Origin (1): Chemistry

en.wikipedia.org/wiki/Image:Petroleum.JPG en.wikipedia.org/wiki/Image:Octane_molecule_3D_model.png

Hydrocarbon

• Oil and gas are made of a mixture of

different hydrocarbons.

• As the name suggests these are large

molecules made up of hydrogen atoms
attached to a backbone of carbon.
Crude Oil
 Origin (2): Plankton
cache.eb.com/eb/image?id=93510

Plant plankton Animal plankton

would fit on a pinhead!
10,000 of these bugs

en.wikipedia.org/wiki/Image:Ceratium_hirundinella.jpg en.wikipedia.org/wiki/Image:Copepod.

• Most oil and gas starts life as microscopic plants and animals
that live in the ocean.
 Origin (3): Blooms
serc.carleton.edu/images/microbelife/topics/red_tide_genera.v3.jpg
• Today, most plankton can be
found where deep ocean
currents rise to the surface

• This upwelling water is rich in

nutrients and causes the
plankton to bloom

• Blooms of certain plankton

called dinoflagellates may
give the water a red tinge

© Miriam Godfrey

Dinoflagellate bloom
 Origin (4): On the sea bed
upload.wikimedia.org/wikipedia/en/0/04/Plankton.jpg

When the plankton dies it rains

down on sea bed to form an
organic mush

en.wikipedia.org/wiki/Image:Nerr0328.jpg

If there are any animals on the

Sea bed sea bed these will feed on the
organic particles
 Origin (5): Black Shale
upload.wikimedia.org/wikipedia/en/0/04/Plankton.jpg
• However, if there is little or no
oxygen in the water then animals
can’t survive and the organic
mush accumulates

• Where sediment contains

more than 5% organic matter,
it eventually forms a rock
known as a Black Shale

© Earth Science World Image Bank

 Origin (6): Cooking

As Black Shale is buried, it is heated.

Organic matter is first changed by the

increase in temperature into kerogen,
Kerogen which is a solid form of hydrocarbon

Around 90°C, it is changed into a liquid

state, which we call oil
Oil

Around 150°C, it is changed into a gas

Gas

A rock that has produced oil and gas in

www.oilandgasgeology.com/oil_gas_window.jpg
this way is known as a Source Rock
Carrier beds
Oil on the move
• Oil is less dense than water
and will rise through the fluid
system of the surrounding rock
• Carrier beds are rock layers
that allow fluids to pass
through them
– Ex: Sandstone
• If petroleum stays buried, it
can become post-mature
 Origin (7): Migration
www.diveco.co.nz/img/gallery/2006/diver_bubbles.jpg • Hot oil and gas is less dense than
the source rock in which it occurs

• Oil and gas migrate upwards up

through the rock in much the same
way that the air bubbles of an
underwater diver rise to the surface

Rising oil

• The rising oil and gas eventually gets

trapped in pockets in the rock called
reservoirs
 Origin (8): Ancient Earth
© Ron Blakey, Arizona Flagstaff

• During mid-Mesozoic times

around 150 million years ago,
conditions were just right
to build up huge thicknesses
of Black Shale source rocks

Ancient Earth

The world’s main oil deposits all formed in warm shallow seas
where plankton bloomed but bottom waters were deoxygenated
Source Rocks
Organic Matter

• Sedimentary rocks rich in

organic matter
– 0.5 - 2% by weight
• Most commonly
microscopic marine
material, but it can be land
based material
• Organic material cannot
decay too much
– It has to keep its carbon
Traps
• If nothing stops oil from
rising, it will reach
surface
– Ex: The La Brea tar pits
• Traps can be rocks that
do not allow fluids to
pass through them, or
folds and faults in the
rock can trap petroleum
 Reservoir rocks
The oil needs to be trapped in a good place

• A good reservoir
rock is:
– Porous: holes
– Permeable: holes are
connected
– so that its fluids can
be produced
(removed from
them)
 EXPLORATION

• Geologic Survey
• Geophysical Surveys
1) Gravity Survey
2) Magnetic Survey
3) Seismic Survey
4) Remote Sensing

14
 Exploration and Production: Seismic
Surveys
Drill here!

Earth Science World Image Bank Image #h5inor Earth Science World Image Bank Image #h5inpj

• Seismic surveys are used to locate likely rock structures

underground in which oil and gas might be found
• Shock waves are fired into the ground. These bounce off layers
of rock and reveal any structural domes that might contain oil
 Oil and Gas fields
Oil and natural gas are produced by the same geological process according fossil
fuel suggestion: anaerobic decay of organic matter deep under the Earth's surface.
As a consequence, oil and natural gas are often found together.

In common usage, deposits rich in oil are known as oil fields, and deposits rich in
natural gas are called natural gas fields.

17
 WHAT DOES A REFINERY DO?
 Manufacturing step that converts crude oil (input) into finished product
(output). Examples of finished product:
• Motor Gasoline (Mogas)
• Jet Fuel
• Diesel Fuel
• Lubricating Oils
• Asphalt

 Consists of equipment grouped into processing blocks with supporting

facilities. Examples of processing blocks/ units:
• Pipestills
• Cat Cracker
 The Petroleum Refinery
 Amounts of each product produced depend on;

• Product demands and prices

• Nature and cost of crude oil being run
• Processing costs
• Facilities available to the refiner

 Product stored to handle seasonal fluctuations in demand

 The Petroleum Refinery
Types of Refineries

A small refinery : will take in 2000 to 10000 tons of crude oil/ day .
A large refinery : 20000 to 40000 tons/day and these are a few refineries larger than this up to 60000
tons/day.

Refineries vary in complexity ;i.e. in the variety of processes operated and of products that are sent
out.
Simple refinery : may make only gasoline, diesel fuel, and heavy fuel.
The crude oil is distilled into:
1) Gaseous hydrocarbons, which are burnt as refinery fuel
2)Light gasoline , which will need sweetening, a simple chemical treatment, and then use for
automotive use except for its low octane number.
3) Naphtha of very low octane number, perhaps 40 compared with a market of 90. It is catalytically
reformed, by which octane number of 90 to 95 can be obtained.

A simple refinery consist of a crude oil distilling unit, a gasoline sweetening unit and a catalytic
reformer. Refineries having just this usually small of 2000 to 4000 tons/day of crude oil.
Refining Processes
Crude Distillation
Crude oils are first desalted and then introduced with steam to an atmospheric
distillation column. The atmospheric residue is then introduced to a vacuum
distillation tower
Refinery Property Estimation

The following list summarizes the refinery process and product properties required
for process design calculations:

1. True boiling point curve (always given) of crude and intermediate/product streams
2. Volume (Mean) average boiling point (VABP)
3. Mean average boiling point (MEABP)
4. Weight average boiling point (WABP)
5. Molal average boiling point (MABP)
6. Characterization factor (K)
7. Vapor pressure (VP) at any temperature
8. Viscosity at any temperature
9. Average sulfur content (wt %)
10. Degree API
11. Enthalpy (Btu/lb)
12. ASTM conversion to TBP and vice‐versa
13. Viscosity of a mixture using viscosity index
14. Flash point of a mixture using flash point index
15. Pour point of a mixture using pour point index
16. Equilibrium flash vaporization curve
 Physical properties of feedstocks and products

API
API = (141.5/SG 15oF) – 131.5 The purpose of this equation was to extend the range
of the specific gravity scale. Crude oil SG changes, although small, may be
Important.
Crude Oils oAPI = 10 – 50
Higher oAPI, more paraffinic crude, higher yields of gasoline.
Lower oAPI, more aromatic crude, lower yields of gasoline.

Salt Content
Measured by ASTM – 3230 (lb NaCl/1000 bbl)
Desalting is necessary because NaCl content > 10 lbs/1000 bbl leads to corrosion
Metals
Measured by EPA Method 3040. These include Ni, V, Ag, Hg, Na, and Ca. Metals
can cause catalyst deactivation and corrosion.
Sediment and Water
Measured by ASTM D – 96 These inorganic particles can lead to operational
problems.
Acidity
Measured by ASTM – 664
Pour Point
Measured by ASTM D-97 – temperature at which oil ceases to flow. Diesel may
contain waxes, smaller than candle wax, which could solidify in cold weather.
Flash Point
Temperatures above which the oil will spontaneously combust. Fractions in vacuum
tower are the least combustible. They are the heaviest.
Vapor Pressure
Measured by ASTM D-323 Also know as Reid vapor pressure (RVP). True vapor
pressure is usually 5-9% > RVP
Carbon Residue
The solid residue (%wt) remaining after heating to coking temperatures (700-800oC)
ASTM D-524 Ramsbottom Carbon
ASTM D-189 Conradson Carbon
CCR incr. then Asphaltene incr.
 Base of crude oil

1. (Mallison classification according to residuum) a material left behind after

distillation of fractions.

Residue > 50% paraffins Paraffinic base

Residue < 20% paraffins Asphaltic base
Residue 20-50% paraffins Mixed base

2. The U .S. Bureau of Mines designated base of crude oil.

 Base of crude oil
3. Characterization Factor

The most widely used index is characterization factor (Watson, Nelson and Murphy).
It was originally defined as:
In which:

TB is the average molal / Mean boiling point (R)

S is the specific gravity at 60oF
It has since related to viscosity, aniline, temperature, molecular weight, critical
temperature, percentage of hydrocarbon etc.
K ≥ 12.15 (Paraffinic Base)
K< 11.5 (Aromatic Base)
K between 11.5-12.15 (Napthenic Base)

4. Correlation Index (C .I)

Like (C.F) related to boiling point and gravity
C.I for Parafine =0 C.I for Benzene =100
C.I =0-15 Parafine C.I =15-50 either Naphtenes or mix (Parafine Naphtenes)
C.I = above 50 Aromatic
 Base of crude oil
5. Viscosity Index: (V. I)

A series of numbers ranging from 0-100 which indicate the rate of change of
viscosity with temperature.
Paraffinic base V.I =100
Naphthenic base V.I = 40
Refinery Products
 The Petroleum Refinery
Refinery Products

Gas from petroleum is classified under several names

a) Natural gas : It is readily available in nature, in almost as a finished product. It contains mainly
methane It may be accompanied by other dry fractions like ethane and propane to a small extent. In
addition to these combustibles some inert like CO2 ,N2 , noble gases are also present. The proportion
of methane ranges from 85% to 98%.

b) Associted gas : This is obtained from oil reservoirs and this exists as a separate gas cap over liquid
phase. The proportion of CH4, C2H4 , C3H8 vary depending on reservoir conditions. When the gas phase
is taken out, it may still contain some liquid , hyrocarbons mainly of volatile range like butane and
pentane which when condensed are treated as (Natural Gasoline ).

c) Disolved gas : Gas may be present in liquid HC mainly in the dissolved state depending upon the
formation pressure. When the pressure dercreased, this dissolved gas comes out of the oil. This gas is
separated before transportation in pipe lines or tankers . The remaining is first to come out of the
distillation column because of higher temperature.
 The Petroleum Refinery
d) Refining off gas : In refinery , gas is formed in cracking and reforming operations due to the thermal
degradation of liquid hydrocarbons. During stabilization of wild gasoline or processed gasoline, the
gases are vented. This forms a major source of heat energy for refinery, as wall as feed stock for
petrochemicals. All the gases contain impurities like CO2 ,N2 , mercaptans, H2S, water vapor, suspended
impurities. First three paraffins are gases at room temperature. The mixture of methane and ethane is
called dry gas , propane and butane mixture is called wet gas.

e) Liquefied Petroleum Gas (LPG) : Propane is frequently used as LPG after being mixed with butane.
The most important property of this fuel is the vapor pressure. For factility leak detection, the gas is
mixed with small amount of odorous mercaptans.
 The Petroleum Refinery
Gasoline
Most refiners produce gasoline in two grades, regular and premium and in addition supply a low-lead
or non-lead gasoline to comply with antipollution requirements.

The principal difference between regular and premium fuels is the antiknock performance.

Gasoline is a complex mixture of hydrocarbons C4-C12 having a boiling range from 100 to 400 oF as
determined by ASTM method. Components are blended to promote :

1) high antiknock property.

2) ease of starting.
3) quick warm-up.
4) low tendency to vapor lock.
5) low engine deposits.

Normal butane is blended into gasoline to give the desired vapor pressure which is a compromise
between high RVP to improve starting characteristics and a low RVP to prevent vapor lock and reduce
evaporation losses. As butane has a high blending octane number as much as vapor pressure
limitation permits.
 The Petroleum Refinery
Reid Vapor Pressure
Reid vapor pressure (RVP) is a way to measure how quickly fuels evaporate; it's often used in determining
gasoline and other petroleum product blends. The higher a fuel's RVP, the more quickly it evaporates. The
more quickly a fuel evaporates, the more it contributes to the ozone layer. RVP represents the fuel's
evaporation at 100 degrees Fahrenheit (37.8 degrees Celsius), and is measured in pounds per square inch, or
PSIs. The property that RVP measures often is referred to as the gasoline's volatility. To obtain the RVP, a
chilled sample is placed in a special vapor chamber that is heated to 100 degrees Fahrenheit (37.8 degrees
Celsius). The reading records the observed constant pressure in the chamber. There are national industry
standards for the bath, the thermometer and the pressure monitoring device so that consistency can be
maintained among RVPs.

The RVP for gasoline should always be below 14.7 PSI, which is normal atmospheric pressure. If the RVP is
higher than 14.7 PSI, excess pressure will build up, and the fuel might boil and evaporate while in the car's
gas tank. The Environmental Protection Agency (EPA) regulates RVP for gasoline that you buy at retail gas
stations during the summer months to help reduce emissions [source: Environmental Protection Agency].
The summer generally includes the dates June 1 through September 15, except in certain areas with
extended summer seasons. The summer fuel volatility regulations exclude Alaska, Hawaii and U.S. territories,
but otherwise are outlined by state and county. During summer months, RVPs typically can go no higher than
9.0 PSI and usually are between 7.0 and 7.8 PSI in metropolitan areas. The precise regulations and amounts
on county borders are managed by regional EPA offices.

Measuring vapor pressure of gasoline also reveals the fuel's tendency to vapor lock in high operating
temperatures or at high altitudes. Vapor pressure affects starting and warm-up of car and plane engines. For
crude oils, understanding vapor pressure can help oil companies more safely gather, refine, store and
transport their products .
 The Petroleum Refinery
Gasoline specifications
The most important properties are :

1) Boiling Range :
This governs ease of starting, rate of acceleration, and tendency towards vapor lock.

Engine warm-up time is affected by the % distilled at 158oF and the 90% ASTM distillation
temperature.

Warm up is expressed in terms of the miles of operation required to develop full power without
excessive use of the choke.
 The Petroleum Refinery
Crankcase dilution is controlled by the 90% ASTM distillation temperature and is also a function of
outside temperature.

Tendency to vapor lock is directly proportional to the RVP of the gasoline.

RVP is approximately the vapor pressure of the gasoline at 100 oF in Lb/in2 absolute.

2) Antiknock Properties :
There are two types of octane numbers for gasoline engines : those determined by
- the motor method (MON)
- the research method (RON)

both methods use the same basic test engine but operate under different conditions.

The RON (ASTM D-908) represents the performance during low-speed driving when acceleration is
relatively frequent, and the MON (ASTM D-357) is a guide to engine performance and high speeds or
under heavy load conditions.

The difference between the RON & MON of gasoline is an indication of the change of performance
under both city and highway driving and is known as the "sensivity" of the fuel.
 The Petroleum Refinery
Obviously, the driver would like for the fuel to perform equally well both in the city and on the
highway, therefore low sensitivity fuels are better.

Since the posting of octane numbers on the service station pump has been required in the United
States, the posted octane number (PON) is the one most well-known by the typical driver. This is the
arithmetic average of the research and motor octane numbers [(RON + MON)/2].

In the mountain and high altitude regions, altitude affects several properties of gasoline, the most
important of which are losses by evaporation and octane requirement.

Octane number requirement is greatly affected by altitude and, for a constant spark advance, is about
three units lower for each 1000 ft (305 m) of elevation.

Octane requirements for the same model of engine will vary by 7 to 12 RON because of differences in
tune-up, engine deposits, and clearances.
 The Petroleum Refinery
Distillate Fuels
1)Jet Fuels: Commercial jet fuel is a material in the kerosene boiling range and must be clean burning.

One of the critical specification of jet fuels is its smoke point and this limits the % of cracked products high in
aromatic that can be incorporated. Specification limit the aromatic conc. to 20%. Hydrocracking saturates the
aromatics in the cracked products and raise the smoke point.
Smoke point is the maximum flame height in mm at which kerosene will burn without smoking. Generally
the more aromatic the fuel the smokier the flame. High smoke point indicate a fuel of low smoke
producing tendency.

The freeze point specification is very low (-40 oF to -58 oF) max. and hydrocracking is also used to isomerizes
paraffin and lower the freeze point. In addition the other limiting specification is flash point (110 to 150 oF).

Naphtha jet fuel is produced for military and is a wide- boiling- range stock which extends through the
gasoline and kerosene boiling range.

2) Diesel Fuels: The major performance characteristics of diesel fuels, some what in the order of importance
are : (cleanliness, ignition quality, volatility, viscosity)

No.1 diesel fuel: is generally made from virgin stocks having cetane No. above 50 . It has a boiling range from
360 to 600 oF (250 to 320 oC) and is used in high- speed engines in trucks and buses, it is called some time
super diesel.
No.2 diesel fuel : is similar to No.2 fuel oil, and has a wider boiling range (350 to 650 oF) than No.1. It is
usually contains some cracked stocks and may be blended from naphtha, kerosene , and light cracked cycle
oils.
 The Petroleum Refinery
Limiting specifications are:

Flash point ( 120 to 125 oF min.)

Dist. Range
Cetane No. (52 min.)
Pour point (-10 to +10 max.)

The ignition properties of diesel fuels are expressed in terms of cetane number which expressed the
volume % of cetane (C16H34 , high ignition quality) in a mixture with alpha-methl-naphthalene (C11H10 ,
low ignition quality).

3) Heating Oils

No.1 fuel oil is very similar to kerosene but has a higher pour point and end point.

Limiting specification are

Distillation, pour point, flash point and sulfur content.
No.2 fuel oil is very similar to No. 2 diesel fuel, contains cracked stock, and is blended from naphtha,
kerosene, diesel and cracked- cycle oils.
 The Petroleum Refinery
Limiting specification are:

Sulfur content ( 0.25 to 0.5% max. )

Pour point ( -10 to +5 max. )
Distillation
Flash point ( 120 oF min.)
Aviation Turbine Fuels , ( ATF) , Jet Fuels
Modern jet engines use fuel similar to kerosene. It is a most flexible fuel in its boiling range ( upto 300
oC )

Important properties
Pour point not higher than -30 oC
Smoke point high
Volatility
Water content
 The Petroleum Refinery
Naphtha:

These fractions are highly volatile and fall in the boiling range of motor spirits.

These are mostly used as solvents in paints, perfumery and other industries. Solvent grades are
produced by distilling wide cut naphthas into small boiling range cuts.

Naphthas are not suitable for combustion because of the rapid flame propagation, resulting in
explosions.

Kerosene
Approx. boiling point range 150-250 oC
Low viscosity
Good degree of refinement to be fairly stable.
Light in colour
Free from smoke
Used as illuminating oil and converted into aviation fuels.
 The Petroleum Refinery
Diesel Fuels

Boiling point range 250-320 oC

Mainly two types : classification of diesel oils is done according to speed and load of the engine as
1) high speed diesels
2) low speed diesels

Lube Oils

The principal source of lubricating oil is the fraction that is left after components, namely gasoline,
kerosene, diesel oil during crude distillation.
Boiling point >350 oC obtained from vacuum distillation units.

Residuum after precipitation of asphaltenes are known as bright stocks and form good source for lube
oils.
 Boiling Point Curves
ASTM distillation or TBP distillations
characterize the volatility of petroleum
fractions and crude oils.

Both are batch distillations which differ

mainly in the degree of fractionation
obtained during distillation.
 ASTM Distillation
Minimum fractionation occurs in ASTM
distillation, and components in the mixture
do not distil one by one in the order of their
boiling points, but rather as mixtures.

Nevertheless, because ASTM distillations are

quickly conducted and have been successfully
automated, require only a small sample, and
are quite reproducible, they are widely used.
ASTM Distillation
 True Boiling Point Distillation
Data from TBP distillation provides more
detailed characterization of the volatility of
crude oil or petroleum fraction.

Operation is at 760 mm Hg for boiling points

below 400 C (750 F). For higher boiling point
fractions, the distillation is conducted at
reduced pressures as low as 0.5 mm Hg.
 True Boiling Point Distillation
Because the degree of separation for a TBP
distillation test is much higher than that of
the ASTM distillation test, its IBP is lower and
its EP is higher than those of the ASTM test.
 Conversion between ASTM and TBP Distillation

Since 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 while at the same time achieving
the benefit of the detailed separation of TBP
with the little effort of the ASTM distillation.
 Riazi and Daubert Method
The following equation suggested by Riazi
and Daubert (1980) and published by the API
(1993) is used for the inter conversion,
referred to as API method:

where a and b are constants varying with

percent of liquid sample distilled
TBP is true boiling point temperatures at 0,
10, 30, 50, 70, 90, and 95 volume percent
distilled, in degrees Rankin.

ASTM D86 is the observed ASTM D86

temperatures at corresponding volume
percent distilled, in degrees Rankin. Average
error between the calculated and measured
TBP is in the range of 5 C (41 F).
 Daubert Method
More recently, Daubert (1994) published a
new method for distillation curves
interconversion using the following
equations:
The symbols T and T’ stands for ASTM D86
and TBP temperatures, respectively, both in F.

The subscripts 0 and f stand for the initial and

final temperatures, respectively.

The reported average error for this method is

about 3 C (37.4 F).
 Evaluation Of Oil Stock
Characterization Factors
There are several correlations between yield and
the aromaticity and paraffinicity of crude oils,
but the two most widely used are the UOP or
Watson ‘‘characterization factor’’ (KW) and the
U.S. Bureau of Mines ‘‘correlation index’’ (CI).
This method is for calculating the UOP
Characterization Factor of petroleum oils from
API gravity and distillation data.
The UOP Characterization Factor, commonly
called KUOP, is indicative of the general origin
and nature of a petroleum stock.
 Evaluation Of Oil Stock
Watson characterization factor:

SG: Specific Gravity at 15C (60 F)

Tb: mean average boiling point (R) (MeABP)
The Watson characterization factor ranges from less
than 10 for highly aromatic materials to almost 15 for
highly paraffinic compounds.
Crude oils show a narrower range of KW and vary
from 10.5 for a highly naphthenic crude to 12.9 for a
paraffinic base crude.
 Evaluation Of Oil Stock
Mean Average Boiling Point (R) (MeABP)
Given the ASTM D86 distillation the VABP can be calculated as the average of the
five boiling temperatures at 10, 30, 50, 70 and 90 percent distilled.

Where all temperatures are in F

The MeABP is calculated using the following equation:

 Problem

Calculate the MeABP of the petroleum fraction . If the API

gravity of this fraction is 62, calculate the Watson’s
characterization factor.
Evaluation Of Oil Stock
 Evaluation Of Oil Stock
UOP characterization factor:
KUOP has the same expression as Kw, but Tb transfer to
Volume average boiling point (VABP)
Additional notes related to the application of the above
characterization factors:
• Aromatics would have lower KUOP
• The use of boiling point indicates a relationship to the
interactive forces between the molecules.
• The use of specific gravity relates to how tightly the
molecules are packed (i.e. density)
 Evaluation Of Oil Stock

correlation index (CI)

The correlation index is useful in evaluating individual
fractions from crude oils. The CI scale is based upon
straight-chain paraffins having a CI value of 0 and
benzene having a CI value of 100. 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.
 Thermophysical Properties Calculation
1. 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 of petroleum fractions is achieved

through the following equation (Pedersen et al., 1989):
where M is the molecular weight of the petroleum fraction,
Tb is the mean average boiling point of the petroleum fraction in K,
and SG is the specific gravity, 60 F/60 F.
2. Viscosity
The following equations can be used to calculate the liquid viscosities of
petroleum fractions at atmospheric pressure and at temperatures of 37.8
C (100 F) and 98.9 C (210 F) (Pedersen et al., 1989):
1. Saybolt universal second used for oils with flowing time up to 5600 seconds
machine oil

2. Saybolt Furol seconds When the flowing time surpasses 5600 seconds, Saybolt
Furol seconds (SFS) should be used instead of Saybolt universal seconds. Saybolt
Furol seconds is measured with a controlled temperature of 50 degC.
3. 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.

The following equation may be used:

where a, b, c, d, e, and f are the constants varying with molecular weight
range (Table 3.4),

n is the refractive index at 20 C (68 F),

I is the Huang characterization parameter at 20 C (68 F),

Tb is the mean average boiling point, in degrees Rankin,

M is the molecular weight of petroleum fractions, and

SG is the specific gravity of petroleum fraction, 60 F/60 F.

 Evaluation Of Oil Stock

The following equations are used to predict the fractional composition of

paraffins, naphthenes and aromatics (PNA) contained in both light and heavy
petroleum fractions. The viscosity, specific gravity and refractive index of the
desired fraction are used as input parameters. For heavy fractions (M> 200):
 Evaluation Of Oil Stock
where a, b, c, d, e, f, g, h, and i are the constants varying with molecular weight range as
given in Table; xp, xn, and xa are the mole fraction of paraffins, naphthenes, and
aromatics, respectively; Ri is the refractivity intercept as given by the equation below

where n = refractive index at 20C (68F) and 1 atmosphere, d is the liquid density at
20C (68F) and 1 atmosphere in grams per cubic centimetre, VGC is the viscosity
gravity constant as given by equations below.

The Saybolt (SUS) universal viscosity (V ) is related to the kinematics viscosity (ν)
in cSt by the relation:
Evaluation Of Oil Stock
 Evaluation Of Oil Stock
Calculate the paraffins, naphthenes and aromatic mole fraction for the
crude which has a MeABP of 320C and API gravity of 34.

Solution:
SG = 0.855 then d = 0.855 g/cm3, n = 1.481 then Ri = 1.0535
M = 257.1 which can be considered heavy fraction n100 =5.777 cSt
then VGC = 0.8348 By substituting the constants for the heavy
fraction, Ri and VGC

xp = 0.789;
xn = 0.164 and
xa = 0.046
Evaluation Of Oil Stock
Evaluation Of Oil Stock
Problem
 Evaluation Of Oil Stock
The Bureau of Mines analysis is reported in two parts:
the first is the portion of the distillation performed at
atmospheric pressure and up to 527°F (275°C) end
point, the second at 40 mmHg total pressure to 572°F
(300°C) end point.
The portion of the distillation at reduced pressure is
necessary to prevent excessive pot temperatures,
which cause cracking of the crude oil.
The distillation temperatures reported in the analysis
must be corrected to 760 mmHg pressure. Generally,
those reported in the atmospheric distillation section
need not be corrected, but if carried out at high
elevations it may also be varied.
CH-406 : Evaluation Of Oil Stock
CH-406 : Evaluation Of Oil Stock
 Evaluation Of Oil Stock

The distillation temperatures at 40 mmHg pressure can be converted to 760 mmHg

by use of charts developed by Esso Research and Engineering Company [6]. Figure on
slide 22 shows the relationships between boiling temperatures at 40 mmHg and 760
mmHg pressure. The 572°F (300°C) end point at 40 mmHg pressure corresponds to
790°F (421°C) at 760 mmHg. Refinery crude oil distillation practices take overhead
streams with end points from 950 to 1050°F (510 to 566°C) at 760 mmHg.
The gravity mid-percent curve is plotted on the same chart with the TBP curve. The
gravity should be plotted on the average volume percent of the fraction, as the
gravity is the average of the gravities from the first to the last drops in the fraction.
For narrow cuts, a straight-line relationship can be assumed and the gravity used as
that of the mid-percent of the fraction. Smooth curves are drawn for both the TBP
and gravity mid-percent curves.
PP-407 : Basic Definitions and Correlations
 Evaluation Of Oil Stock
Cut Point:
A cut point is defined as that temperature on
the whole crude TBP curve that represents
the limits (upper and lower) of a fraction to
be produced.
 Pseudo-Components
Calculations involving crude oil and petroleum fractions require the
composition of each process stream.

Since most of the actual components are not known, the petroleum
fractions are characterized as a mixture of discrete pseudo-components
with defined boiling point ranges or cut points on the TBP distillation
curve.

Each pseudo-component corresponds to several unknown actual

compounds (e.g. paraffins, naphthenes and aromatics) which boil in a
given temperature range.

Usually each pseudo-component is characterized by an average normal

boiling point, specific gravity and molecular weight.
 CH-406 : Evaluation Of Oil Stock
Pseudo Components
Crude oil and its fractions are not expressed in
terms of pure components, but as ‘cuts’
expressed between a range of boiling points.
These ‘cuts’ are further defined by splitting them
into smaller sections and treating those sections
as though they were pure components. As such,
each of these components will have precise
properties such as specific gravity, viscosity,
mole weight, pour point, etc. These components
are referred to as pseudo components and are
defined in terms of their mid boiling point.
Evaluation Of Oil Stock
 Problem
Divide the TBP curve of the petroleum cut as calculated from API method
into 20 pseudo-components. Calculate the liquid volume percentage of
each pseudo-component.
Solution:
The TBP curve extends to 95 volume percent distilled only. In order to obtain the average
boiling point of the last cuts, the curve is extrapolated to the final point of the distillation
(100%) by fitting the curve to a suitable polynomial function and extrapolating the results.
The end point of the cut is 218.2 oC (425oF) and the IBP is -5.4oC
(22oF). Therefore each pseudo-component has a temperature
interval of (218.2+ 5.4)/20 or 11.2oC. Then the curve can be cut
as follows. The EBP of the first cut is IBP = 11.2oC or 5.8oC. The
average boiling point for the first pseudo-component is (-5.4 +
5.8)/2 or 0.2oC. The Vol% is 2.84 as read from the TBP curve. The
second cut has an end boiling point of 17oC and an end volume
percent of 6.19.
Therefore, the Vol% of this cut is 6.19 - 2.84 or 3.36 Vol%. .The
average boiling point for the second cut is (17 + 5.8) /2 or 11.4oC.
Pseudo-components
 Evaluation Of Oil Stock

Mid boiling point components

For these pseudo-components, the average
boiling point can be estimated as either mid-
boiling point or mid-percentage boiling point. 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.
 Evaluation Of Oil Stock
Mid boiling point components
In compiling the assay narrow boiling fractions
and are analyzed to determine their properties.
These are then plotted against the mid boiling
point of these fractions to produce a smooth
correlation curve. To apply these curves for a
particular calculation it is necessary to divide the
TBP curve of the crude, or fractions of the crude,
into mid boiling point components.
CH-406 : Evaluation Of Oil Stock
 Evaluation Of Oil Stock

Mid Per Cent Curves

Distillation is a means of arranging of
chemical compounds in order of their
boiling points. The properties such as color,
specific gravity, and viscosity are found to
be different for each drop or fraction of the
material distilled. The rate at which these
properties change from drop to drop may
plot as mid per cent curves.
 Evaluation Of Oil Stock
In reality, the specific gravity or viscosity of a
fraction is an average of the properties of the
many drops that constitute the fraction. If each
drop is equally different from the last drop and
from the succeeding one, then the drop that
distills at exactly half of the fraction has the
same property as the average of all the drops.
The arithmetical average of the properties of
these small fractions is the property of the total
or large fraction, or even the entire sample.
These properties are termed as Additive
properties.
 Evaluation Of Oil Stock
Integral- averaging by adding together the
properties of a series of short fractions and
dividing by number of fractions can not be used
on properties that are not additive.
Specific gravity (not API gravity) is an example of
an additive property, e. g. 10 volumes of an oil of
specific gravity 0.8 when mixed with an equal
volume of 0.9 specific gravity oil yields a mixture
that has a specific gravity 0.85.
 Evaluation Of Oil Stock

Additive Properties Non additive Properties

Boiling Point (T.B.P) API Gravity
Vapor Pressure Viscosity
Specific Gravity Color
Aniline Point Flash Point
Sulfur Content
Hydrogen/Carbon ratio
 Evaluation Of Oil Stock
Use of Gravity Mid percent curve :(Pg 106
Nelson)
Example1: Compute the SG of a 41.4 API
(0.8183 SG) mixed base crude oil from the SG
mid percent curve.
Evaluation Of Oil Stock
Evaluation Of Oil Stock
Evaluation Of Oil Stock
EFV curve is used to define temperature/pressure conditions in
distillation.
Yield Curve
Equilibrium Flash Vaporization (EFV).
The feed material is heated as it flows
continuously through a heating coil. As vapor is
formed it kept cohesively with liquid at some
temperature and a sudden release of pressure
quickly flashes or separates the vapor from the
mixture without any rectification. By successive
flash evaporation like this the stock can be
progressively distilled at different increasing
temperatures. a curve of percentage vaporized
vs. temperature may be plotted.
 Evaluation Of Oil Stock
Hempel: (Semi fractional).
It is considered as a semi-fractionating type of
distillation like Saybolt 's, Where TBP data is
insufficient , this can be used.
 Estimation of EFV Distillation Curve using
NELSON method
1. Estimate of t 50% of ASTM/ TBP using:
 Basic Definitions and Correlations
2. Estimate the 10 to 70% slope of ASTM/TBP by
using the fig. above

i.e

3. Use Fig. (5) to convert slope (ASTM/TBP) to

slope of EFV
Evaluation Of Oil Stock
Evaluation Of Oil Stock
 Estimation of EFV Distillation Curve using
MAXWELL method
A- Estimation of the straight line EFV curve:
1. Estimate of t 50% of ASTM/ TBP
2. Estimate the 10 to 70% slope of ASTM/TBP using
Slope ( ASTM / TBP ) =(𝑡70 − 𝑡10)/60
3. Use Fig. (5) to convert slope (ASTM/TBP) to slope of
EFV
4. Estimate t 50% of EFV from Fig. ( 4 )
t 50 %EFV = (DRL -FRL)
5. Draw a straight line through t50% EFV with slop of EFV.
6. t 0% ( bubble point ) = t 50 % EFV - slope*(50) EFV
7 . t 100% (dew point) = t 50 %EFV + slope*(50) EFV
Evaluation Of Oil Stock
Desalting & Dehydration
Downstream process
 Outlines
• Where is the desalter?
• What is desalting?
• what does a desalter do?
• How does a desalter work?
 What is Desalting??
• Crude oil contains water, inorganic salts, suspended
solids, and water-soluble trace metals.
• First step in the refining process is to remove salt and
solids to reduce corrosion, plugging, and fouling of
equipment and to prevent poisoning of the catalysts in
processing units.
• contaminants must be removed by desalting
(dehydration).
• If the salt content of the crude is greater than 10
lb/1000 bbl (expressed as NaCl), the crude requires
desalting to minimize fouling and corrosion caused by
salt deposition on heat transfer surfaces and acids
formed by decomposition of chloride salts.
Desalting Objectives
Where is a Desalter?
 Operation of a Desalter
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. The process is
accomplished through the following steps:

• Water washing: Water is mixed with the incoming crude oil through
a mixing valve. The water dissolves salt crystals and the mixing
distributes the salts into the water, uniformly producing very tiny
droplets. Demulsifying agents are added at this stage to aide in
breaking the emulsion by removing the asphaltenes from the
surface of the droplets.

• Heating: The crude oil temperature should be in the range of 48.9–

54.4oC (120–130oF) since the water–oil separation is affected by the
viscosity and density of the oil.
• Coalescence: The water droplets are so fine in diameter in the
range of 1–10 μm that they do not settle by gravity. Coalescence
produces larger drops that can be settled by gravity. This is
accomplished through an electrostatic electric field between two
electrodes. The electric field ionizes the water droplets and orients
them so that they are attracted to each other. Agitation is also
produced and aides in coalescence.

• Settling: According to Stock’s law the settling rate of the water

droplets after coalescence is given by

where ρ is the density m is the viscosity, d is the droplet diameter

and k is a Constant.,
• A typical desalter contains two metal electrodes as shown
in Figure, A high voltage is applied between these two
electrodes. For effective desalting the electric fields are
applied as follows:
• A high voltage field called the ‘‘secondary field’’ of about
1000 V/cm between the two electrodes is applied. The
ionization of the water droplets and coalescence takes
place here.
• A primary field of about 600 V/cm between the water–
crude interface and the lower electrode is applied. This
field helps the water droplets settle faster.
• The desalter of this design achieves 90% salt removal.
However 99% salt removal is possible with two-stage
desalters. A second stage is also essential since desalter
maintenance requires a lengthy amount of time to remove
the dirt and sediment which settle at the bottom.
Therefore, the crude unit can be operated with a one stage
desalter while the other is cleaned
two-stage desalters
 Desalter Operating Variables
For an efficient desalter operation, the following
variables are controlled:
• Desalting temperature (120-140oC)
• Washing water ratio (4-8 vol %)
• Water level
• Washing water injection point
• Demulsifier injection rate (3-10ppm Vol/Vol%)
• Type of washing water
• Pressure drop in the mixing valve
 Fractionation Towers
PROCESS DESCRIPTION
 After desalting, the crude oil is pumped through a series of
heat exchanger and its temperature raised to about 550 oF
(288 oC ) by heat exchange with product and reflux streams.
 It is then further heated to about 650 oF (399 oC ) in a furnace
(i.e. direct fired heater or "pipe still" ) and charged to flash
zone of atmospheric fractionators.
 The furnace discharge temperature is sufficiently high to cause
vaporization of all products with drawn above the flash zone
+20% of the bottom product.
 The 20% "over flash" allows some fractionation to occur on
the trays just above the flashing zone by providing internal
reflux in excess of side stream withdrawals.
 In many petroleum distillations, steam is admitted to the
space in which vaporization occurs, the steam increases
the partial pressure to make it equal to total pressure so
the boiling point of a material may be reduced. This
reduction in boiling point could be possible in only two
ways:
1) the pressure may be reduced,
2) or some inert gas such as steam may be introduced.

 The distillation causes the fractions to separate in

increasing order of boiling point. The top product being
highly volatile has to be condensed in a reflux condenser.
Some portion of the condensed fraction goes back as
reflux. All other fractions form the side draw products of
distillation column. There fractions are usually classified as
heavy naphtha, kerosene, gas oil.
Bottom product of atmospheric column is now again routed
through a furnace to reach a temperature of 350 to 400 oC
and is allowed to flash in a vacuum column, vacuum gas oil,
heavy diesel, lubrications oil cuts / pressure distillates shall
be the side cuts.
Degree of separation & Difficulty of
separation.
 FRACTIONATION
Fractionation is the difference between 5% ASTM curve of
Heavy cut and the 95 % point on the ASTM curve of a
lighter cut of two adjacent side product.
 Positive difference is called Gap.
 Negative difference is called overlap.
 ASTM Boiling range gives general composition of
fractions.
 5- 95 GAP: Defines the relative degree of separation
between adjacent fractions.
 Determined by subtracting 95 vol.% ASTM Temperature
of a fraction from the 5 Vol. % ASTM temperature of the
adjacent heavy fraction.
a gap indicating good
fractionation

some of the light product

is still in the heavier
product
 FRACTIONATION
The ability to separate the fractions efficiently decreases as the products
become heavier. Thus, one can expect an ASTM gap between the
overhead product and the first side stream to be around 25◦F, while that
between a third and fourth side stream to have an ASTM gap
around−10◦F (an overlap of 10F).

 (5-95) Gap = (t5H-T95L)ASTM

 5H=5% OF THE HEAVIER FRACTION
 95L= 95% OF THE LIGHTER FRACTION
 TBP CUT POINT = (TOH+ T100L)/2
 TBP Over lap= [T100L – TOH]
Fractionation requirements: ASTM gap and overlap

Knowing gaps as the design parameters correlate deviation or gap with F factor( product of number
of plates between two adjacent side draws off stream and internal reflux ratio.

Packie’s Method

 Degree of difficulty of separation : The difference between 50 vol.%

temperatures of the fractions under study.
 Convert 50% TBP temp to ASTM.
 Separation Capability (F):defined as the product of the reflux to feed ratio
at the upper draw tray as calculated on the volumetric basis and the number of
actual trays in that section.(F, Factor related to gap and overlap).
 Packie method: Based on Gap and overlap.
 Number of plates in particular section depends on gap and reflux ratio.
 F= Reflux ratio x Number of plates in that section.

F=(LN/DN)NT,(NT: No of trays of distillation column)L/D= Reflux ratio

 Problem

In a refinery side stream operation the fraction to

be collected is diesel. The diesel entering the side
stripper is 4000 bbl/h, the 50 percent point of the
cut is 275oC and contained with Kerosene whose
mid boiling point is 145oC. If the stripper is having 4
plates find the actual amount of diesel coming
out of the stripper if the ASTM GAP is 20oC.