptane is given a scale of 0. Therefore, the octane number of a fuel is equivalent to a mixture of a iso-octane
and n-heptane that provides the same compression ratio in a fuel engine. Thus an octane number of 80 indicates that the fuel is equivalent to the performance
characteristics in a fuel engine fed with 80 vol % of isooctane and 20 % of n-heptane. Octane numbers are very relevant in the reforming, isomerisation and
alkylation processes of the refining industry. These processes enable the successful reactive transformations to yield long side chain paraffins and aromatics that
possess higher octane numbers than the feed constituents which do not consist of higher quantities of constituents possessing straight chain paraffins and non-
aromatics (naphthenes).

• Bottom Sediment and Water – It measure the quantity of residual sediment mostly settleable from the crude oil (if sufficient time is allowed for settling) and water.
This may contain both heavy asphaltic hydrocarbon oil and non- hydrocarbons, such as inorganic salts. An amount of BSW is routinely tested for every batch of
crude oil received in a refinery. Water, salt, and sediment are removed from the storage tanks, followed by electrical desalting.
 Petroleum products and test methods
• Domestic fuels
• Liquified Petroleum Gas (LPG) – It is a mixture of propane and butane in liquified form at a pressure of
about 10–15 atm, depending on the proportion of the components present. This is the first product of
distillation from crude oil.
• Raw hydrocarbon gases contain sulfurous hydrocarbons, which may be odorous and corrosive. Hence,
treatment of these gases is carried out to remove unwanted impurities, such as mercaptans, hydrogen
sulfide associated with the gases, and moisture
• LPG quality – Weathering test
• 100 mL of liquid LPG is kept in a test tube with a mercury-in-glass, thermometer dipped into it. Liquid
LPG starts vaporising through the open mouth, after 95 mL of liquid is vaporised, the residual liquid
temperature is noted. If the temperature is very low (below 0°C), then the proportion of propane in the
mixture is more and if it is high (above 2°C), then the proportion of butane will be more. For domestic use,
the maximum weathering temperature should be 2°C.
• In order to avoid excessive pressure in the filled cylinder for the required mass (usually 14.2 kg for
domestic cylinders) it is required to test the vapour pressure of LPG at a temperature slightly above room
temperature. This is measured in a high-pressure vessel (known as a Reid vapour pressure vessel) fitted
with a pressure gauge and a constant temperature bath with a thermometer. The experiment is known as
Reid’s vapour pressure test and the pressure measured is reported as Reid vapour pressure (RVP).
Domestic LPG has a maximum RVP of 8 kg/cm2 at a temperature of 37.8°C.
• In fact, commercial LPG may not have a uniform composition of only propane and butane, but may
contain an amount of lighter gases in traces and also contain some olefinic gases obtained from
petrochemical plants.
• The presence of mercaptans and hydrogen sulfide causes corrosion to vessels, pipelines, and joints, which
may be further aggravated by the presence of moisture. LPG is tested for its corrosive properties by the
copper strip corrosion test. In this test, a standard polished copper strip is dipped into liquid LPG in a
thick-walled small vessel, known as a bomb, kept at a constant temperature, usually 30°C. After 1 h (or
maybe more depending on its end use), the bomb is opened and the copper strip is removed and compared
its brightness of surface against a set of standard copper strips indicating different degrees of corrosion as
ASTM 1, 1a,1b, 2, 2a, etc. The desired specification is that the surface brightness of the strip under study
should not be any worse than ASTM 1.
 Petroleum products and test methods
• Kerosene - Kerosene or superior kerosene oil (SKO) is another domestic fuel mainly used for lighting or
lamp oil. It is also used as a domestic stove oil. It is a petroleum product that boils in the range of 140°C–
280°C and is available from crude petroleum oil. It is heavier than naphtha or petrol (motor spirit, MS), but
lighter than diesel oil. The major properties of kerosene that determine its burning quality are the smoke point
and the flash point.
• Smoke point
• Flash point
• Char Point and bloom
• Distillation test
• Sulphur content and corrosion
 Petroleum products and test methods
• The smoke point is determined as the
height of the flame (in millimetres)
produced by this oil in the wick of a
stove or a lamp without forming any
smoke. The greater the smoke point, the
better the burning quality. Domestic
kerosene should have a smoke point of
20 mm (minimum).
 Petroleum products and test methods
• Automotive Fuels
• Motor Spirit - MS is known as petrol in India and Europe but as gasoline in the U.S. It is an automotive fuel
for running motor cars. Diesel is the other automotive fuel. Petrol or MS is suitable for spark ignition (SI) type
engines and diesel for compression ignition (CI) engines.
• American Standard for Testing Material Distillation – ASTM & TBP
• Octane Number – Knocking tendency
• Corrosion – Mercaptan sulphur
• Reid Vapour Pressure - RVP of MS should not exceed 0.7 kg/cm2 (gauge) otherwise there will be the tendency for vapour locking in
the engine and vapour loss as well during its storage.
• Oxidation Stability - components may contain much unsaturated hydrocarbons especially the di-olefins, which are susceptible to
mild polymerisation when in contact with oxygen or air. These polymerised products make layers of fi lms or gum like substances
and reduce the effectiveness of the fuel while used. This gum formation is a slow process but may cause severe damage to fuel if
stored for a long time. Therefore, the storage ability of MS is measured in terms of the period during which the fuel does not form
any gum.
• Additives - Various additives, like colour (to distinguish octane numbers), anti-icing (to reduce ice formation), anti-static (to disperse
the generation of statical electric charges), anti-oxidant, anti-corrosive, and octane boosting agents are added to the fuel.
• High Speed Diesel
• Cetane Number, Diesel Index (Paraffin/Aniline point/API gravity/Cetane number), Sulfur, Corrosion,
Flash point, flame point, pour point, viscosity
Petroleum products and test methods
 Petroleum products and test methods

• Aviation fuels
• Furnace fuels – gaseous fuel and Liquid fuels
• Lubricating oils – viscosity, Saybolt method, Redwood method,
Brookfield method, viscosity index, cloud point, pour point
• Miscellaneous products – carbon black feed stock, Bitumen,
Petroleum Coke, wax,
 Refinery flow sheets
• Crude distillation unit (CDU)
• Vacuum distillation unit (VDU)
• Thermal cracker
• Hydrotreaters
• Fluidized catalytic cracker
• Separators
• Naphtha splitter
• Reformer Sub Processes
• Alkylation and isomerisation  Crude desalter
 Furnace
• Gas treating
 Pre-flash column
• Blending pools  Crude distillation column supplemented with side columns. These columns
• Stream splitters produce the desired products
 Pump around heat exchanger units
 Heat exchanger network that facilitates energy recovery from hot product and
reflux streams to heat the crude oil.
Furnace
• Furnace
• The furnace is an important constituent in the crude distillation unit
• Here, fuel oil and fuel gas (heavier products) obtained from the refining process itself
are burnt to increase the crude oil temperature.
• Typically in refineries, the crude oil is heated to a temperature that enables over flash
conditions in the main crude distillation column.
• The concept of over flash is that the crude is heated to such a temperature that
enables an additional 5 % vaporization with respect to the residue product. In other
words, the residue fraction vapors amounting to 5 % of the total volume of the crude
oil are desired.
• Depending upon the quality of the crude, the desired temperature for the crude oil is
about 600 - 700 oF.
Pre-flash column

• Pre-flash column
• - The crude oil enters the pre-flash column after leaving the furnace
• - The pre-flash tower separates the lighter fractions of the already heated crude oil.
• - The heavier fractions of the crude oil leave from the bottom section of the pre-flash
tower.
• - Both lighter and heavier streams emanating from the pre-flash tower are fed to the
main crude distillation column at various sections
• - Pre-flash column enables better refluxes in the main column by distributing the streams
effectively between various processing zones of the crude oil.
• - Pre-flash column may or may not be included i.e., it is optional. In other words, the pre-
flash column can be avoided and the heated crude oil from the furnace can be fed to the
main column directly.
 Crude Desalting
• It is a separation process. Here, water along with other trace chemicals such as caustic and acid
Process Variables
are allowed to enter a mixing unit along with the crude oil.
• Pressure drop through mixing valve
• The mixture of crude oil and water is subsequently passed through an electrostatic precipitator • Chemical addition
• Water injection rate
cum gravity settler. The electrostatic field enables the agglomeration of water droplets and aids
• Conductivity
faster gravity settling. • Voltage
• An essential issue for the good performance of crude desalter is the temperature of the
• Desalter temperature
• Desalter pressure
operation. Usually, high efficiency of salt removal is possible between 100 – 300 oF. • pH value
• Therefore, the crude oil is heated to about 250 oF before it enters the desalter unit. • Solid at water-oil interface

• The clean desalted crude oil flows from the top of the gravity settler and the water along with

other dissolved impurities is removed as a bottom product from the gravity settler unit.

• A high degree of salt removal is desired (95 – 99% removal of the dissolved salt in the crude

oil). Usually, a two stage desalting process is deployed. When higher salt removal efficiencies

are desired, three stage units are deployed.

How to remember the refinery process flow sheet in a simple way?

• Well, visualize the refinery into four blocks namely

• the separation block
• the treating block
• the reactive transformation block and
• the rest
• The separation block consists of CDU, VDU, naphtha splitters, C4, C3 and other separators
• The treating block consists of all hydrotreaters and gas treating unit
• The reactive transformation block consists of thermal cracker (termed as cracking), alkylator,
isomerizer and reformer
• The last block consists of other units such as blending units, kerosene splitter, n-butane splitter.
• This way the refinery can be easily remembered after thoroughly understanding the functional role
of each process.
 Crude Oil Distillation
• Distillation in ADU and VDU
• Different from conventional distillation in following ways
• A large part of heat of vaporization supplied to feed stream
• Several products of volatility intermediate between overhead
and bottoms
• Live stream injected to bottom or side stream strippers for
secondary control of initial boiling points of the fraction
• Operation of fractionating columns
• Temperature
• Column pressure
• Flow rates
• Reflux
• Reboiling/Stripping
• Stability of Column operation – Flooding, Coning, Blowing,
dumping, entrainment
 Thermal conversion processes
• A critical observation of the overall refinery process block diagram indicates that the straight run gasoline (this is
the gasoline obtained from the CDU) does not have good octane number (40 – 60) and needs to be upgraded to
obtain the desired octane number (85 – 95)

• Typically, cracking, reforming and isomerisation are regarded as the three most important processes that contribute
towards upgradation of the octane number

• Typically cracking involves the thermal or catalytic decomposition of petroleum fractions having huge quantities of
higher molecular weight compounds. Since heat is required, typically cracking reactions are carried out in furnaces
that are supplied with either fuel oil or fuel gas or natural gas or electricity as heat source

• Cracking facilitates initiation, propagation and termination reactions amongst the hydrocarbon themselves.
However, when steam cracking is carried out, in addition to the energy supplied by the direct contact of steam with
the hydrocarbons, steam also takes part in the reaction to produce wider choices of hydrocarbon distribution along
with the generation of H2 and CO

• Thermal conversion processes – thermal cracking, visbreaking and coking

 Cracking
• Cracking involves the decomposition of heavier hydrocarbon
feedstocks to lighter hydrocarbon feed stocks.
• Cracking can be carried out to any hydrocarbon feedstock but it is
usually applied for vacuum gas oil (VGO)
• Cracking can be with or without a catalyst.
• When cracking is carried out without a catalyst higher operating
temperatures and pressures are required. This is called as thermal
cracking. This was the principle of the old generation refineries.
• Now a days, cracking is usually carried out using a catalyst. The
catalyst enabled the reduction in operating pressure and temperature
drastically.
 Cracking chemistry
• Long chain paraffins converted to olefins and olefins
• Straight chain paraffins converted to branched paraffins
• Alkylated aromatics converted to aromatics and paraffins
• Ring compounds converted to alkylated aromatics
• Dehydrogenation of naphthenes to aromatics and hydrogen
• Undesired reaction: Coke formation due to excess cracking
• Cracking is an endothermic reaction
• Therefore, in principle cracking generates lighter hydrocarbons constituting
paraffins, olefins and aromatics. In other words, high boiling low octane
number feed stocks are converted to low boiling high octane number products.
Thermal Cracking - Free radical mechanisms

Cracking reactivity varies with the type of hydrocarbon abd decreases in the following order:
n-paraffins > isoparaffins > cycloparaffins > aromatic > aromatics/naphthenes > polynuclear aromatics