PETROLEUM REFINING AND PETROCHEMICALS

Rationale: Petroleum refining as well as petrochemical industries constitute a

major part of chemical Sector. Every chemical engineer has to invariably handle
the enormous consumption of petroleum products, their diversity and increasing
applications. Chemical engineer has to apply the relevant concepts for Operating
petroleum refinery or petrochemical plant in a safe manner. Beside this, a
chemical engineer must be aware about the various properties of petroleum
fractions as well as petrochemicals. Hence, this course has been designed to
develop such expertise and skills.

PETROLEUM REFINING
1. Basics of Petroleum:
a. Introduction
b. Role of Crude Oil in Global Economy,
c. Present Scenario of Crude Oil Refinery,
d. Importance of crude oil,
e. Origin(Formation) of Crude Oil,
f. Composition of Crude Oil,
g. Classification and Evaluation of Crude Oil,
h. Crude Assay Analysis,
i. Distillation Characteristics such as TBP,ASTM & EFV etc.

Chapter 01: Basics of Petroleum:

a. Introduction:
(1) Petroleum, also called crude oil, is a fossil fuel. Like coal and
natural gas, petroleum was formed from the remains of ancient
marine organisms, such as plants, algae, and bacteria.
(2) Petroleum is a dark coloured, thick crude oil found deep below
the ground in certain areas.
(3) The word petroleum comes from the Latin word petra, meaning
“rock,” and oleum, meaning “oil.”
(4) Crude oil is usually black or dark brown, but can also be
yellowish, reddish, tan, or even greenish. Variations in color
 indicate the distinct chemical compositions of different supplies
of crude oil.
(5) Crude oil and other hydrocarbons exist in liquid or gaseous form
in underground pools or reservoirs, in tiny spaces within
sedimentary rocks, and near the earth’s surface in tar (or oil)
sands.
(6) Petroleum is referred to as “Black Gold”. This name itself is an
indication of its importance to humans. Crude oil is considered to
be the “mother of all commodities” as it is used to manufacture
various products such as pharmaceuticals, plastics, gasoline,
synthetic fabrics, etc.

What do you mean by Petroleum refining?

(1) The process of separating crude petroleum oil into more useful fractions is
called refining. The refining of petroleum into different fractions is based on the
fact that the different fractions of petroleum have different boiling point. The
refining of petroleum is carried out in an oil refinery.
(2) Petroleum refining separates crude oil into components used for a variety of
purposes. The crude petroleum is heated and the hot gases are passed into the
bottom of a distillation column. The liquids are then drawn off the distilling
column at specific heights to obtain fuels like gasoline, jet fuel and diesel fuel.
(3) Petroleum refineries convert crude oil into petroleum products for use
as fuel for shipping, cooking, paving roads and electricity production and
as feedstocks for chemical manufacturing. The refining cycle breaks down
crude oil into its different components and is then gradually reconfigured
into new products.
(4) Petroleum refining or oil refining is an industrial process that extracts crude oil
from the earth and converts it into useful items such as liquefied petroleum gas
( LPG), kerosene, asphalt base, jet fuel, diesel, heating oil, fuel oils, etc.
(5) Petroleum refining or Oil refining is an industrial process in which crude oil is
extracted from the ground and transformed and refined into useful products like
Liquefied Petroleum Gas (LPG), kerosene, asphalt base, jet fuel, gasoline,
heating oil, fuel oils etc.
There are three steps in the Petroleum refining process

a. Separation, b. Conversion and c. Treatment

Separation process :
• Modern separation involves piping crude oil through hot furnaces. The
resulting liquids and vapors are discharged into distillation units. All
refineries have atmospheric distillation units, while more complex refineries
may have vacuum distillation units.

• Inside the distillation units, the liquids and vapors separate into petroleum
components called fractions according to their boiling points. Heavy
fractions are on the bottom and light fractions are on the top.

• The lightest fractions, including gasoline and liquefied refinery gases,

vaporize and rise to the top of the distillation tower, where they condense
back to liquids.

• Medium weight liquids, including kerosene and distillates, stay in the

middle of the distillation tower.

• Heavier liquids, called gas oils, separate lower down in the distillation
tower, while the heaviest fractions with the highest boiling points settle at
the bottom of the tower.

Conversion :
• Cracking, coking, and vis-breaking processes are used to break
large petroleum molecules into smaller ones. Polymerization and
alkylation processes are used to combine small petroleum molecules
into larger ones. Isomerization and reforming processes are applied to
rearrange the structure of petroleum molecules to produce higher-
value molecules of a similar molecular size.

• There are still many too heavy hydrocarbon molecules remaining after
the separation process. To meet demand for lighter products, the
heavy molecules are “cracked” into two or more lighter ones.
• The conversion process, which is carried out at 500°C, is also known
as catalytic cracking because it uses a substance called a catalyst to
speed up the chemical reaction. This process converts 75% of the heavy
products into gas, gasoline and diesel. The yield can be increased
further by adding hydrogen , a process called hydrocracking , or by
using deep conversion to remove carbon.

• The more complex the operation, the more it costs and the more
energy it uses. The refining industry’s ongoing objective is to find a
balance between yield and the cost of conversion.

Treatment:

∆ Petroleum treating processes stabilize and upgrade petroleum

products by separating them from less desirable products and by
removing objectionable elements. Undesirable elements such as sulfur,
nitrogen, and oxygen are removed by hydro-desulfurization, hydro-
treating, chemical sweetening, and acid gas removal.
{Role of Crude Oil in Global Economy} & {Present Scenario of Crude
Oil Refinery} :
• Oil is one of the most important Commodities in the world. When
transformed into petroleum, it is a key energy source used in vehicles,
planes, heating, asphalt, and electricity. Outside of being a crucial
energy source, petroleum is used in plastics, paints, chemicals, tape,
and so much more. It’s hard to imagine a world without oil. The total
revenues for the oil and gas drilling sector came to approximately $2.1
trillion in 2021.
• Oil prices are strongly influenced by the global economic outlook.
• Changes in supply and demand and geopolitical tensions cause price
fluctuations.
• The largest global producers of oil are the United States, Saudi Arabia,
and Russia. These three countries produced approximately 40 million
barrels of oil per day in 2020. That is 43% of total world production.
• From estimation it is found that to meet the projected increase in
world oil demand the total Petroleum supply in 2030 is required to
reach 118 million barrels per day.
• Most countries are significantly affected by developments in the oil
market, as producers, consumers, or both.
• Many variables affect oil prices, including the basic economic theory
of supply and demand. The law of supply and demand states that if
supply increases, prices will go down. Conversely, if demand rises, so
too should prices.
• Globally, crude oil is one of the most important fuel sources and,
historically, has contributed to over a third of the world’s energy
consumption.
• Crude oil is one of the most important energy sources used globally.
• Due to the importance of this energy source, a vast market, which
includes physical trading, as well as derivatives trading, exists for crude
oil.
• We use petroleum products to propel vehicles, to heat buildings, and
to produce electricity. In the industrial sector, the petrochemical
industry uses petroleum as a raw material (a feedstock) to make
products such as plastics, polyurethane, solvents, and hundreds of
other intermediate and end-user goods.
• On fractional distillation of crude oil, it gives gasoline (44 %), heating
oil and diesel fuel (19 %), Jet Fuel (8 %), residual fuel oil (5 %), and
asphalt (3 %), and other ducts products (21 %), in which some of these
products are used as fuel for industrial as well as of the domestic
purpose. Also, various petrochemicals are prepared using these
fractioned products.
• Petrochemicals in general are compounds and polymers derived
directly or indirectly from of oil petroleum and used in the chemical
market. Among the major petrochemical products are plastics,
synthetic fibers, synthetic rubber, detergents, and nitrogen fertilizers.
Many other important chemical industries such as paints, adhesives,
aerosols, insecticides, and pharmaceuticals may pace involve one or
more petrochemical products within their manufacturing steps.
Importance of Crude oil:
•Globally, crude oil is one of the most important fuel source and is undoubtedly
the king 👑 of commodity in the world today, and it supplies 40% of the world’s
total energy needs.
•On fractional distillation of crude oil, it gives gasoline (44 %), heating oil and
diesel fuel (19 %), Jet Fuel (8 %), residual fuel oil (5 %), and asphalt (3 %), and
other products (21 %), in which some of these products are used as fuel for
industrial as well as domestic purpose.
• Also, various petrochemicals are prepared using these fractioned products.
Petrochemicals in general are compounds and polymers derived directly or
indirectly from petroleum and used in the chemical market. Among the major
petrochemical products are plastics, synthetic fibers, synthetic rubber,
detergents, and nitrogen fertilizers.
• Many other important chemical industries such as paints, adhesives, aerosols,
insecticides, and pharmaceuticals may involve one or more petrochemical
products within their manufacturing steps. The primary raw materials for the
production of petrochemicals are natural gas and crude oil.
• It has vital role in Industrialization and Urbanization.
• Crude oil contributes 97% of the energy for transport such as cars, trains,
airplanes in the world. Crude oil is necessary as without it no automobile,
industries etc runs. It is the most important raw material of the industrialized
nations. It can generate heat, drive machinery and fuel vehicles and airplanes.
¥ OCCURRENCE AND ORIGIN OF CRUDE OIL:
*Occurrence of Crude(Petroleum)* :
• Petroleum—or crude oil—is a fossil fuel that is found in large
quantities beneath the Earth’s surface and is often used as a
fuel or raw material in the chemical industry
• Petroleum is found in fault traps between porous and non-
porous rocks. Petroleum is found in 500 meters to 2000 meters
depth. It is always found mix with saltwater, being lighter than
saltwater, Petroleum always floats over it.
• Petroleum occurs in the earth’s crust, in all possible states
and varies in color from light brown to dark brown or black
mixture.
• Crude oil is a naturally occurring Fossil fuel meaning it comes
from the remains of dead organisms. Crude oil is made up of a
mixture of Hydrocarbons which exists in liquid form in
sedimentary rocks.
• It is always found along with Natural gas and Saline water.
• Petroleum is a natural or mineral oil, which mainly occurs in
well-defined areas. Now it has been proved that oil is formed
by slow chemical and biochemical decomposition of the
remains of organic matter entombed in sedimentary rocks.
These rocks are marine or estuarine in origin.
*Origin of Crude oil*
There are two theories of Origin (1) Inorganic( abionic ) , (2)
Organic( bionic ). Organic theory are Engler theory and
Modern-Organic theory.

(a).Inorganic theory: Inorganic origin theories state that

petroleum is formed from Earth itself, due to Chemical
interactions deep within the Earth.
Hydrogen and carbon came together under great temperature
and pressure, far below the earth’s surface and formed Oil and
Gas where chemical reaction have occurred.
Dmitri Mendele’ev (1877), a Russian and the father of the
periodic table of elements, reasoned that metallic carbides
deep within Earth reacted with water at high temperature to
form Acetylene(C2H2)Which subsequently condensed to form
heavier Hydrocarbons.
Other hypothesis ( Berthelot, 1860 , Mendele’ev, 1902) were a
modification of the acetylene theory. They theorized that the

mantle contained Iron- Carbide which would react with

Percolating water to form Methane.
Metals like Ca, Al under the conditions of higher temperature
and pressure, under the earth’scrust form respective Carbides
which in-turn react with water to form hydrocarbon or by atm.
Radioactivity/Cosmic radiation.
 Engler theory

(b). Organic theory

Modified Organic
theory

Engler theory: According to this theory decay and

decomposition of dead organic marine organisms, animals
under the conditions of higher temperature and pressure
(Plankton) are responsible for formation of Crude oil.

Modern Organic theory:

Petroleum is believed to be formed by the decay and
decomposition of marine animals as well as that of vegetable
organism of the pre- historic forests. It is thought that due to
earthquake prehistoric forests and sea animals got buried
under the earth’s crust. Due to prolonged action of high
temperature and pressure in the interior of earth for ages, the
biological matter decomposed into Petroleum.
It explains the presence of Brine and Coal in Vicinity of
Petroleum.

Exploration of Crude oil:

• Oil and gas exploration encompasses the processes and methods
involved in locating potential sites for oil and gas drilling and extraction.
• Requires Knowledge of Geology, Geophysics and Geography. Crude
exist in geological structure like fault traps and salt domes.
• When it comes to exploration of Crude oil resources, there are many
different methods that petroleum geologist and geophysicists use to
discover them. Three geophysical methods used in petroleum
exploration comprise magnetic, gravimetric, and seismic (including
refraction/reflection) techniques.
1).Gravity Survey: A gravity reader(gravimeter) measures the
gravitational pull in certain rock formations to determine what could lie
beneath the surface. Method is used frequently in Mining application
to map subsurface geology. The objective is to associate variation with
difference in the distribution of densities & he che rock type.
2). Magnetic survey: Magnetic reader (magnetometer) is usually flown
on the back of an aircraft in order to detect whether certain rock
formations have magnetic anomalies, which can indicate an oil reserve
at certain levels of a magnetic reading. This type of survey is especially
useful in hard to explore areas, like mountainous regions.
3). Seismic Reflection Survey: A seismograph is used underground, but
operated from above ground. The shallowest depth in which a
seismograph can be used is 3-5 meters. There are quite a few methods
that geologists and geophysicists use to operate a seismograph to
detect petroleum, but the most effective methods geophones, which is
a device that converts ground movement into voltage in the form of
waves that a seismograph can read.
4). Drilling: There are several methods for exploratory drilling, but they
include drilling anywhere from a half of a mile to three miles from
known reserves to determine if there are reserves nearby This method
is usually higher risk, as it is more costly and does not rely on much data
collection beforehand. This does not rely on data without drilling, so it
is generally more useful in areas that are not populated.
5). Oil seeps: It's just what it sounds like-visual evidence of an oil
reserve. This can include topographical visuals, bubbling, upwelling
seawater, and many others. This can be a negative and positive, It is
cheap because it requires no equipment, but it can indicate harm to
wildlife or water supplies depending on where these seeps are found.
Composition of Crude oil:

Composition of petroleum basically depends upon the origin of

formation. Crude petroleum is made of thousands of different chemical
substances including solids, liquids and gases, ranging from methane
(C1) to asphalt (C70). Petroleum (Crude oil) consists of mainly carbon
(83-87%) and hydrogen (12-14%) having complex hydrocarbon mixture
like paraffins, naphthenes, aromatic hydrocarbons, gaseous
hydrocarbons. Beside, crude oil also contains small amount of non
hydrocarbons [nitrogen compounds (0.1-2%), sulphur compounds
(0.05-6%), oxygen compounds (0.05-1.5%)).
Depending on predominance of hydrocarbons, Petroleum is
classified as
 Paraffin base
 Intermediate base
 Naphthenic base/Asphaltic base
 Major components of Hydrocarbons in Crude oil are:
a)Paraffins
Paraffins series is the largest fraction of petroleum crudes having
general formula of C₂H₂. In this series, first four compounds i.e. C1, to
C4, are in gaseous form. Compounds C5 to C16 are liquid form and C17
to C30 are semi-solid form. Beyond C30, compounds are assuming solid
form, even sometimes crystalline form.
There are two types of paraffins in petroleum: (i) normal paraffin and
(ii) iso-paraffins, but generally normal paraffins are predominantly
present in the petroleum compared to iso-paraffins. Lower paraffins are
soluble in water, though higher paraffins are insoluble in water, ether
and alcohol. They are stable towards sulfuric acid and other oxidizing
agents. However, paraffins of higher order > C30 are oxidized with
several oxidizing agents.

b)Naphthenes (Cycloparaffins):
This series is consider as second largest series is crude oil having
general formula of CnH2n. It exhibit both the properties saturated
paraffin and unsaturated aromatic, so also known as hybride series.
Cycloparaffin hydrocarbons in which all of the available bonds of the
carbon atoms are saturated with hydrogen are called naphthenes.
Examples are Cyclopentane, Cyclohexane, Decaline, Methyl
cyclopentane, Methyl cyclohaxane.

c) Olefin and diolefin:

Olefin: The general formula of olefins is CnH2n, also known as alkene
series. Olefins do not naturally occur in crude oils but are formed during
the processing. They are very similar in structure to paraffin’s but at least
two of the carbon atoms are joined by double bonds. Due to its unsaturate
nature, it is very unstable, and easily attacked by sulfuric acid and also,
polymerized. They are produced by Cracking reactions. Examples of olefins
are Ethylene, Propylene, Butenes (1-Butene and 2-Butene).
Olefins are generally undesirable in finished products because double
bonds are reactive and the compounds are easily Oxidized and Polymerized
to form Gums and Varnish.
Diolefin: An olefin that contains two carbon-to-carbon double bonds in its
molecules, is known as Di-olefins series having general formula CnH2n-2. Di-
olefins are very unstable compounds, readily attacked by sulfuric acid and gets
polymerized. They are also produced by cracking reactions. They are differ from
alkynes series, because it does not react with ammonical solution of copper salts
but react with HgCl₂ and form precipitates.

d) Alkyne: This series is known as alkyne series having general formula of C n H

2n-2 Due to unsaturated nature, they are readily attached by sulfuric acid. It
forms crystalline compound after reaction with ammonia solution of copper salts.

e) Aromatic :
Very small amount of aromatic is found in petroleum. Aromatic series of BTC do
not exceed even 5% of crudes of general nature. Bulk of the aromatics exists in
heavier portion of crude with side chain and naphthalene. The aromatic series of
hydrocarbons is chemically and physically very different from the paraffins and
cycloparaffins (naphthenes). Aromatic hydrocarbons contain a benzene ring which
is unsaturated but very stable and frequently behaves as a saturated compound.
Some typical aromatic compounds are

Aromatics are usually having High boiling points, low pour

points(freezing point), High Octane numbers , High Viscosity and low
viscosity Index and burn characteristically with a red flame with much
soot( Sooty flame ).
f) Asphalts, Resins and Bitumen :Asphalt is high molecular weight complex
with black in color. It is preferably soluble in aromatic solvents and carbon
disulfide. Mostly, resins are highly condensed ring structure compounds
containing oxygen, sulfur and nitrogen with some inorganic compounds. Bitumen
is manufactured using three components: (i) Asphalt, (ii) Resins and (iii) Mineral
oil. In this process, asphalt is suspended in oil and resin contribute to the stability
to the system.

g) Inorganic compounds: Crude oils contain hundreds of different

hydrocarbons and other organic and inorganic substances including atoms of
sulfur, nitrogen, and oxygen, as well as metals such as iron, vanadium, nickel, and
chromium. Collectively, these other atoms are called heteroatoms.

Sulphur: Sulfur is always an undesirable constituent of petroleum. Generally

they are in range of 0.05 to 5%, but they are in higher percentage is certain areas
such Venezuela (5.25%), California (5.21%), Iraq (7%). Sulfur in crude occurs in
different forms like free sulfur. Hydrogen sulfide, polysulfide, mercaptans,
sulfonates, sulfates and thiohenes, etc. When free hydrogen sulfide is available in
crude, then it is known as sour crude. The presence of thiol in the petroleum
fractions causes corrosion problems, catalyst poisoning and unpleasant laboratory
and plant odor’s.

Nitrogen: The nitrogen content in most crudes is very low and does not exceed
0.1 wt%. In some heavy crudes, however, the nitrogen content may reach up to
0.9 wt %. Organic nitrogen compounds occurs in crude oils either in a simple
heterocyclic form as in Pyridine(C5H5N) and Pyrrole(C4H5N) or in a complex
structure as in porphyrin.
The nitrogen compounds are divided to: (1) Basic nitrogen compounds and (2)
Non-basic nitrogen compounds.

Oxygen: The oxygen content of crude oil is usually less than 2 percent by

weight and is present as part of the heavier hydrocarbon compounds in
most cases. For this reason, the heavier oils contain the most oxygen. The
concentration of Oxygen increase from lighter Fractions to heavier ones.
Other compounds (Metallic compounds): A large number of elements
have been reported in a variety of crude oils. Some of the most
abundant are sodium(Na), calcium(Ca), Magnesium (Mg), Aluminium
(Al), Iron(Fe) and nickel(Ni). When crude oil is processed sodium and
magnesium chlorides produces HCl, which is corrosive. Desalting crude
oil is a necessary step to reduce this salts.

*Classification of Crude *🪔:

• Composition and classification of any crude oil is necessary to know what kind
of product we can get from it and it serves the refinery engineer to know the
nature of refinery operations the crude oil is subjected and the difficulties
encountered in processing too.
• It also help in designing the topping tower( Crude oil distillation column).

 Classification by chemical composition:

1) Paraffin base crudes
These contain higher molecular weight paraffins. Hydrocarbon chain and
branched chains can contain more than 50 carbon atoms, saturated, presence in
all matters when C1-C4: gas, C5-C15: liquid, C15 and above: solid. All are mixed as
a complex in form of light Paraffinic- Oil or light oil. Crude oils on distillation yield
residues containing gasoline, paraffin waxes and High-grade lubricating oils .

A crude oil containing paraffin wax but very few asphaltic materials.
This type of oil is suitable for motor lubricating oil and kerosene.

2) Intermediate base crude: If residue on atmospheric distillation of crude

oils contains asphaltic materials then the crude oils are classified as asphaltic
base. Many crudes on atmospheric distillation yield residues that contain both
paraffin waxes and asphaltic materials.

3)Naphthenic base or Hybrid base crudes:

Naphthenes are cyclic aliphatic hydrocarbons. It contains high percentage of
Saturated cycloalkanes derivatives, we also call them CycloParaffins.
Crude oil containing asphaltic materials but very little or no paraffin wax. This type
of oil is suitable for making gasoline, lubricating oil, and asphalt. It is also called
asphalt-base crude.

•According to flash point:

# It is classified according to value of flash point. Flash point of any petroleum
means the lowest temperature at which it yields a vapor which will give a
momentary flash when ignited or given an ignition source.
# The temperature at which Vapors of Crude oil starts to Flash when a test flame
is brought near it.
Classifications are:

 (1) Petroleum Class A : Petroleum having a flash point below 230 °C.
 (2)Petroleum Class B : Petroleum having a flash point of 230° and above
but below 650 °C.
(3)Petroleum Class C : Petroleum having a flash point of 650 degrees °C
and above but below 930 degrees °C

• Classification by API or specific gravity:

# Another classification of petroleum is as per physical characteristics like API or
specific gravity, API stands for the American Petroleum Institute, which is the
major United States trade association for the oil and natural gas industry. Specific
gravity is a ratio of the density of one substance to the density of a reference
substance, usually water. The API gravity is used to classify oils as light, medium,
heavy, or extra heavy. As the weight of an oil is the largest determinant of its
market value, API gravity is exceptionally important. The API values for each
weight are as follows:
() Light Petroleum: Petroleum having API greater than 31.1
(ii)Medium Petroleum: Petroleum having API between 22.3 and 31.1
(iii) Heavy Petroleum: Petroleum having API less than 22.3
(iv) Extra Heavy Petroleum: Petroleum having API less than 10.0
Classification by Carbon Distribution: For the characterization of the
various fractions of petroleum, the use of the n.d.M method (n =
refractive index, d = density, M = molecular weight; is suggested. This
method enables determination of the carbon distribution and thus
indicates the percentage of carbon in aromatic structure (% CA), the
percentage of carbon in naphthene structure (% Cn), and the
percentage of carbon in paraffin structure (Cp). A high value of % CA at
500 °C boiling point usually indicates a high content of asphaltenes in
the residue, whereas a high value of % CnP at 500 °C boiling point
usually indicates a waxy residue.

Classification by Characterization Factors:The characterization factor is

a measure of the aromaticity/paraffinicity of a crude oil or of a crude oil
fraction. Since the early days of the petroleum industry, some physical
properties of crude oil were used to define characterization factors for
classification of crude oil with respect to hydrocarbon types these are
Watson characterization factor
Viscosity gravity constant (VGC) or
Mines correlation Index(BMCI)
Correlation Index
For calculation of Watson characterization factors (K), mean average normal
boiling point and specific gravity at 15.6°C is required. Depending on the value of
the Watson characterization factor, crude oils are classified as paraffinic (Kw= 11 -
12.9) naphthenic (Kw= 10 - 11) or aromatic (Kw< 10) The viscosity gravity constant
depends on viscosity expressed in Saybolt Universal Seconds (SUS) and specific
gravity; and determined according to a standard method (ASTM D2501). VGC
varies between 0.74 to 0.75 for paraffinic, 0.89 and 0,94 for naphthenic, and 0.95
and 1.13 for aromatic hydrocarbons. Further, U.S. Bureau of Mines Correlation
Index (BMCI) or Correlation Index (CI) is determined using the values of mean
average boiling point specific gravity. According to this CI scale, all n-paraffins
have a CI value of 0, while cyclohexane (the simplest naphthene), has a CI value
50, and benzene has a CI value of 100. Using the CI values, crude oils can be
classified as CI < 29.8 (paraffinic), CI < 57.0 (naphthenic) and CI > 75.0 (aromatic)

Classification by Viscosity:
Viscosity provides a measure of a fluids internal resistance to flow. It is measured
in “Centipoise” . If material having Viscosity less than 10,000 CP are conventional
petroleum and heavy Oil.
Tar and Bitumen has a viscosity greater than 10,000CP.

Evaluation of Crude oil:

Evaluation is required to get crude oil of required composition by measuring
various properties:
1)Evaluation by Residuum: Crude oil is evaluated by percentage residuum left
behind after distillation of crude oil Residue containing more than 5 % is
paraffinic, it is less than 2% is naphthalene. And if value of residue is between 2-
5% , than it is called mixed base.
2)Evaluation by API: Another classification of petroleum is as per physical
characteristics like API or specific gravity.
API stands for the American Petroleum Institute, which is the major United
States trade association for the oil and natural gas industry.
The proper method of evaluation of Crude was given by United States
bureau of Mines (USBM) on basis of two fractions and their API gravity
which is defined as

Specific gravity at 15.6°C

 °API gravity magnifies the specific gravity of closer boiling point fractions
and also used a classification parameter
Key fraction 01: (Kerosene)
Boiling range : 250-275°C at 1atm
Key fraction 02: (Lube)
Boiling range: 275-300°C at 40 mmHg
289-400°C at 1atm.
The °API gravity of these fractions are found out and based on that crude is
classified as…

When,
Key fraction No. 1: API gravity is 40 or more than 40, than it is paraffinic base,
gravity is less than 33, it is naphthaenic. And value is in-between 33-40, than it is
mixed base. Further, Key fraction No. 2: API gravity is 30 or more than 30, than it
is paraffinic base, gravity is less than 20, it is naphthaenic. And value is in-between
20-30, than it is mixed base.

3) Watson characterization factor

The characterization factor is a measure of the aromaticity/paraffinicity of a crude

oil or of a crude oil fraction. The Watson K factor will range from less than 10 for
highly aromatic hydrocarbons and almost 15 for highly paraffinic hydrocarbons.
The range for whole crudes is 10.5 to 12.9.

where: Tb = volume, or mean average normal boiling point in R (degree Rankine)

and SG = specific gravity at 15.6°C (60°F). To calculate K UOP or KW, volume average
boiling point (VABP) or mean average boiling point is used, respectively. Depending
on the value of the Watson characterization factor, crude oils are classified as
paraffinic (Kw = 11-12.9), naphthenic (Kw =10-11), or aromatic (Kw <10)

4)Viscosity gravity constant: Another parameter defined in the early years of

petroleum characterization is the viscosity gravity constant (VGC). This parameter depends
on viscosity expressed in Saybolt Universal Seconds (SUS) and specific gravity. According to
 a standard method (ASTM D2501), VGC can be calculated at a reference temperature of
100°F as follows in Equation

where V(100°F) is the viscosity in SUS and SG is the specific gravity at 15.6°C (60°F). VGC varies
between 0.74 to 0.75 for paraffinic, 0.89 and 0,94 for naphthenic, and 0.95 and 1.13 for
aromatic hydrocarbons.

5)Correlation Index(CI):The U.S. Bureau of Mines Correlation Index (BMCI) or

(CI) is useful for characterization of crude oil fractions. CI is defined in terms of
Mean Average Boiling Point (Tb) and specific gravity (SG) at 60°F as shown in
Equation
According to this CI scale, all n-paraffins have a CI value of 0, while
cyclohexane (the simplest naphthene), has a CI value of 50, and
benzene has a CI value of 100. Using the CI values, crude oils can be
classified as follows

Crude Assay Analysis:

A crude oil assay is the chemical evaluation of crude oil feedstocks by petroleum
testing laboratories. Each crude oil type has unique molecular and chemical
characteristics. No two crude oil types are identical and there are crucial
differences in crude oil quality.
Crude oil assay consists of a compilation of data on properties and composition of
crude oils. The assay provides critical information on the suitability of crude oil for
a particular refinery and estimating the desired product yields and quality. It also
indicates how extensively a given crude oil should be treated in a refinery to
produce fuels that are in compliance with environmental regulations. A typical
crude assay should include the following major specifications:
For design of topping tower to know the quality of crude oil(base of crude oil, %
Petroleum fractions) by performing preliminary TBP distillation and plotting
temperature vs % distillation curve(TBP curve) and determining distillation
characteristics.Is known as crude oil analysis

Distillation Characteristics:
Complex mixtures such as crude oil, or petroleum products with
thousands of different compounds, boil over a temperature range as
opposed to having a single point for a pure compound. The boiling
range covers a temperature interval from the initial boiling point (IBP),
defined as the temperature at which the first drop of distillation
product is obtained, to a final boiling point, or endpoint (EP) when the
highest-boiling compounds evaporate. The boiling range for crude oil
may exceed 1000 °F.

The ASTM D86 and D1160 standards describe a simple distillation

method for measuring the boiling point distribution of crude oil and
petroleum products. Using ASTM, D86 boiling points are measured at
10, 30, 50, 70, and 90 vol% distilled. The points are also frequently
reported at 0%, 5%, and 95% distilled. ASTM D1160 is carried out at
reduced pressure to distill the high-boiling components of crude oil. As
an alternative method, distillation data can be obtained by gas
chromatography (GC)
Distillation Methods:
Three different distillation methods are commonly used to generate
laboratory data on crude oil:

True Boiling Point Distillation (TBP)

ASTM Distillation (ASTM)
Equilibrium Flash Vaporization (EFV)
The degree of separation between the distillation fractions obtained in
these methods decreases significantly as one moves down the list from
TBP through ASTM to EFV. Each method and the associated distillation
data have different applications in the refinery practice.

As the user of crude oil products are world-wide. So, their test methods
and specifications are mentioned by various bodies. The bodies are
namely ASTM (American Standard Test Method). United States
Pharmacopeia with the National Formulary (a formulary) as the USP-NF
(NF). International Organization for Standardization (ISO), Bureau of
Indian Standards (BIS), Indian Pharmacopeia (IP) etc.
True Boiling Point Distillation (TBP): This method, described in Figure 4.7a
and b, uses a batch distillation operation that incorporates more than 100
theoretical plates and a high reflux ratio (R/P) of 100, as described in Figure 4.7a.
This is an idealized method to achieve the best possible separation in distillation,
made possible by a large number of theoretical plates (stages) for liquid vapor
contact in the column and an extremely high reflux ratio. As an example, consider
distillation of a binary mixture of compounds A (70% by volume) and B (30% by
volume), with boiling points Ta and Tb, respectively. Figure 4.7b illustrates the
distillation curve that would be obtained if this mixture were distilled using the
TBP method, with perfect separation of A and B as pure compounds. Because of
the TBP distillation conditions, first the lower boiling component A is distilled off
without any contamination with B, and following the complete vaporization of A,
B is distilled off as a pure compound. Note that because a large number of plates
and a high reflux ratio in the column, temperature remains constant during
evaporation of A until all of this compound is boiled off, as would be seen in the
distillation of a pure compound
ASTM Distillation (ASTM):
ASTM distillation also uses a batch operation, but in contrast to TBP, it operates
without the presence of a contact plate and a reflux ratio (R/P, or RR) of zero, as
shown Figure 4.8a. There may be a slight unintentional reflux because of the
condensation of the vapor on the tube that connects the flask to the condenser.
Equilibrium Flash Vaporization (EFV):
Equilibrium flash vaporization involves heating a flowing feed and the separation
of the liquid and vapor in a flash drum. A distillation curve may be obtained by
conducting this distillation at varying heater outlet temperatures. Figure 4.9
shows the diagram of an EFV set up and compares the distillation curves from the
three methods, TBP, ASTM, and EFV. From the comparison of the curves and the

relationship between IBP and EP obtained in each case, one concludes that EFV
gives the lowest degree of separation between A and B, even lower than that
given by the ASTM distillation.

TBP, ASTM, and EFV Compared: The TBP, ASTM, and EFV distillation
methods achieve different levels of separation for a given sample, as
related to the different techniques used in these analyses. Figure 4.10
shows TBP, ASTM, and EFV curves for a middle distillate fraction crude
oil, showing significant differences in IBP and EP of the three curves
[6]. Note that three curves converge near 50% volume distilled. TBP
distillation achieves a higher degree of separation than ASTM and
ASTM achieves better separation than EFV, as can be seen in the
curves in Figure 4.10. Empirical correlations have been developed to
convert one set of distillation data to another

Each distillation method discussed in this section has an application in

petroleum refining. TBP distillation is used to characterize crude oils
and constitute a significant component of crude essay. ASTM methods
are usually used for refinery products and property calculations and
correlations for distillate fractions. EFV provides useful data for flashing
operations in the refinery.

There are no standard methods for TBP distillation, but ASTM D-2892
method is used to approximate the TBP distillation. This method is also
referred to as 15-5 distillation, because of 15 theoretical plates and a
reflux ratio of 5 used in the distillation. A simulated distillation method
described in ASTM D2887 may also be used to obtain TBP data for
crude oils.
ASTM D86 (atmospheric distillation) and ASTM D1160 (vacuum
distillation) are used for low-boiling, and high-boiling fractions,
respectively.

Cut Points:
Using a crude TBP curve, cut points are defined as the temperatures that
represent the limits of a distillate fraction, as illustrated in Figure 4.11. For
example, for kerosene, fraction Ta represents the lower cut point, and Tb
represents the upper cut point in Figure

Boiling ranges between the cut points represent distillate products,

such as naphtha, kerosene, light gas oil, etc. The difference between the
cumulative volume percent at upper and lower cut points is reported as
the yield (in volume %) for the particular distillate fraction. For example,
for the crude represented in Figure 4.11, the kerosene yield can be
calculated as 40%(at Tb) -20% (Ta) = 20% by volume. Table 4.1 shows
the TBP cut points for crude oil distillate fractions