UNIT-1

CRUDE OIL COMPOSITION AND CLASSIFICATION

1. CRUDE OIL/PETROLEUM
Crude oil is a naturally occurring, unrefined petroleum product composed of
hydrocarbon deposits and other organic materials. It is often called "black gold".
Crude oil has ranging viscosity and can vary in colour from black and yellow
depending on its hydrocarbon composition.

1.1ORIGIN AND FORMATION OF PETROLEUM

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STEP1:
DIAGENESIS-FORMS KEROGEN
Diagenesis is a process of compaction under mild conditions of temperature
and pressure When organic aquatic sediments (proteins, lipids, carbohydrates)
are deposited, they are very saturated with water and rich in minerals. Through
chemical reaction, compaction and microbial action during burial, water is
forced out and carbohydrates breakdown to form new structure that comprise
waxy materials known as kerogen.
STEP 2:
CATAGENESIS-TURNS KEROGEN INTO CRUDE OIL AND NATURAL
GAS:
As temperatures and pressure increases, the process of catagenesis begins,
which is the thermal degradation of kerogen to form hydrocarbon chains. The
process catagenesis is catalyzed by the minerals that are deposited and persist
through marine diagenesis. The conditions of catagenesis determine the product,
such that higher temperature and pressure lead to complete cracking of the
kerogen and progressively lighter and smaller hydrocarbons Formation of crude
oil through combination of physical and biological processes rather than
individually.
1.1.1 Physical Methods:
It depends upon the factors like
1. Heat
2. Pressure
3. Heat and pressure
4. Catalysts
5. Radioactivity
1.1.2 Biological Methods:
All the biological methods are governed by source and environment such as'
1. By preservation of hydrocarbons synthesized by the source sediment
organisms.

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 2. Biological reduction: (anaerobic or aerobic) source being.
➤ Fatty acids
➤ Proteins and amino acids
➤ Carbohydrates

1.1.3 Biological And Physical Methods

➤ By condensation of bacterially produced methane under high pressure
and temperature in presence of catalysts.
➤By bacterial modification of sediments

There are two theories that explained about the origin of petroleum:

1.1.4 Inorganic Theory:

It states that the hydrogen and carbon came together under great
temperature and pressure for below the earth's surface and formed oil and gas.
The oil and gas then seeped through porous rock to deposit in various natural
underground traps.

1.1.5 Organic Theory :

According to organic theory, the oil and gas are formed from remains of
dead plants and animals. Remains of plants have transformed to coal and
animals to oil and gas. This remains were settled into seas and lands along with
other minerals.
As the rocks and slit settled, layer upon layer into rivers along coastlines
and on sea bottom. Over the time, the layers of the organic materials were
compressed under the weight of the sediment above them. The increase in
pressure and temperature changed the mud sand, slit into rock and organic
matter in petroleum.
The rock containing the organic matter that turned into petroleum is
referred as source rock.(trap fold-formed to changes in the structure of
subsurface)
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1.2 EXPLORATION AND PRODUCTION OF PETROLEUM
The search for oil and gas requires a knowledge of geography, geology
and geophysics. Crude oil is usually found in certain types of geological
structures such as anticlines, fault traps and salt domes which lie under various
terrains and in a wide range of climates.
They are three methodologies used to find hydrocarbon in the subsurface.
Geophysical
Remote sensing
Wild catting

1.2.1 Geophysical Surveys

Geophysical techniques used for petroleum exploration utilize equipment
to measure such things as electric currents, gravitational and magnetic
anomalies, heat flow, geochemical relationships and density variations from
deep with the earth.

1.2.2 Seismic Surveys

Seismic studies provide information on the general characteristics of the
subsurface structure. Measurements are obtained from shock waves generated
by setting off explosive charges in small diameter holes, from the use of
vibrating or percussions devices on both land and in water and from underwater
blasts of compressed air. The elapsed time between the beginning of the shock
wave and the return of the echo is used to determine the depth of reflecting
substrata.
The echoes are detected by electronic devices called geophones which
receive the reflected sound waves and the data are recorded on magnetic tape
which is printed to produce a two dimensional graphic illustrating the
subsurface geology.
1.2.3 Magnetometer

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 A magnetometer is a device that is pulled behind an airplane on a long
cable that detects variations in the earth's magnetic field. Sedimentary rocks
generally have low magnetic properties compared to other rock types. It is
carried out either on the ground or from the air by air borne magnetometer. It is
based on the principle that the magnetic attraction on the surface depend on
magnetic the rock and distance from the surface.

1.2.4 Gravimeter
A gravimeter measures minute differences in the pull of gravity at the
earth's surface. Mapping these differences reveals large masses of dense
subsurface rock which allow geologists to have better idea of the structures
below ground.

1.2.5 Radiographic Surveys

Radiography is the use of radio waves to provide information similar to
that obtained from seismic surveys.

1.2.6 Stratigraphic Surveys

Stratigraphic sampling is the analysis of cores of subsurface rock strata
for traces of gas and oil. A cylindrical length of rock called a core is cut by a
hollow bit and pusped up into A tube attached to the bit. The core barrel is
brought to the surface and core is removed for analysis.

1.2.7 Offshore Surveys

Boats tow cables containing hydrophones in the water which is similar to
geophones on land sound waves use to be created by dynamite but this method
killed a variety of sea life. The most acceptable method today is to generate
sound waves using pulses of compressed air which create large bubbles that
burst beneath the water surface creating sound. The sound waves travel down to
the sea floor, penetrate the rocks beneath and return to the surface where they
are intercepted by the hydrophones.

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1.2.8 REMOTE SENSING
Remote sensing is the use of aerial photographs to locate and map surface
features. Once an area is selected and the satellite imagery obtained, the
exploration geologist utilizes mapping techniques to produce a geologic map.
Another type of remote sensing techniques uses imagery that was created
from radar looking at the ground called side looking airborne radar. Some of
this imagery is flown with an aircraft while some of it is onboard satellite. These
types of map allow geologists to determine where hydrocarbon might be
located.

1.2.9 Wild Cat

It is drilled in an effort to locate undiscovered accumulation of
hydrocarbons. Wildcat wells are generally drilled at a smaller diameter than
normal.
1.2.10 Production Of Petroleum
Production is the process of extracting the hydrocarbon and separating the
mixture of liquid hydrocarbons, gas, water and solids, removing the constituents
that are non saleable and selling the liquid hydrocarbon and gas.
➤ At the time of initial drilling, almost all crude oil is under pressure.
This natural pressure decreases as oil and gas is removed from the reservoir.
During the first phase, flush production the flow is governed by the natural
pressure in the reservoir which comes from dissolved gas in the oil, gas trapped
under pressure above the oil and hydraulic pressure from water trapped under
the oil.
➤ Artificial lift, the second phase involves pumping pressurized gas into
the reservoir when the natural pressure is expended.
➤Phase three, stripper or marginal production occurs when wells only
produce intermittently.

Basics of Hydrocarbon Chemistry:

Hydrocarbons are organic compounds that contain only carbon and

hydrogen. The four general classes of hydrocarbons are: alkanes, alkenes,
alkynes and arenes. Aromatic compounds derive their names from the fact that

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many of these compounds in the early days of discovery were grouped because
they were oils with fragrant odors.

The classifications for hydrocarbons, defined by IUPAC nomenclature of

organic chemistry are as follows:

1. Saturated hydrocarbons (alkanes) are the simplest of the hydrocarbon

species. They are composed entirely of single bonds and are saturated with
hydrogen. The general formula for saturated hydrocarbons
is CnH2n+2CnH2n+2 (assuming non-cyclic structures). Saturated
hydrocarbons are the basis of petroleum fuels and are found as either linear
or branched species.The simplest alkanes have their C atoms bonded in a
straight chain; these are called normal alkanes. They are named according to
the number of C atoms in the chain. The smallest alkane is methane

2. Unsaturated hydrocarbons have one or more double or triple bonds between

carbon atoms. Those with double bond are called alkenes and those with one
double bond have the formula CnH2nCnH2n (assuming non-cyclic
structures). Those containing triple bonds are called alkynes, with general
formula CnH2n−2CnH2n−2. The smallest alkene—ethene—has two C
atoms and is also known by its common name ethylene:

The smallest alkyne is ethyne, which is also known as acetylene:

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 3. Cycloalkanes are hydrocarbons containing one or more carbon rings to
which hydrogen atoms are attached. The general formula for a saturated
hydrocarbon containing one ring is CnH2nCnH2n.
4. Aromatic hydrocarbons, also known as arenes, are hydrocarbons that
have at least one aromatic ring. Aromatic compounds contain the benzene
unit. Benzene itself is composed of six C atoms in a ring, with alternating
single and double C–C bonds:

Because of differences in molecular structure, the empirical formula remains

different between hydrocarbons; in linear, or "straight-run" alkanes, alkenes and
alkynes, the amount of bonded hydrogen lessens in alkenes and alkynes due to
the "self-bonding" or catenation of carbon preventing entire saturation of the
hydrocarbon by the formation of double or triple bonds.

The inherent ability of hydrocarbons to bond to themselves is known as

catenation, and allows hydrocarbon to form more complex molecules, such as
cyclohexane, and in rarer cases, arenes such as benzene. This ability comes
from the fact that the bond character between carbon atoms is entirely non-
polar, in that the distribution of electrons between the two elements is somewhat
even due to the same electronegativity values of the elements (~0.30)

1.2 TYPES OF CRUDE OIL

Crude oil are classified based on
➤ API gravity and Viscosity
➤ Sulphur content
➤ Geographical location

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1.3.1 Based On API Gravity
➤ Light crude oil - having an API gravity higher than 31.1° API
➤Medium crude oil - having an API gravity betwcon 22.3° APl and 31.1°
API
➤ Heavy crude oil - having an API gravity below 2° API

1.3.2 Based on Sulphur Content

➤ Sweet crude oil - crude oil with low sulphur content
➤ Sour crude oil - crude oil with high sulphur content

1.3.3 Based on Geographical Location

Brent Blent
It is found in the northsea with an API gravity of 38.3 degrees and 0.37%
of sulfur, this blend of crude oil comes from 15 various oil fields in the
northsea.

West texas intermediate (WTI)

It otherwise known as texas light sweet, opec reference basket and dubai
crude. It is a light sweet crude oil with an API gravity of approximately HO and
sulphur content of 0.3%

Russian export blent

It is a mixture of several crude grades used domestically or sent for
export. Russian export blend is a medium, sour crude oil with an API gravity of
approximately 32 and a sulphur content of approximately 1.2%

1.4 COMPOSITION OF CRUDE OIL

An average crude oil content about

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 ➤Carbon - 84%
➤ Hydrogen - 14%
➤Sulphur - 1+0.3%
➤N2, O2, metals & salts - <1%

1.4.1 Hydrocarbons
Paraffins
Formula: Cn H2n+2
It can be either straight chains (normal) or branched chains(isomers) of
carbon atom. The lighter straight chain paraffin molecules are found in gases
and paraffin waxes. The branched chain paraffins are usually found in heavier
fractions of crude oil and have higher octane numbers than normal paraffins.

Aromatics
Aromatics are unsaturated ring type hydrocarbon (cyclic) compounds.
These are found in heavier fractions of crude oil. It usually having high boiling
points, low pour point (freezing points), high octane number, high viscosity and
low viscosity index and these burn characteristically with a red flame with much
soot. Actually the light aromatics (BTX) do not exceed even 5% of crude of
general nature

Olefins CnH2n
The first four are gases and unto C15 are liquids and beyond C15 are
solids. Unsaturated compounds like olefins, diolefins in general, do not appear
in crudes to measurable quantities, but detected in some crude. These are
formed during cracking operations.

Alkynes Cn H2n-2

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 These are isomeric with diolefins. Acetylene yield crystalline compounds
with ammonical solution of copper salts and are attacked by sulfuric acid.
Acetylene can be readily hydrogenated to give stable compounds.

Diolefins CaH2-2
These are produced during cracking operations they do not form salts
with ammonical solutions of copper salts. But with mercuric chloride it forms
precipitates.
Naphthenes Cn H2n
Ring structure starts with C5 atoms. It is isomeric with olefins, but differ
in properties. It exhibit both the properties of saturated paraffins and unsaturated
aromatics.

Inorganic Sulphur
➤Sulfur is found in most of the crudes in variable amounts. It present in
more quantities in higher molecular weight stocks.
➤ It occurs in different form like free sulfur, H2S, mercaptans and
thiophenes etc..
➤ Heavier fraction contain sulfides, polysulfides, sulphonates and
sulphates.
➤ It creates problem like corrosion and pollution problems Oxygen and
nitrogen
Oxygen and Nitrogen :
➤ Oxygen and nitrogen do not occur in free state either in crudes or in
fractions.
➤ Oxygen occurs as oxygenated compounds like phenols, cresols.
Naphthenic acids, sulphonates, sulfates and sulfoxides.
➤ Nitrogen exists in the form of indoles, pyridines, quinolines and
amines usually below 2%
Asphalts, Resins And Bitumens

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 ➤ Asphalts are high molecular weight complex molecules black in colour
soluble in aromatic solvents and carbon disulphide.
➤Resins are mostly compounds of highly condensing structures,
containing O2, sulfur and N2
➤Bitumen is made up of asphaits, resins and mineral oil.
➤ These three components comprise a colloidal system, asphalt are
suspended in oil and resin contribute to the stability of the system.
Less Inorganic
➤Nickel, Vanadium, Iron, Silica, Sodium, Magnesium, and Halogens.

1.5 CHARACTERISTIC AND CLASSIFICATION OF CRUDE OIL

Characterization Factors
➤Uop (or) Watson (kw)
➤ Correlation index (CI)
1.5.1 Watson characterization factor
1/ 3
(TB)
Kw =
G

TB - mean average boiling point R

G - specific gravity at 600 F
➤It provides a means of determining the paraffin city of a crude oil.
➤Kw-12.5 or greater indicates hydrocarbons compound predominantly
paraffinic in nature.
➤Lower value (Kw<10) highly aromatic materials .Kw vary from 10.5 to
12.5 highly naphthenie crude. Kw vary from paraffin city of crude oil.

1.5.2 Correlation Index

It is useful in evaluating individual fractions from crude oils. The CI scale
is based upon straight chain paraffins having Cl value of O and benzene having
a CI value of 100.
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 87552
CI = TB + 473.7G – 456.8

CI value ↓ - greater the concentration of paraffin in fraction.

CI value ↑ - greater the concentration of naphthenes and aromatics
➤ CI value between 0 to 15 indicates a predominance of paraffin
hydrocarbon in fraction.
➤CI value 15 to 50 - either naphthenes or of mixtures of paraffins,
naphthenes and aromatics.
➤ CI value > 50-aromatic species.

1.5.3 Characteristics Of Crude Oil

➤ Crude oil has been defined as naturally occurring mixture consisting of
hydrocarbons and/or of sulphur, nitrogen and/or oxygen derivates of
hydrocarbons, which is removed from the earth in a liquid state or is
capable of being removed.
➤ Brownish to brownish black in colour
➤ Specific gravity - 0.73 to 1.02
➤ Kinematic viscosities-0.7 to 1300 centistokes at 37.8° C

1.5.4 Classification Of Crude Oil Based On Hydrocarbon Present lu The

Crude
Paraffinic Base
Crude oil which on distillation yield residues obtaining paraffin waxes are
called paraffinic crude.
Asphalt Base
If the residues on atmospheric distillation of crude oil contain less than
2% wax.
Intermediate Base
If the residues contain both paraflin and asphalt material.

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Hybrid Base (Or) Naphthenic Base
` Crude which contain asphaltic material with small amount of paraffin
wax.

1.5.5 Based On Density

➤ Light crude oil - <870 kg/m³ [>31.1° API]
➤ Medium erude oil - 870 to 920 kg/m³ [31.1° API to 22.3° API]
➤ Heavy crude oil - 920 to 1000 kg/m³ [22.3° API to 10° API]
➤ Extra heavy > 1000 kg/m³ [less than 10° API]

1.6 EVALUATION OF PETROLEUM

➤ A crude oil is the chemical evaluation of crude oil feedstocks by
petroleum testing laboratories. Each crude oil type has uique molecular
and chemical characteristics. No two crude oil types are identical. It
provide a detail about detailed hydrocarbon analysis data.
➤ Evaluation of crude oil by U.S. Bureau of mines

Key Fraction No.1

➤Boiling range : 250 °C - 275°C & at normal pressure.
➤ 40 or more API gravity - paraffinic
➤<33 API gravity - naphthenic
➤33-40 API gravity - mixed base
Key Fraction No 2
➤Boiling range - 275°C - 300°C at pressure 40 WMHg
➤30 or more API gravity - paraffinic

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 ➤ <20 API gravity - naphthenic
➤20 - 30 API gravity - mixed base

1.7 PROPERTIES OF CRUDE OIL

Thermal Properties Of Crude Oil
1.7.1 Specific Heat
➤The amount of heat needed to raise the temperature of any kilogram of
mass by 1 degree celusis.
➤Sp.heat of petroleum fraction lies in the range of 0.3 to 0.85
➤It depends upon temperature and gravity lighter fractions have values
with increasing density, the specific heat decreases.
1
Sp.heat = ρ (0.4024 +0.00081 t)

ρ = sp gravity at 15.6/15.6°C t=tem p0 C

sp heat = [0.355 +1280(API) 10−6+(503+1.17* API) (3.2+1.8 t) 10−6 ] (0.05k
+0.41)
k = characterization factor t = ° C

1.7.2 Heat Of Combustion

➤ The energy released as heat when a compound undergoes complete
compustion with oxygen under standard conditions.
➤ In order of paraffins to aromatics, the heat of combustion decreases.
➤ Heating value (kj/kg) = 43,434 +93.2 (ΑΡΙ-10)
heat of combustion
➤ Wobble No =
√ sp . gravity

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1.7.3 Latent Heat Of Vaporisation
The heat absorbed per unit mass of a given material at its boiling point
that completely converts the material to gas at the same temperature. It is related
to molecular weight, ° API and molar average boiliog point.
T
L = γ LB TB

L = latent heat at any temperature (T absolute)

LB = latent heat at temperature (Тв. absolute)
Y = correction factor depends upon reduced temperature

1.7.4 Ignition Temperature

➤The temperature are which a material can catch fire and burn
continuously without the aid of external firing agencies.
➤Paraffins have high ignition temperatures
➤Aromatics have high ignition temperatures
➤ Ignition temperature decreases with increases in molecular weight as
well as with the oxygen content of molecule.

Physical Properties of Crude Oil

1.7.5 Viscosity And Viscosity Index
➤is defined as the resistance to flow of a liquid.
➤The viscosity of oil is largely determined by its content of large, polar
molecules namely resins and asphaltens.
➤ The greater the percentage of light components such as saturates and
the lower the amount of asphaltenes, the lower the viscosity.
➤In all refinery operations instead of absolute viscosity, kinematic
viscosity is used.
Absolute viscosity
Kinematic viscosity = Sp . gravity

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Viscosity index = indicates the variation characteristics of viscosity with
temperature.
L−U
V.I = L−H

Where, L= viscosity of reference oil of zero viscosity in degree at 37.8℃

H=viscosity of a reference oil of 100 viscosity index at 37.8° C
U = viscosity of test sample at 37.8° C paraffinic base oil have high V.I
(100 for reference) Napthene base oil have low value (0)
` Thermo viscosity = 15+ 148* kinematic viscosity
=SSU *46-1183
ThermoViscosity
Ring No = 5
-10 (46 – API)

Ring No in the range of 60 to 130.

1.7.6 Pour Point

➤The lowest temperature at which oil will move, pour or flow when it is
chilled without disturbance under definite condition.
➤The lower the pour point, the lower the paraffin content and the greater
the content of aromatics.
1.7.7 Sulfur Content
➤It is expressed as percent of sulfur by weight and varies from less than
0.1% to greater than 5%
➤ Crude with greater than 0.5% sulfur generally require more extensive
processing to low sulfur content.

1.7.8 Carbon Residue

➤ It is determined by distillation to a coke residue in the absence of air. It
related to the asphalt content of the crude and to the quantity of
lubricating oil, that can be recovered.

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 ➤ Lower then carbon residue the more valuable the crude, expressed
interns of 1) Rams bottom 2) Conrad son.

1.7.9 Salt Content

If the salt content of the crude, when expressed as Nacl is greater than 10
ib/1000 bbl, it is necessary to desalt the crude before processing.

1.7.10 Nitrogen Content

Undesirable in crude oils crude contain more than 0.25% by weight
require processing to remove N2

1.8 INDIGENOUS AND IMPORTED CRUDE

1.8.1 Sources Of Indigenous Crude
➤ Assam crude, Bombay high and satellite fields, north Gujarat &
Ankhleshwar
➤ KG basin - Rava crude
➤ Cauvery basin crude
➤ Rajasthan crude
1.8.2 Sources Of Imported Crude
Arab mix, Lavan blend, Upper Zakum Iron mix, Dubai, Kuwaiti crude,
Suez mix, zelt bay, quaiboe, mirilight, Bonny light.

1.9 CRUDE AVAILABILITY VS DEMANDS

➤The world supply and demand balance as projected by the international
energy agency began. posting periodic quarterly deficits over a year ago and us
oil production growth has been largely offset by the oil producers. This leaves
economic growth / oil demand growth as the swing factor for price action in the
second half of 2017.

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  The EIA (U.S energy information administration) forecasts that the
global crude oil supply and demand gap will average around
290,000 bpd (barrels per day) in 2017.
 Excess supply, combined with a market expectation for softening
global demand, has weighted on oil prices.

➤Global supply will likely continue to outpace demand this year due to
significant production increases from OPEC and the lag in production
slowdown from both us shale and from non OPEC.
 Chinese oil imports will continue to expand in the second half of 2017
because of strong Chinese passenger car sales. Given the significant
increase in vehicles on the road in china over the last two years, H is
likely that product demand will prompt more imports and more
aggressive refining activity in china.

1.9.1 Global Oil Demand Vs Supply / Production By Region Through 2030.

World overall oil consumption is forecast to grow at 1.2% per year over
the next 25 years. Organization for economic co operation and
development (OECD) is forecast to grow at 0.3% per year over the same
period, while non-OECD world oil demand is forecast to grow at 2.2%
per year.
➤The fastest growing market will be china demand is ever increasing,
especially due to growth of Chinese economy.
➤China oil imports
➤Of half of its import from middle east.
➤One third its oil imports from Africa.

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