CLPE11

PETROLEUM AND PETROCHEMICAL ENGINEERING

INTRODUCTION
Energy
• One of the basic requirements of the human society is Energy.
• Petroleum Industry - one of the most important sources of energy.
Introduction
• Petra (rock) + Oleum (oil) = Rock oil = Petroleum
Petroelum
• Occurs as gas, liquid, semi-solid, or
solid.

• (Or) More than one of these states.

• Mixture of Hydrocarbons and minor

amount of N2, O2 and S.
Petroleum
• “Mineral Hydrocarbons” – Dictionary Definition.
• Can Petroleum be called mineral?

• Geological definition of mineral:

• An inorganic substance with chemical and physical properties either uniform or
varying within narrow ranges.

• Because of its association with rocks, petroleum is included among “Mineral Resources”.

• Combustible minerals form the special family of minerals named "caustobolites“ - meaning
combustible organic stone.

• Caustobolites contain carbon, hydrogen and oxygen.

Age

Kerosene Age Gasoline Age Petrochemicals

At Present
1859-1900

Emerging
Petroleum

Liquid form Gas form

Commercially important. Commonly called Natural Gas

Called crude oil Contains predominantly CH4 + lighter HC

What will be taught in this course?
Course Flow
• Composition
Crude Oil • Characterization

• Atmospheric Distillation
Primary • Vacuum Distillation
Processing

• Thermal and Catalytic Cracking

Secondary • Alkylation, Isomerization, Polymerization
Processing
 •Treatment of the products
Treatment to improve their quality.
Techniques

•Pollution Control
HSE •Safety Aspects
Complexity of a Refinery!
Major Processes and Products
 Crude Oil
• Petroleum/crude oil has Earlier Uses
been known for more than • Recipes of medicines.
6000 years.
• Construction work.
• The most ancient known oil
• Water proofing material.
wells are those at
• Ephrata and the Kerch coast in
the Chinese province of • Embalming mummies.
Sychuan.
• "Greek fire" = Petroleum +
saltpeter.
 Early Mediterranean civilizations used to dig
shallow pits around seepages to collect oil.

• ITTU-name for
Bitumen-used as
caulking agent in
wooden ships.

• Only small quantity of it

was used till recently.

• On the other hand, up to middle of the 19th century, oil derived

from vegetable and animal sources were used for lighting
purposes.
• Initially, Machines were lubricated using castor or whale oil.
• In 1850, James Young of Glasgow developed a process for making lamp
oil by distilling either coal or oil shale.

• In the USA, an enterprising oil peddler wanted to improve the

taste of oil used as medicine by distilling the petroleum in a
whisky still.

• He obtained a clear liquid, which worked well as a lamp oil.

• This clear liquid was named kerosene.

• 1854 is the starting point for the first American oil company –
Pennsylvania Rock Oil Company.
• Edwin Drake discovered oil in Pennsylvania in 1859.

• August 27, 1859 - real production of crude oil began in Oil

Creek, Pennsylvania.

• Oil was found at a depth of 21 m and produced 200 barrels

per year.

• A pipeline of 5 cm in dia built in 1863 near Titusville was

the first pipeline laid to transport oil.
• 1878 - the Swedish businessman Alfred B. Nobel
together with his brothers formed the Naphtha
Company Brothers Nobel.

• The company extracted the crude oil in Baku, Russia

• Transported to the refinery via the pipelines built by

Naphtha Co., which still exists now.
 • The USA and USSR are the major
producers till the middle of the twentieth
century.

• Lamp oil was the major product initially from crude oil.

• Gasoline was obtained as a byproduct.

 • Invention of IC engines

• Henry Ford-Mass production of

automobiles.

• The above two scenarios made the refinery as one of the world’s largest industry.

• The use for gasoline in IC engines tremendously increased the production of gasoline.

• The discovery of oil in the Arab lands is the turning point. Oil was found in Iran in 1908, Iraq
in 1923, Bahrain in 1932, and Saudi Arabia and Kuwait in 1938.

• However the USA was the leader till 1960. Thereafter middle east surpassed all other
countries.
• 1961 - Organization of the Petroleum Exporting Countries (OPEC) comprising of 11 countries was
established.
• Purpose - To avoid exploitation of member countries.

• 1974 - International energy agency was established by oil consuming industries.

• Saudi Arabia - World’s largest oil producer and Russia is the second.

• Russia is moving forward with a record production of 7.65 million barrels/day and this is because of deep water
oil fields.

• Oil companies have technologies to drill wells up to 3075 m under the sea.
Estimated worldwide reserve of crude oil = 1028 billion barrel.

OPEC Share = 814 billion barrels.

India = 4.7 billion barrels.

Total worldwide refining capacity = 81.3 million barrels/day.

About 742 refineries operate all over the world.

Exxon Mobil refines 5.4 million barrels per day.

Exxon Mobil has 34 refineries.

Shell refines 4 million barrels per day.

 Largest Refineries

• Jamnagar Refinery (India)

• Ulsan Refinery (South Korea)

• Paraguaná Refinery (Venezuela)

Indian Scenario
• Exploration activity was started in India way back in
1866 in the northeastern state of Assam.

• Burma oil company was doing this exploration

activity.

• We have started drilling just after 7 years of

Pennsylvania well establishment.

• But for about a century the exploration and

production activity was restricted to the North-East
part of the country.

• First oil well was in Digboi.

 In 1947, India was producing 0.25 million tonnes of oil per year.

In 1947, India had only one refinery, which was processing 0.5 MMTPA.
But at that time the domestic consumption was 2.6 MMTPA.

This forced the Government to setup oil and natural gas commission
(ONGC).

Burma oil was merged with Oil India Limited in 1981.

ONGC became public limited company in 1993.

ONGC and OIL market their products except natural gas, which is
distributed through GAIL.
 • Now there are 26 sedimentary basins in India
covering an area of 1.78 million square km.
• Out of 1.78 million square km
• Onshore – 1.46 million
• Offshore – 0.32 million
• Out of 26 basins, very few were explored till now.
• Six are operated by ONGC and OIL operations are
confined to the upper Assam basin.
• Major oil fields are located in
• Bombay high
• Ankleshwar in Gujarat
• Upper Assam
• IOC was started in 1964.
• Today India is the global refining hub with refining capacity of 248.9 MMTPA and is the
fourth largest in the world after the United States, China and Russia.
• There are total 23 refineries in the country, 18 in the Public Sector, 2 in the Joint Venture
and 3 in the Private Sector.
 Pricing Mechanism
• Administered pricing mechanism was lifted in April 2002.

• Market Determined Pricing Mechanism (MDPM) was implemented

to ensure competition among oil companies.
Origin of Petroleum
CARBIDE THEORY : BERTHELOT (1866)
• Hydrocarbons present in petroleum are formed by the action of water
on inorganic carbides.

• Inorganic carbides formation = Rxn. of metal + carbon under high T&P

prevailing inside the earth.

• (Calcium carbide)
• (Aluminium carbide)
Lower Hydrocarbon formation
• + (Acetylene)

• + (Methane)

• Hydrogenation

• + (Ethane)

• (Benzene)

• (Cyclohexane)
Support for Carbide Theory Drawbacks of Carbide Theory
• Inorganic theory of crude oil formation • Failed to explain
received support from astrophysics. • Presence N and S compounds
• Research on the spectra of planets showed • Presence of Porphyrins- Chlorophylls
that, • Presence of optically active compounds
• there are hydrocarbon compounds in
the atmosphere of Jupiter and other
large planets as well as in gas • A long time ago in Wyoming (USA), the
inhabitants heated their houses using pieces of
environments of comets. asphalt, which they collected from the cracks in
• If hydrocarbons are widespread in space, mountain layers in the Copper Mountains.
natural synthesis of organic substances
from inorganic substances are possible. • But the minerals, of which these mountains
consisted, could not accumulate petroleum and
gas.

• This means that the asphalt (similar to oil) could

only be formed according to the inorganic
theory.
 Space Hypothesis – Cosmic Theory
• Sokolov (1892) stated that the dust cloud from which the Earth and
other planets of the solar system were formed consisted of
hydrocarbons.

• In the process of the formation of the Earth, hydrocarbon substances

were buried in the core of the earth.

• Further, during the cooling or consolidation of the planet, the

hydrocarbons were pushed out.
 Engler Theory (1900)
• According to Engler , Petroleum is of • The largest fraction of evaporated
animal origin. material was oil (299 kg, or 61%) with
a density of 0.8105 g/cm3.
• Formed by the decay and
decomposition of marine animals • Subsequent evaporation of the oil
under high T&P. Produced saturated hydrocarbons
(ranging from pentane to nonane),
paraffins, lubricant oils as well as
• The experiments were performed by olefins and aromatic hydrocarbons.
evaporation of fish blubber at 400°C
and 1 bar.
• This theory fails to explain the
presence of chlorophyll in petroleum.
• Oil, combustible gases, water, fats and
different acids were formed from the
492 kg of fat used.
 Vegetative Origin
• Russian scientist (N.D. Zelinskiy) carried out a similar experiment in 1919.

• Initial material = organic silt (vegetative origin) from Lake.

• Evaporation products:
• Crude pitch - 63.2%,
• Coke - 16.0%,
• Gases (methane,carbon oxides, hydrogen, hydrogen sulfide) - 20.8%.

• Processing of pitch yielded gasoline, jet oil and heavy oil.

Organic Hypothesis
• The oil pool is an end product to a 5-stage sequence of events:

• Raw materials
• Accumulation
• Transformation
• Migration
• Geologic time
 Organic Hypothesis
• Carbon-hydrogen-organic matter connection.

• Carbon and Hydrogen are the primary constituents of organic

material, both plant and animal.

• Nitrogen and porphyrins (chlorophyll derivatives in plants, blood

derivatives in animals) are found in all organic matter; they are also
found in many petroleums.
Formation at Anaerobic Conditions
• Presence of porphyrins confirms that anaerobic conditions must have
developed early in the formation process.
• Porphyrins are rapidly oxidized under aerobic conditions.
• Additionally, low Oxygen content also implies a reducing
environment.

• Thus there is a high probability that petroleum originates within an

anaerobic and reducing environment.
Marine origin/Temperature
• All petroleum occurs in sediments are primarily of marine origin.
• Petroleum contained in non-marine sediments probably migrated into
these areas from marine source materials located nearby.

• Temperatures in the deeper petroleum reservoirs seldom exceed

141oC .
• But temperatures never exceeded 200oC where porphyrins are present
because they are destroyed above this temperature.
• Therefore, the origin of petroleum is most likely a low-temperature
phenomenon.
 Organic Hypothesis
• Organic matter - material composed of organic molecules derived
directly or indirectly from the organic part of organisms.

• Organic matter is synthesized by living organisms.

• Upon the death, these organisms are either oxidized back to its
simple inorganic constituents (mainly CO2 and water)
(or)
• deposited along with inorganic sediments, in usually small but
sometimes surprisingly large concentrations.
 Oil Formation in the World's Oceans
• Most significant role in petroleum formation is played by
microorganisms.

• Typically plankton, 90% of which is microscopic seaweed

(phytoplankton).

• 95% of living matter in the ocean is plankton.

• Planktons are present in silts at the bottom of seas or lakes/dispersed

or dissolved in water.
 Plankton
• Plankton (Phytoplankton, Zooplankton) create the oil by synthesizing fatty
acids.

• Fatty acids are essential constituents of animal fats and animal/plant oils.

• The general formula for these acids are CnH2n+2COOH or CnH2nO2 and they
form the largest known source of long-chain molecules.

• This is important because the molecular structure of fatty acids is similar to

the molecular structure in crude oil.
Formation of Petroleum – Organic origin
• Broadly speaking, the depth of burial at which most fluid petroleum
hydrocarbons are generated ranges from about a thousand meters to
a few thousand meters.

• The series of chemical changes in organic matter upon burial of a

sediment is conventionally subdivided into three stages:
• Diagenesis
• Catagenesis
• Metagenesis
• 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 proteins and carbohydrates break down to
form new structures that comprise a waxy material
known as “kerogen” and a black tar like substance
called “bitumen”.

• All of this occurs within the first several hundred

meters of burial.

• The bitumen comprises the heaviest components

of petroleum, but the kerogen will undergo further
change to make hydrocarbons.
• As T and P increase (deeper burial) the
process of catagenesis begins.
• It is the thermal degradation of kerogen to
form hydrocarbon chains.
• Catagenesis is catalyzed by the minerals that
are deposited.
• The conditions of catagenesis determine the
product.
• Temperature may range from about 50 to
150°C and geostatic pressure may vary from
300 to 1000- 1500 bars.
• Higher T and P lead to more complete
“cracking” of the kerogen and progressively
lighter and smaller hydrocarbons.
• Petroleum formation, then, requires a
specific window of conditions;
• Too hot and the product will favor natural
gas (small hydrocarbons), but too cold and
the plankton will remain trapped as kerogen.
 Petroleum System
• Source Rock: A rock with abundant hydrocarbon prone organic matter

• Reservoir Rock: A rock in which oil and gas accumulates

• Porosity: space between rock grains in which oil accumulates

• Permeability-Passage ways between pores through which oil and gas moves

• Seal Rock: A rock through which oil and gas cannot move effectively (such as
mudstone and claystone)

• Migration Route: Avenues in rock through which oil and gas moves from source rock
to trap

• Trap: The structural and stratigraphic configuration that focuses oil and gas into an
accumulation
 Oil Migration
• The process of petroleum displacement in the native minerals (i.e.
from which it is formed) is referred to as primary migration or
emigration.

• It is a slow process, both because of the relatively high viscosity of the

liquid petroleum (the natural gas component moves faster) and
because of the low permeability of shales.

• Shales are of low permeability for two reasons: low porosity, and
small size of the passageways that connect that porosity.

• The liquid moves in the direction of most rapidly decreasing pressure,

which for various reasons may be at some angle to the vertically
upward direction.
 Water Associated
• The basic pore fluid in all subsurface sedimentary rocks is, of course,
water, with various dissolved constituents.

• At the depths of petroleum generation, such pore waters (called

formation waters/fossil water at that stage) are usually very salty
(brines).

• Connate water is groundwater that has been trapped within the pore
space of sedimentary rock since its original deposition.
 Secondary Migration
• By getting into loose solid minerals (collectors or traps), petroleum
begins a new life.

• Wherein it travels much faster.

• Such migration in more porous rock is called secondary migration.

• Petroleum migration through collectors proceeds as long as it does

not encounter a trap (i.e. a layer that is capable of keeping the
petroleum as a trapped deposit).
Trap • A petroleum trap is an
arrangement of effectively
impermeable rocks above
permeable rocks in a
geometry such that the
boundary surface or zone
between the permeable rock
below and the impermeable
rock above has upward
convexity.

• This formation may be found

from a few kilometers (as
deep as 2 km and as deep as
7 km) below the earth’s
surface.
 Types of Traps
• A structural trap is a trap whose
geometry originates by
deformation.
Anticlinal oil traps
• Structural traps result from a local
deformation such as folding
and/or faulting of the rock layers.

• Faulting can also produce traps by

juxtaposing a reservoir against an
impervious stratum.
Structural oil trap caused by faulting
Anticline traps
 Stratigrapic traps
• Most basins contain facies changes, unconformities with resulting truncated
beds, and buried erosional or constructive surfaces such as reefs, hills, barrier
sand bars, channels, and other related geologic phenomena which form the
basic requirements for the creation of stratigraphic traps.

• Stratigraphic trap is a general term for traps that are chiefly the result of a lateral
variation in the lithology of the reservoir rock, or a break in its continuity.

• For example a permeable reservoir rock changes to a less permeable or to an

impermeable rock.

• Two common types:

• Pinchout Type
• Truncated Type
The termination by thinning or tapering .out
("pinching out") of a reservoir against a nonporous
sealing rock creates a favorable geometry to trap
hydrocarbons, particularly if the adjacent sealing
rock is a source rock such as a shale.
• Salt domes form when salt is less
dense than the overlying rock, and
the salt moves slowly upwards due
to its buoyancy.

• For this to happen, there must be a

minimum overburden and the
thickness of the salt deposits must
be more than ~100 m.

• Upward movement of salt through

the sedimentary strata, and
associated deformation is termed
halokinetics or salt tectonics.

• Movements may continue for several

hundred million years.
 Prospecting
• A prospect of hydrocarbon deposits is declared by the geologist when the
area under study satisfies the geological structure and conditions.

• The area where oil and gas are stored is known as formation.

• Drilling is started only in the prospect area as declared by the geologists.

• Oil reserves are classified into three categories, namely,

• Proven reserve
• Probable reserve
• Possible reserve
 Reserves
• Proven reserves are worth for economic exploitation.

• Probable reserve has a certain degree of probability (about 50%) for

economic exploitation.

• Possible reserve has very little probability (about <10%) for economic
exploitation with current technology.

• Commercially viable formation is also known as pay or pay zone.

Oil Exploration
 Oil Exploration
• In the early days, most oil findings were the result of digging or
drilling near known oil and gas seeps or of accidental finds while
drilling for water.

• A good definition of a seep is ''the surface expression of a migration

pathway, along which petroleum is currently flowing, driven by
buoyancy from a sub-surface origin'‘.
 Remote Sensing
• Remote sensing refers to using infrared or other means to map an area.

• This method is used to study the basics of petroleum geological conditions.

• The remote sensing images have characteristics of realty and provide

accurate visual data for directly determining geometric shapes of
sedimentary basins.

• Remote sensing equipments can be carried by airplanes or by satellites.

• Companies using remote sensing data, however, still need traditional

exploration information to pinpoint the location of commercial deposits.
 Geophysical Methods
• Four popular geophysical methods

• Magnetic prospecting

• Gravimetric prospecting

• Seismic prospecting

• Electric prospecting
 Magnetic Prospecting
• Sedimentary rocks generally have a very • It transmits data to a device on board which
small magnetic susceptibility compared with records the information onto paper or
igneous or metamorphic rocks, which tend to magnetic tape.
have a much higher magnetite (a common
magnetic mineral) content.
• A development of airborne magnetics is the
micromagnetic technique for oil exploration.
• By conducting a magnetic survey over a given
area, a prospector can determine where oil-
bearing sedimentary rock is more likely to be • An airplane tows a micromagnetometer from
found. a low altitude, normally about 300 ft above
the ground.
• The magnetometer is used to measure the •
magnitude of the earth's total magnetic field • It detects micromagnetic anomalies, or
over a large area. deviations from the norm.

• A magnetometer can be towed behind a ship • Geologist use these data to predict the
or an airplane to cover large areas. characteristics of the overlying sediments.
 Gravity Methods
• The Earth's gravitational attraction varies slightly from one place to
another on the Earth's surface.

• Some of this variation occurs because the Earth is not a perfect sphere, and
some is related to differences in elevation on the Earth's surface.

• In gravity prospecting, geophysicists measure variations in the force of

gravity from rocks up to a few miles beneath the earth's surface.

• Different types of rocks have different densities, and the denser rocks have
the greater gravitational attraction.
 Gravity Methods
• If the higher-density rock formations are arched upward in a
structural high, such as an anticline, the Earth's gravitational field will
be greater over the axis of the structure than along its flanks.

• A salt dome, on the other hand, which is generally less dense than
the rocks into which it is intruded, can be detected from the low value
of gravity recorded compared with that measured on either side.
 Seismic Prospecting
• Seismic reflection, a powerful technique for underground
exploration, has been used for over 60 years.

• It will give more precise details on the formations beneath the

surface.

• Seismic waves are essentially sound waves that travel

underground at velocities of 2 to 4 miles per second (3 to 6 km
per second), depending upon the type of rock through which
they pass.

• The reflections are recorded by detecting instruments

responsive to ground motion (geophones).

• They are laid along the ground at distances from the shot point.
• Variations in the reflection times from place to place on the
surface usually indicate structural features in the strata below.
 Electrical Logging
• This method is based on the fact that the resistivity of
a rock layer is a function of its fluid content.
• Oil-filled sand has a very high resistivity.
• In this method, current is passed between an
electrode at the surface and the one which is
lowered into the hole, the latter being uncased and
filled with drilling mud.
• Any change in resistivity will affect the flow of current
and the voltage distribution.
 GEOCHEMICAL METHODS
• Inorganic content of surface or shallow cuttings or core are sampled
and analysed for inorganic materials, such as salts and carbonates.

• Organic content is detected by heating a sample in a crucible and the

loss of mass of the sample is an indication of the presence of organic
matter.

• The ratio of organic mass to inorganic matter in a sample is used to

ascertain the presence of hydrocarbons
 RESOURCE ESTIMATION
• The quantum of oil and/or gas present in the reservoir pores is called
oil and/or gas in place.

• The amount of hydrocarbon oil that can be economically produced

and marketed is called reserve.

• The oil and gas volume/quantities can be estimated by the volumetric

method.
 RESOURCE ESTIMATION
( )
Volumetric oil in place in million metric tons =

A = Area of oil pool in square kilometres

H = Oil pay thickness in metres
Θ = Porosity of the reservoir rocks
ρ0= Density of oil
b0= Volume fraction of oil in the formation
sw = fraction saturated by water in the pores
 RESOURCE ESTIMATION

θ(1 − sw)
Gas in place =

A: area of oil pool in square kilometres

H: oil pay thickness in metres
θ: porosity of the reservoir rocks
sw: fraction saturated by water in the pores
pr: reservoir pressure in the formation
ps: pressure at the surface of earth
Tr: absolute temperature in the formation
Ts: absolute temperature at the surface
DRILLING
 Drilling
• Drilling is done to fracture and penetrate the rocky layers to reach the oil
formation below the Earth’s surface.

• A hollow steel pipe containing the drill bit with perforations at its mouth is
used for drilling.

• Mud fluid is pumped through the top end of the drill pipe through a hose
which moves down with the pipe as the drilling progresses.

• The drill pipe and the hose are suspended from the crown of a pyramidal
structure called a rig.
Cable tool method of drilling
(Until 1900)
Rotary Drilling • Derrick, the tall tower-like structure that
extends vertically from the well hole.

• Rotating equipment from top to bottom

consists of swivel, a short piece of pipe called
the kelly, rotary table/topdrive, drill string and
bit.

• A component called the swivel, which is

attached to the hoisting equipment, carries
the entire weight of the drillstring, but allows
it to rotate freely.

• The drill bit is located at the bottom end of the

drillstring, and is responsible for actually
making contact with the subsurface layers,
and drilling through them.
Circulating System
• A high pressure pump is employed to pump
the mud solution from the mud pit through
the hose.
• The cuttings at the drill bit are washed out
through the mouth of the drill bit and returned
to the top surface through the annular space
between the drill pipe and the hole developed.
• Cuttings with the mud solution are collected
and separated from each other.
• Clarified mud along with fresh mud are
pumped back to the drill pipe continuously.
• Mud is consumed due to absorption and
seepage through the pores and crevices of the
layers.
 Drilling
• After drilling to a depth of 30–40 ft, a steel pipe is introduced into the
hole to protect the wall of the hole formed.

• This is called the casing string, which is then cemented to the wall of
the hole by pumping a fast-setting cement solution (usually Portland
cement without sand) to the annular space between the pipe casing
and the wall of the hole.
• Top of the well (well head) along with
the casing hanger are fitted with the
necessary piping and collection
headers.

• A pipe riser is inserted in the well to lift

the oil and is connected to the well-
head piping and valves.

• The diameter and design of the pipe

riser (tubing) may differ depending on
the facility of the oil lifting mechanism.

• The well-head connection consists of a

tubing header and a Christmas tree
header for collection of oil, gas, and
water to the respective storage tanks.
 Recovery
• Primary Recovery
• Recovery of hydrocarbons from the reservoir using the natural energy of the
reservoir as a drive.
• Secondary Recovery
• Recovery aided or driven by the injection of water or gas from the surface.
• Tertiary Recovery (Enhanced Oil Recovery – EOR).
• EOR methods are applied to reservoirs in order to improve flagging production.
• Infill Recovery.
• Carried out when recovery from the previous three phases have been completed. It
involves drilling cheap production holes between existing boreholes to ensure that
the whole reservoir has been fully depleted of its oil.
 Drive Mechanism
• The natural energy of the reservoir used to transport hydrocarbons
towards and out of the production wells.
• Five important drive mechanisms (or combinations).
• Solution Gas Drive.
• Gas Cap Drive.
• Water Drive.
• Gravity Drainage.
• Combination or Mixed Drive
• A combination or mixed drive occurs when any of the first three
drives operate together or when any of the first three drives operate
with the aid of gravity drainage.
 Solution Gas Drive
• This mechanism (also known as depletion drive) depends on the associated gas of the oil.

• The virgin reservoir may be entirely liquid, but will be expected to have gaseous
hydrocarbons in solution due to the pressure.

• The bubble point pressure is known as the pressure at which the first bubble of gas
comes out from the liquid at a given temperature.

• As the reservoir depletes (due to production), the pressure falls below the bubble point,
and the gas comes out of solution to form a gas cap at the top.

• This gas cap pushes down on the liquid helping to maintain pressure.

• The exsolution and expansion of the dissolved gases in the oil and water provide most of
the reservoirs drive energy.
 Gas Cap Drive
• In reservoirs already having a gas
cap (the virgin pressure is already
below bubble point), the gas cap
expands with the depletion of the
reservoir, pushing down on the
liquid sections applying extra
pressure.

• The presence of the expanding gas

cap limits the pressure decrease
experienced by the reservoir
during production.
 Water Drive
• The drive energy is provided by an aquifer
that interfaces with the oil in the reservoir at
the oil-water contact (OWC).

• As the hydrocarbons depleted (production

continues), and oil is extracted from the
reservoir, the aquifer expands slightly.

• If the aquifer is large enough, this will

translate into a large increase in volume,
which will push up on the hydrocarbons, and
thus maintaining the reservoir pressure.

• wo types of water drive are commonly

recognised: Bottom water drive and Edge
water drive.
• The density differences
between oil and gas and water
result in their natural
segregation in the reservoir.

• This process can be used as a

drive mechanism, but is
relatively weak, and in practice
is only used in combination
with other drive mechanisms.
 Combination Drive

• In practice a reservoir usually

incorporates at least two main
drive mechanisms.
 Secondary Recovery
• Secondary recovery is the result of human intervention in the
reservoir to improve recovery when the natural drives have
diminished to unreasonably low efficiencies.
• Two techniques are commonly used:

• Waterflooding – involve injection of water at the base of a reservoir to

maintain the reservoir pressure, and displace oil towards production wells.

• Gas Injection - This method is similar to waterflooding in principal, and is used

to maintain gas cap pressure even if oil displacement is not required
•The gas lift method employs high pressure gas, usually air
or carbon dioxide, which is introduced into the well through
the annulus.

•Oil is carried through the inner tubing, leading to the well-

head piping.

•Initially, the well is filled with the mud fluid and the oil
cannot move up owing to the hydrostatic head of the mud
fluid.

•As the gas enters the annulus and piping, the density of the
mud column decreases and the hydrostatic head decreases.

•As a result, the mud fluid is lifted by the oil pressure.

•A mud–oil mixture is collected and separated on the

surface tanks.

•When complete displacement of mud takes place from the

well, oil production starts.
•A sucker rod lift well contains a piston (or a plunger)
pump lowered into the inner tubing.

•The piston is operated by a metallic wire or rod leading

through the tubing and above the well head and
connected to a wire rope from a hanger attached with a
reciprocating driving system at the base of the well head.

•The piston is contained in a cylinder with non-return

valves fitted at both ends.

•During the upstroke of the piston, the bottom valve

opens, keeping the top valve closed and, as a result, the
cylinder pressure falls below the reservoir pressure,
forcing oil to enter the cylinder.

•While during the down stroke of the piston, the upper

valve opens and the bottom valve closes and oil in the
cylinder is pushed up to the tubing through the upper
valve.
 Tertiary Recovery (EOR)
• Primary and secondary recovery methods usually only extract about
35% of the original oil in place. Clearly it is extremely important to
increase this figure.

• Many enhanced oil recovery methods have been designed to do this.

They fall into three broad categories:
• Thermal EOR
• Chemical EOR
• Miscible Gas

• All are extremely expensive, are only used when economical.

 Wells
• The amount of paraffins in different crude oils varies from 2 to 50%.

• The light paraffins are mainly components of natural gas, which

dissolve in the crude oil in the oil wells.

• Depending on the composition and conditions in the oil well, one can
specify well classes such as
• gas wells
• gas condensate wells
• crude oil wells
 Gas Wells
• Gas wells contain mainly - light paraffins - methane, ethane, propane
and butane, all of which are gases at normal conditions (0.1 MPa and
20°C).

• Apart from these hydrocarbon gases, gas wells also contain

• CO2
• H2
• H2S and inert gases such as N2, Ar, He, Ne and Xe.
 • The region between the green curve and the red curve
is the two-phase envelope.
• The region outside of the two-phase envelope is the
single-phase region.
• Single-phase liquids exist to the left (lower
temperatures) and above (higher pressures) the
bubble-point locus (green curve);
• Single-phase gases exist to the right (higher
temperatures) of the dew-point locus (red curve).
• The green curve in this figure represents the Bubble-
Point Locus of this multi-component system;
• The red curve represents the Dew Point Locus of the
system.
• Dashed lines in the two-phase region represents
the quality lines of the system (lines of constant
Phase Diagram of a Multi-Component System Typical volume-fraction of the liquid phase).
of Real Hydrocarbon Reservoir Fluids
• Pmax in Figure is the cricondenbar (the maximum
pressure in which two phases can coexist);
• Tmax is the cricondentherm (the maximum temperature
in which two phases can coexist).
Gas Condensate Wells
 Gas Condensate Wells
• At the time of discovery, gas condensates are often found as single-
phase gas in the reservoir.

• As the reservoir is being produced, the pressure decreases from the

reservoir to the wells and to the surface installations, leading to
condensation of liquids out of the gas.

• This isothermal condensation as the pressure drops below the dew

point pressure of the original fluid is known as retrograde
condensation.
• Gas condensate reservoirs are gas
systems that reside in reservoirs
with the original temperatures
lying between TC and the
cricondentherm (Tmax).

• If the original reservoir pressure is

greater than the dew-point
pressure, then a single-phase gas
system will occur in the reservoir
as in Figure.

• As we deplete the pressure due to

gas production the pressure-
temperature path of the system
enters the two-phase region of
the phase envelope.

• Liquid hydrocarbons condense

from the gas in the reservoir (thus
the name gas condensate
reservoir.)
• Think of a four-component mixture of oxygen, carbon-
dioxide, nitrogen, and water vapor (a mixture of air) and its
phase envelope.

• If we started at a point in the single-phase gas region with a

pressure below the cricondenbar (pmax).

• Reduce the temperature under constant pressure conditions

(isobaric conditions), then we would cross the dew point
locus of the phase envelope.

• This would be the pressure and temperature where we

would see the first dew forming .

• If we were to continue reducing the temperature, then the

percent volume of liquid (water) would increase and it
would begin to rain.

• What is happening in this simple example is that

the heaviest component in our system (water
vapor) is condensing out of the gas phase (air
mixture) and forming a second phase (liquid
water) in the two-phase region.
 Gas Condensate Wells
• As we pass through the dew point pressure, the heaviest hydrocarbon
components in the system begin to drop out and form a second, liquid
hydrocarbon phase in the two-phase region of the phase envelope inside
the reservoir.

• Due to lower permeability to liquid and a high liquid-to-gas viscosity ratio,

most of the condensed liquid in the reservoir is unrecoverable and
constitutes the “condensate loss”.

• Condensate loss is one of the greatest economical concerns since the

condensate contains valuable intermediate and heavier components of the
original fluid now trapped in the reservoir.
 • retrograde behavior
• Path A-A’-A’’
• Pass through the dew-point pressure
• Increase the volume % of the liquid
hydrocarbon phase (Point A’)
• Further reduction in pressure resulting in
a lower vol % of the liquid hydrocarbon
phase.
• We could also continue the isothermal
pressure reduction, reenter the single-
phase gas region, and stop at Point A’’.

• Pure (single-component) system, the liquid phase occurs at higher pressures than the gas phase.
• Reduce the pressure isothermally to create a gas phase in a pure system.
• For multi-component system if we start at Point A’ and reduce the pressure isothermally, then we would get the
conventional behavior for a pure system along Path A’-A’’.
• Conversely, if we were to start at Point A’ and increase the pressure isothermally to Point A in the single-phase gas
region. The behavior is opposite of that for a pure system along Path A’-A.
• This behavior, opposite to a pure system, is referred to as retrograde behavior.
 Crude Oil Wells
• Crude oil wells contain crude oil as well as gas.
• The amount of gas in the crude oil varies from very little to hundreds
of cubic meters per ton of crude oil.
• These gases, solved in crude oil, can be released from the crude oil at
normal pressures.
• After production, crude oil is stabilized by separating the gas from the
oil.
• The crude oil coming to the refinery usually contains less than1% of
dissolved gas.
WELL PRESSURE PROFILE
 RESOURCE ESTIMATION
• The oil potential of a deposit depends on

Pressure and Temperature of the formation

Surface tension

Density and viscosity of the oil

Porosity and permeability of the rock

 EFFECT OF TEMPERATURE
• The temperature under the surface of Earth increases with depth.

• The rate of increase in temperature per 34 m of depth is called the

geothermal gradient, which may be less than or greater than 1°C per 34 m.

• This may vary from well to well.

• The greater the thermal gradient, the more permeability of oil.

• The bottom hole pressure may be increased by partial combustion of oil or

injection of steam or hot gas into the surrounding wells.
 EFFECT OF VISCOSITY
• Reservoir crude oil is classified as a viscoelastic fluid that exerts normal
stress in addition to tangential stress developed while in the flowing
condition.

• Production rate is inversely proportional to the viscosity of oil and directly

to the pressure of the reservoir.

• In the well, recoverability of oil with respect to water is measured by the

ratio (ξ) of viscosities of oil to water, which is
• ξ = μoil / μwater

• The lower the value of ξ, the greater the oil cut and vice versa.
 Effect of Viscosity
• This value increases with the age of the well and thus increases the
water cut in the production.

• Attempts are made to inject polymer or high viscous compounds,

which is readily soluble in water and increases the viscosity of water
in the well.

• It is common to maintain a ξ value below 3 to have a greater oil cut in

the production.
Composition of Petroleum
 Composition
• Petroleum is a complex mixture of hydrocarbons and other carbon
compounds.

• At the elemental level, it consists of carbon (84-87%) and hydrogen

(12-14%) as well as oxygen, nitrogen and sulfur (1-2%).

• The sulfur content can sometimes be up to 3-5%.

 Petroleum hydrocarbons
• There are three main groups of hydrocarbons in petroleum
• paraffinic, naphthenic and aromatic hydrocarbons.

• The paraffinic series of hydrocarbons - CnH(2n+2)

• It can be either straight chains (normal) or branched chains (isomers)

of carbon atoms.

• The lighter, straight-chain paraffins are found in gases and paraffin

waxes.
 Three main classes of hydrocarbons
• Saturated hydrocarbons contain only carbon–carbon single bonds.
• They are known as paraffins (or alkanes) if they are acyclic, or naphthenes (or
cycloalkanes) if they are cyclic.

• Unsaturated hydrocarbons contain carbon–carbon multiple bonds (double,

triple or both).
• These are unsaturated because they contain fewer hydrogens per carbon than
paraffins. Unsaturated hydrocarbons are known as olefins.

• Those that contain a carbon–carbon double bond are called alkenes, while those
with carbon–carbon triple bond are alkyenes.

• Aromatic hydrocarbons are special class of cyclic compounds related in

structure to benzene.
 Paraffinic hydrocarbons
• Examples of straight-chain paraffinic hydrocarbons are
• methane,
• ethane,
• propane,
• and butane (gases containing one to four carbon atoms, respectively),

• Pentane and hexane (liquids with five and six carbon atoms, respectively).

• The branched chain (isomer) paraffins are usually found in the heavier
fractions of crude oil.

• Paraffinic hydrocarbons are saturated compounds with all carbon bonds

saturated (i.e., the hydrocarbon chain carries the full complement of
hydrogen atoms).
 Paraffins
• Largest fraction of paraffins in the crude oil is composed of molecules from C7 to
C14.

• Methane to butane are gases, from C5 till C17 are liquids, and from C18 onwards
are solid substances.

• The solid paraffins are present in all crude oils in different amounts, often up to
5%, but in some crude oils up to 7% or even 12%.

• Solid fractions of crude oils do not only contain paraffins, but these solids are
complicated mixtures of paraffins, naphthenes, aromatics and other compounds.

• The kind and how the paraffins are present in oil (i.e. gas, solved or dispersed)
depend on the properties of the crude oil and the chemical conditions of
paraffins.
 Naphthenic or cyclic saturated hydrocarbons
• Formula - CnH2n

• All bonds of carbon with hydrogen are saturated.

• Composition in oil can vary from 25 to 75%.

• The increase in napthenic fraction increases the boiling point of crude oil.

• Monocyclic naphthenic compounds are distributed mainly in the light fractions of crude oil.

• Bicyclic naphthenes (C7 - C9) are usually used as an indication of a naphthenic crude oil.

• Activity of the naphthenic compounds is similar to the chemical activity of paraffins.

• Naphthenes are desirable compounds for the production of aromatics and good quality lube oil
base stocks.
Napthenes
 Olefins
• Olefins are unsaturated hydrocarbons, i.e., the double bond is present between two
carbon atoms.

• The generic formula is CnH2n, and the lowest member of this homologous series is
ethylene, C2H4.

• This series is known as alkenes.

• Olefins react readily with acids, alkalies, halogens, oxidizing agents, etc.

• Olefins are not present in crude oil, but they are produced by thermal and catalytic
decomposition or dehydrogenation of normal paraffins.

• Like paraffins, olefins may be straight (normal) chain or branched chain (iso-)
hydrocarbons.
 Aromatics
• Aromatics are unsaturated ring-type (cyclic) compounds that react readily
since they have carbon atoms that are deficient in hydrogen.

• All aromatics have at least one benzene ring as part of their molecular
structure.

• Aromatics may also have two or more of the ring structures fused together.

• An example of a fused double-ring aromatic compound is naphthalene.

• The highest amounts of aromatic compounds are concentrated in crude oil

fractions with high boiling temperatures.
Aromatics
 Asphaltenes and resins
• Asphaltenes and resins are dark substances (from dark red to brown).

• They are soluble in aromatic solvents but insoluble in paraffin

solvents.

• Asphaltenes have various types of hetero-atoms in their structure.

• Asphaltenes are the most complicated known compounds in crude

oil.
 Porphyrins
• Porphyrins, special nitrogen compounds of organic origin, are also
present in petroleum.
• They are believed to be formed from chlorophyll of plants and
hemoglobin of animals.
• Porphyrins can be cracked at temperatures ranging from 200 to
250°C.
 Hetro-Atoms in Crude Oil
• Common hetero atoms in hydrocarbons are sulfur, oxygen, nitrogen,
and metallic atoms.

• The amount of nitrogen in different crude oils varies from 0.02 to

1.5%.

• There are many types of nitrogen compounds in crude oil.

• Nitrogen compounds are present in crude oil mainly as cyclic

compounds
 Nitrogen Compounds
• Nitrogen compounds can be classified as
• alkaline (lye) nitrogen compounds.
• neutral nitrogen compounds.

Pyridines hinolines acredines

Examples for alkaline nitrogen compounds

 Nitrogen compounds
• The substituted anilines, amides and/or imides belong to the weak
alkaline (lye) nitrogen compounds.

• The non-substituted compounds such as indols or carbozoles are

typical nitrogen neutral compounds.

• The nitrogen compounds are very important in their role as natural

surfactants.

• For example, hinoline can prevent the corrosion of metal parts

 Oxygen compounds
• The amount of oxygen in crude oil can vary from 0.1 to 3% or even 4%.

• The amount of oxygen in crude oil fractions increases with the boiling
temperature.

• Almost similar to nitrogen compounds, the oxygen compounds can be classified

as neutral oxygen and acidic oxygen compounds.

• The cyclic and aromatic compounds, ethers, anhydrides, furans and so on usually
belong to the neutral oxygen compound class.

• The acidic oxygen compounds are usually represented by carbon acids.

 Sulfur Compounds
• Sulfur may be present in crude
oil either as
• Hydrogen sulfide (H2S), or as
mercaptans (a),
• Thiophenols (b),
• Cycloalkanethiols (c),
• Thiophenes (d),
• Benzothiophenes (e),
• Alkylbenzothiophenes (f),
• Elemental sulfur.
 Sulfur compounds
• Hydrogen sulfide is a primary contributor to corrosion in refinery
processing units.

• Other corrosive sulfur materials are elemental sulfur and mercaptans.

• The combustion of petroleum products containing sulfur compounds

produce undesirable by-products such as H2SO4 and SO2.

• Catalytic hydrotreating processes such as hydrodesulfurization remove

sulfur compounds from refinery product streams.
 Effect of Sulfur compounds
• Sharply decreases the quality of fuels and oils produced from the crude oil.

• Cause corrosion of equipment during treatment

• Reduce activity of antidetonation additives

• Antioxidizing stability of gasoline

• Raise the propensity to form hard residues in cracking gasoline fractions

• Result an environment pollution.

 Metals
• Metals (including heavy metals) have been found in all crude oils.

• Metals composition varies from 0.01 to 0.04% of crude oil.

• About thirty different metals are found in different crude oils.

• The most common are vanadium, nickel, iron, zinc, mercury, boron,
sodium, potassium, calcium and magnesium.
CRUDE CONDITIONING AND STORAGE
 Crude Oil Pretreatment
• Crude oil comes from the ground admixed with a variety of
substances: gases, water, and dirt (minerals).

• Cleanup is important if the crude is to be transported effectively and

processed without causing fouling and corrosion.

• Cleanup occurs in two ways:

• Field separation
• Crude desalting.
 Field Separation
• It is the first attempt to remove gases, water, and dirt that accompany crude oil extracted
from the ground.

• As the term implies, field separation is done onsite at the production operation.

• Raw crude oil collected from the wells contains sand, mud, and water which may vary
from 20% to 30% by volume.

• The field separator is often no more than a large vessel that gives a quieting zone to
permit gravity separation of the three phases: gases, crude oil, and water (with entrained
dirt).

• The crude oil is lighter than water, but heavier than the gases.

• Therefore, the crude oil appears within the field separator as a middle layer.
 Field Separation
• The water is withdrawn from the bottom and is disposed of at the well site.
• Water and slop (oil and water mixture) from the treatment unit is also
treated in the battery before recycling to wells.

• Gases are withdrawn from the top and piped to a natural gas processing
plant or reinjected back into the reservoir to maintain well pressure .

• Crude oil from the middle layer is pumped to the refinery or to storage to
await transportation by other methods.
 CRUDE CONDITIONING
• Gases lighter than propane have a tendency to escape.

• Propane and heavier gases are found dissolved in crude oil at

atmospheric pressure.

• Proper mixing and repeated heating above room temperature

(usually 45°C–50°C at low pressure and up to 90°C at a pressure of 2–
3 atm) and then cooling to storage temperature increases the
dissolution of gases and homogenise the layers of light and heavy
liquid hydrocarbons.
 CRUDE CONDITIONING
• Segregated wax in crude oil may choke the pipeline and pumping
equipment due to deposition.

• Heating crude with a mixing facility reduces segregation of wax by

making it uniformly distributed in the bulk.

• It can be stored and transported without risk of deposition for many

hours at room temperature or lower temperature above the pour
point.

• Asphaltic and heavy hydrocarbons with high viscosity are also mixed
up with wax.
TRANSPORTATION AND METERING OF
CRUDE OIL
 TRANSPORTATION OF CRUDE OIL
• Treated crude oil is received in
large storage tanks usually under
pressure to avoid loss of
hydrocarbon vapours.

• Despatched by tankers (ships),

trailers (large tank cars), and
most conveniently through
pipelines.

• Pipelines as long as 1000 m or

more from the oil field tanks to
the refineries or to the shipping
ports are most common in any oil-
producing country.
 CRUDE OIL RECEIVING
• In a refinery, crude oil is received and stored in a floating roof tank.

• The roof is made of compartmented deck or pontoon floating over

the oil to avoid loss of hydrocarbon vapours of dissolved hydrocarbon
gases and low boiling fractions present in crude oil.

• The floating roof also floats up and down to compensate for the
breathing operations during pumping in and out of the tank thereby
safeguarding the loss of vapours and ingress of atmospheric air into
the tank.
TRANSPORTATION OF CRUDE OIL
• Booster pumping stations are placed
at the required positions to maintain
delivery pressure to the receiving
ends.

• High pressure centrifugal or screw

pumps are employed for pumping
through pipelines.

• The horse power of such pumps may

vary from 500 to 2,000 hp with a
capacity to transport 500–1,000 m3/h
with a discharge pressure of 100 atm
or more.
TRANSPORTATION OF CRUDE OIL
• Power consumption depends pressure loss and rate of delivery, which
is ultimately determined by:

• viscosity of the oil

• roughness of the surface

• diameter and length of the pipe

• flow rate
 METERING OF CRUDE OIL
• Flow rate through a pipeline is measured by low-pressure drop flow
meters to reduce power loss.

• Ultrasonic, electromagnetic, or tracer type flow meters with signal-

generating devices.
 SAFETY ASPECTS
• Pipeline washing is carried out using
a leather or polymer ball (known as
pig) pushed by pump pressure at one
end and collected at the pig-
trapping-pit end before reaching the
suction of the booster pump.

• Pressure safety valves are located at

places to release oil or gas to prevent
damage to the pipeline during
excessive pressure rise owing to
blockage of the line for any reason.
Crude Oil Characterization
 Classification of Petroleum
• Based on the nature of HC present:
• Paraffinic crude oil (Residue left on distillation is paraffin wax)
• Napthenic crude oil (Residue left on distillation is asphalt + paraffin wax)
• Asphaltic crude oil (Residue: Asphaltic materials)
• Mixed crude oil (Contains all constituents)

• Indian Crudes are mostly mixed crude oil

• Naharkatia crude contains

• 40% Paraffins
• 25% Naphthenes
• 35 % Aromatics
 Classification of crude oil
• Paraffinic base crude (P) Residue : >5% paraffin

• Intermediate (or) mixed base crude (IN) Residue : 2-5% paraffin

• Naphthenic base crude (N) Residue : < 2% paraffins

 API (American Petroleum Institute) Gravity

Deg. API = −131.5

• SG = Specific Gravity of fraction at 15.6 deg C/15.6 deg C
• Greater the SG, lower the API gravity.
• For water API = 10.

+ +……….
• Wa= weight fraction of a component a
• (API)a= API gravity of component a
 Crude Category API Gravity

Light Crudes API>38

Medium Crudes API = 29-38

Heavy Crudes API = 8.5-29

Very Heavy Crudes API<8.5

 Lane and Garton Classification
• The basis of classification begins with two chosen fractions:

• Key fraction 1 : (Kerosene) has a high boiling range of 250 – 275C at a

pressure of 760 mm Hg.

• Key fraction 2: has a high boiling range of 275 – 300  C at a pressure

of 40 mm Hg.
 UOP Characterization Factor or Watson factor
/

• T = Average Boiling Point in K

• SG = Specific Gravity at 15.6/15.6 deg C

• 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 12.5 and above for highly paraffinic hydrocarbons.
• + +……….
 Correlation Index

• CI: 0-15 for Paraffinic crude

• CI: 15-20 for napthenic
• CI: >50 for aromatic

• The CI values are not quantitative, but the lower the CI value, the greater
the concentrations of paraffin hydrocarbons in the fraction; and

• the higher the CI value, the greater the concentrations of naphthenes and
aromatics.
Crude Oil Assay
 Assay
• The crude oil assay is a compilation of laboratory and pilot plant data that
define the properties of the specific crude oil.
• At a minimum, the assay should contain
• a distillation curve for the crude
• a specific gravity curve.
• Most assays however contain data on
• pour point (flowing criteria),
• sulfur content, viscosity,
• and many other properties.
• The assay is usually prepared by the company selling the crude oil.
• It is used extensively by refiners in their
• plant operation,
• development of product schedules,
• examination of future processing ventures.
 TBP Distillation
• Mole percentage, boiling point, specific gravity, and molecular weight of pure
components and reservoir fluid hydrocarbon fractions are used in many
correlations in the chemical and petroleum industries.

• With a true boiling point (TBP) distillation apparatus, a reservoir sample can be
heated at the respective boiling points of the normal paraffins.

• Single carbon number (SCN) fractions of sufficient quantity have to be obtained

for measuring these physical properties.

• Guidelines on the equipment required, equipment design, and operating

procedures are well documented as ASTM International standard D2892-
84(ASTM, 1984).
 TBP Distillation
• Fractions up to C12 are obtained by heating under atmospheric
pressure.

• Fractions beyond C12 and to a maximum of C29 are heated under

vacuum conditions, because heating at reduced pressures lowers the
boiling temperatures and thus prevents cracking.
 TBP Distillation- Idealized Method
• Uses a batch distillation operation that incorporates more than 100
theoretical plates and a high reflux ratio (R/P) of 100.

• 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.
https://www.e-education.psu.edu/fsc432/content/true-boiling-point-distillation-tbp
 TBP Distillation
• It is also performed in columns with 15 theoretical plates or equilibrium stages and a reflux ratio
of 5.

• Rising vapours are condensed and collected either at a constant rate of boiling points or constant
rate of the sample vaporized.

• Operation is at 760 mm Hg for boiling points below 400C.

• For higher boiling point fractions, the distillation is conducted at reduced pressures as low as 0.5
mm Hg.

• Results from vacuum operations are extrapolated to atmospheric pressure.

• The high degree of fractionation in this test gives an accurate component distribution
 TBP Distillation
• The degree of separation obtained in a TBP distillation test is much higher than that of the ASTM
distillation test.

• The temperature at which the first drop of condensate is collected is called the initial boiling
point (IBP).

• The end point (EP) is the maximum vapour temperature when almost the entire sample is
distilled (above 95%).

• Hence, its IBP is lower and its EP is higher than those of the ASTM test.

• The TBP curve (a plot of the NBP versus the percent volume of sample distilled) is usually used as
a basis for the characterization of crude oil or a petroleum product for the purpose of design and
analysis.
 ASTM Distillation
• ASTM distillation is carried out in a relatively simple apparatus.

• This type of distillation curve is used on a routine basis for plant and product quality control.

• It consists of a flask to hold the sample, which is connected to an inclined condenser to condense
the rising vapours.

• The fractions distilled are collected in a graduated cylinder.

• The temperature of the rising vapours is recorded at specific interval of the collected distillates.

• This is essentially a batch distillation with one equilibrium stage and no reflux and minimum
separation of the components of the fractions
ASTM Distillation
 ASTM Distillation
• For gasoline, kerosene, gas oil and similar light and middle distillates,
the ASTM method D86 is followed.
• This is carried out at atmospheric pressure.
• Heavy petroleum products, which tend to decompose in the D86
method but can be partially or completely vaporized at a maximum
temperature of 400 deg C and pressures down to 1 mm Hg, are
distilled using the ASTM D1160 method.

• It is carried out at pressures between 1 and 760 mm Hg.

 ASTM Distillation

• Boiling temperatures at sub-atmospheric pressures (less than 760

mm Hg) can be converted to NBPs (at 760 mm Hg) using procedure
A1.13 of API-TDB.
 ASTM Distillation
• Minimum fractionation occurs in ASTM distillation.

• Components in the mixture do not distil one by one in the order of

their boiling points.

• We get as mixtures of successively higher boiling points.

• ASTM distillations can be quickly conducted and automated, require

only a small sample, and are quite reproducible.
 ASTM to TBP
• TBP distillation is both tedious and time-consuming in comparison with the
ASTM method.

• There has been an incentive to develop correlation to convert ASTM to TBP

distillation.

• The benefit is the obtainment of detailed separation of TBP with the little
effort of the ASTM distillation.

• The equation suggested by Riazi and Daubert (1980) and published by the
API (1993) is used for the inter-conversion, referred to as API method.
 ASTM to TBP
• TBP = a(ASTM D86)b

• TBP is true boiling point temperatures at 0, 10, 30, 50, 70, 90, and 95 volume
percent distilled, in degrees Rankine.

ASTM D86 is the observed

ASTM D86 temperatures at
corresponding volume
percent distilled, in degrees
Rankine.

Average error between the

calculated and measured
TBP is in the range of 5 deg
C
 ASTM to TBP
• More recently, Daubert (1994) published a new method for
distillation curves inter-conversion using the following equations:

•The symbols T and T’ stands for ASTM D86 and TBP temperatures, respectively, both
in deg F.
•The subscripts 0 and f stand for the initial and final temperatures, respectively.
•Ai and Bi are constants. The reported average error for this method is about 3 deg C
Constants Values
•As can be seen from Figure, the
TBP distillation curve is below the
ASTM curve at volume distilled
below 50%

•Above it for volume distilled

above 50%.

•The API and Duabert’s methods

give comparable results except for
the low range, less than 10%
distilled
Equilibrium Flash Vaporization (EFV)
 Equilibrium Flash Vaporization
• Vapour and liquid are in contact at some temperature and sudden release
of pressure quickly flashes out vapor and liquid.

• By successive flash vaporization like this the crude oil can be distilled at
different increasing temperatures.

• Experimentally this is not suggested.

• 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.
Comparison
 Comparison
• 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 assay.

• 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.

 Average Boiling Points
Based on the distillation curve, five different average boiling points can
be estimated.

• Volume average boiling Point

• Weight average boiling Point
• Molal average boiling Point
• Mean average boiling Point
• Cubic average boiling Point
 Average Boiling Points

• Among these, the volume average boiling point (VABP) and the mean
average boiling points (MeABP) are the most widely used.

• The MeABP is utilized in the definition of an important parameter, the

Watson characterization factor K.

• K = (1.8T)1/3/SG
T= Average Boiling Point in K
SG = Specific Gravity at 15.6/15.6 deg C
 Volume average boiling point
• Given the ASTM D86 distillation data, the VABP can be calculated as
the average of the five boiling temperatures at 10, 30, 50, 70 and 90
percent distilled.
 MeABP
• The MeABP is calculated using the following equation:
• MeABP = VABP - 
 Volume average boiling point
TB = (T10% + T20% +T30% +T40% +T50% +T60% +T70% +T80% +T90% )/9

• If such data are not available then

TB = (T30% +T50%+T70% )/3

• All percentages are in volumes
• If the fraction is boiling over a narrow range of temperature then
VABP = T50%
 Weight and Molal Average BP
• TB = (T10% + T20% +T30% +T40% +T50% +T60% +T70% +T80% +T90% )/9
Instead of volume, weight fraction is chosen

• TB = (T1 x1+ T2 x2 +T3 x3)/ x1+x2 +x3

Where x = mole fraction, T = corresponding BP.
 Cubic average boiling point
• TB = (Va(Ta)1/3+Vb(Tb)1/3+Vc(Tc)1/3)3

• All these BP are inter-conversible.

• Inter – convertibility is possible by knowing the slope (SL) of the

distillation curve.

• Different standard plots are available for inter-conversion.

General Eqns
 MeAP Calculation
Calculate the MeABP of the petroleum fraction using given data. If the API
gravity of this fraction is 62, calculate the Watson’s characterization factor.
 Pseudo-Components
• ASTM and TBP distillation can be performed on crude oils and petroleum
products.

• The petroleum fractions are ‘‘cuts’’ from the crude oil with specific boiling
point range and with special properties such as API gravity and viscosity.

• Each of these cuts can be further defined by dividing them into narrow
boiling fractions called pseudo- (not real) components.

• For these pseudo-components, the average boiling point can be estimated

as either mid-boiling point or mid-percentage boiling point.
 Pseudo-Components
• The TBP curve is divided into an arbitrary number of pseudo-components
or narrow boiling cuts.

• The mid boiling point is the average between the IBP and the EP of that
pseudo-component.

• The mid percentage boiling point is the temperature at the arithmetic

average of the volumes distilled at IBP and EP of that pseudo-component.

• Since the boiling range is small, both mid points are close to each other
and can be considered as the VABP or the MeABP for that pseudo-
component.
 Pseudo-Components
• If the petroleum fraction contains components lighter than pentanes,
the composition of the lighter ends has to be available experimentally
through chromatographic analysis of the vapours.
 Steps Involved
• Convert ASTM D86/ASTM D1160/ASTMD2887 into TBP curve if TBP curve is not available.

• Cut the entire boiling range into a number of cut-point ranges which are used to define
pseudo-components.

• The determination of number of cuts is arbitrary.

• Estimate the density distribution of pseudo-components if only the bulk density is

available.

• Estimate the molecular weight distribution of the entire boiling range if not available and
required properties for modeling purpose
General Guidelines
Pseudo-Components
 TBP Test-Extrapolation of Data
• The maximum temperature that can be measured with TBP test is in the
range of 496–526 deg C (925–975 deg F), depending on the crude oil.

• The actual end point of the crude oil can be as high as 790 deg C (1455 F).

• This means that a substantial portion of the TBP curve is not defined by
laboratory data.

• Extrapolation of the measured portion of the TBP curve to a volume

percent approaching the end point is required.
 Extrapolation
• The TBP data can be fitted to the following generalized equation.

•The boiling point Tb is in Kelvin. xc is the cumulative weight, volume or mole

fraction.

•Tb0 corresponds to the boiling point at xc = 0. Therefore, it should be equal or

lower than the IBP given in the assay data.

•The parameters A and B are obtained by fitting the equation to available

assay data.
 Extrapolation
• Since in this equation P = as xc =1, an arbitrary point can be added
to the measured TBP data to limit the actual TBP end point.
 Fitting Procedure
• Calculate P , knowing Tb0 and plot Y versus X.

• Find out correlation parameter R2.

• If Tb0 is not known, the value of Tb0 is assumed and varied until a good
fit is obtained (R2 =0.99).

• This fitting procedure can be easily done using the linear regression fit
of a Microsoft Excel spreadsheet.
 Problem
• The following TBP data for a crude oil sample is available with an IBP
of 17 deg C. Fit the data to the generalized equation and compare
with the polynomial fit.
Thermophysical Properties Calculations
 Molecular Weight
• Any material or energy balance calculations would certainly require
the estimation of molecular weight of a petroleum fraction.

• Experimentally, the average molecular weight can be determined by

several methods, such as freezing point depression osmometry, or gel
permeation chromatography.

• Most oil fractions have molecular weights in the range of 100–700.

 Prediction of the molecular weight

•M is the molecular weight of the petroleum fraction

•Tb is the mean average boiling point of the petroleum fraction in K

•SG is the specific gravity, 60F/60  F.

 Viscosity

where 100 and  210 are the kinematic viscosities at 100 and 210 F, in
centistokes.
 Problem
Calculate the kinematic viscosities for oil which has a MeABP of 320 °C
and API gravity of 34.
 Solution
• The boiling point is 593.15 K or 1067.7 R.
• Specific gravity is 0.855.
• Watson K factor is 11.95.
• v100= 5.777 cSt and v210 = 1.906 cSt
 Pour Point
• The pour point is defined as the lowest temperature at which the
sample will flow.
• It is a rough indicator of the relative paraffinicity and aromaticity of
the crude.
• A lower pour point means that the paraffin content is low and greater
content of aromatics.

where Tp is the pour point (ASTM D 97) in kelvin, M is the molecular weight, and
v38(100) is the kinematic viscosity at 37.8°C (100F) in cSt.
 Flash Point
• Flash point TF, for a hydrocarbon or a fuel is the minimum temperature at which
vapor pressure of the hydrocarbon is sufficient to produce the vapor needed for
spontaneous ignition of the hydrocarbon with air in the presence of an external
source, i.e., spark or flame.

• From this definition, it is clear that hydrocarbons with higher vapor pressures
(lighter compounds) have lower flash points.

• Generally flash point increases with an increase in boiling point.

• Flash point is an important parameter for safety considerations, especially during

storage and transportation of volatile petroleum products (i.e., LPG, light
naphtha, gasoline) in a high-temperature environment.
 Refractive Index
• The refractive index is a readily measured property that can be used
as an input parameter for other correlations.

• It is defined as the speed of light in vacuum with respect to the speed

of light in the medium.

• Since refractive indices of petroleum fractions are not always known,

it is important to predict the refractive index.
 Refractive Index

• where a, b, c, d, e, and f are the constants varying with molecular weight range.
• n is the refractive index at 20 deg C.
• I is the Huang characterization parameter at 20 deg C.
• Tb is the mean average boiling point, in degrees Rankine.
• M is the molecular weight of petroleum fractions.
• SG is the specific gravity of petroleum fraction, 60 deg F/60 deg F.
Constants
 Molecular Type Composition of Petroleum
Fractions
• Prediction of the fractional composition of paraffins, naphthenes and
aromatics (PNA) contained in both light and heavy petroleum
fractions is possible using the following correlations.
 Ri
• Ri is the refractivity intercept as given by the equation below
Constants
Viscosity Gravity Constant
 Saybolt (SUS) Universal Viscosity
• The Saybolt (SUS) universal viscosity (V ) is related to the kinematic
viscosity () in cSt by the relation:
 Viscosity Gravity Function (VGF)
• For light fractions, M < 200, The viscosity gravity function (VGF) can
be calculated as:
 Generalized Equation for Thermo-physical
Properties
• Riazi and Al-Sahhaf (1996) presented a method for the calculation of
different properties such as:

• NBP, density, refractive index

• Critical temperature, pressure and density
• acentric factor, solubility parameter and surface tension

• given only the molecular weight

Generalized Equation
Properties can be calculated
Constants
 Problem
• Use the Riazi and Al-Sahhaf (1996) equation to calculate the
properties for an oil which has a MeABP of 320 deg C and 34 API
gravity.
Desalting of Crude Oil
 Desalting
• The crude oil contains salt in the form of dissolved salt in the tiny droplet of water
which forms a water-in oil emulsion.

• To remove the salts from the crude oil, the water-in oil emulsion has to be
broken, thus producing a continuous water phase that can be readily separated
as a simple decanting process.

• This water cannot be separated by gravity or through mechanical means.

• The salt content of the crude measured in pounds per thousand barrels (PTB) can
be as high as 2000.

• The salt content should be lowered to between 5.7 and 14.3 kg/1000m3 (2 and 5
PTB).
 Desalting
• Crude oil received in a refinery contains much water, salts, clay, and
sand, which do not settle in the tank.

• The amount of water and settleable solids present in crude oil is

indicated by bottom sediment and water (BSW) analysis.

• The presence of salts of magnesium, sodium, alkaline earth metals in

crude oil varies from crude to crude.
 Impact of Poor Desalting
• Salts in water are responsible for corrosion.

• For example, chloride salts of magnesium generate hydrochloric acid at a temperature

above 150°C and may cause severe corrosion both in the liquid and vapour phases.

• Salts deposit inside the tubes of furnaces and on the tube bundles of heat exchangers
creating fouling, thus reducing the heat transfer efficiency;

• Corrosion of overhead equipment; and,

• The salts carried with the products act as catalyst poisons in catalytic cracking units.
 Chemical Desalting
• In chemical desalting, water and chemical surfactant (deemulsifiers)
are added to the crude.

• Then it is heated so that salts and other impurities dissolve in water.

• Then the contents are held in a tank where they settle out.
 Electrical Desalting - Steps involved
• Water is mixed with the incoming crude oil in a mixing valve.

• Water dissolves salt crystals and mixing distributes salts in water uniformly
producing very tiny droplets.

• Demulsifying agents are added at this stage to aid in breaking the emulsion by
removing the asphaltenes from the surface of the droplets
 Desalting
• Heating: The crude oil temperature should be in the range of 49-55
deg C (120–130 F) since the water–oil separation is affected by
viscosity and density of the oil.

• Coalescence:
• The water droplets are so fine in diameter in the range of 1–10 micron that
they do not settle by gravity.
• Coalescence produces larger droplets that can be settled by gravity.
• This is accomplished through an electrostatic electric field between two
electrodes.
 Desalting
• The modern method of electrical desalting removes water and the
dissolved salts simultaneously from crude oil.

• Crude oil enters the bottom of a horizontal vessel provided with two
flat electrodes supplied with a very high voltage (20–33 kV AC).

• The optimum temperature for solubilising the salts to the aqueous

phase is 120°C–130°C.

• Hence crude must be preheated to this temperature before it enters

the desalter.
 Desalting
• Crude, water, and salt travel upward as an emulsified mixture and are brought in
contact with the flat electrodes.

• Droplets of water are ionised by electric charge and coalesce to form bigger
droplets of water, which then fall by gravity toward the bottom of the vessel.

• Thus, emulsion is broken as long as the crude–water mixture is in contact with

the electrodes.

• De-emulsifying agents are also injected in small amounts to break the unbroken
emulsion.

• The practice of electric desalting can reduce the salt content by 90%–98%.
 Desalter
• Single or multiple desalters in a series may be employed depending on the concentration
of salt in the incoming crude.

• At the desalting temperature, low boiling hydrocarbons may vaporise and the desalting
operation is affected.

• This also causes cavitation to the discharging pump at the exit of the desalter.

• Pressure in the drum is usually maintained at a pressure slightly above the vapour
pressure of mixed hydrocarbon gases, usually 8–10 kg/cm2 to maintain the liquid phase.

• Caustic solution is injected with the incoming crude and the pH of the aqueous phase is
monitored and controlled to maintain a pH near 7.
 Desalter Operating Variables
• Desalting temperature : typical desalting temperature can vary between 50 and 150 deg C.

• Washing water ratio: Kuwait crude (31.2 API) requires 7–8 vol% water addition relative to the
crude rate.

• Water level: If the water level gets too high and reaches the lower electrode, it shorts out the
desalter.

• Washing water injection point

• Demulsifier injection rate

• Type of washing water

• Pressure drop in the mixing valve