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Petroleum Refining

Oil History A chronology

1814 First oil well in Caldwell, Ohio
1829 Oil discovered in Burkesville KY; (50,000 bbls)
1850 Samuel Kerr distilled oil shale to produce oil
1857 E. L. Drake hired to drill for industrial oil in Pennsylvania
1866 First gusher in Texas, PA oil was about $6 a barrel
1901 Lucas Spindletop gusher near Beaumont, Texas, and Big
Oil began
1900s 1940s, oil found in many places (Louisiana, California,
Iran, Middle East)
1950s, oil and natural gas replaced coal due to the lower pollution
and ease of use; natural gas predominated

Petroleum Pathway

Petroleum Products

Petroleum or crude oil is a complex hydrocarbon mixture (mostly
gasoline) that is refined to get its constituents or feedstock for chemical
The typical fuels refinery has as a goal the conversion of as much of the
barrel of crude oil into transportation fuels as is economically practical.
Although refineries produce many profitable products, the high-volume
profitable products are the transportation fuels gasoline, diesel and
turbine (jet) fuels, and the light heating oils, and etc.

Overview (continue)
Modern refinery operations are very complex processes.
Crude oils with low API gravities (high specific gravities) and high
sulfur contents require additional hydrotreating equipment.
The quality of the product in refinery can be easily alter (to worsen
quality) if sulfur contents and densities increase.
The greater densities will mean more of the crude oil will boil above
566C (1050F).
High-boiling material or residue has been used as heavy fuel oil but
the demand for these heavy fuel oils has been decreasing because of
stricter environmental requirements.
This will require refineries to process the entire barrel of crude
rather than just the material boiling below 1050F (566C).

Processing Challenges
Sulfur restrictions on fuels (coke and heavy fuel oils)
will require extensive refinery additions and modernization and the
shift in market requirements among gasoline and reformulated fuels
for transportation will challenge catalyst suppliers and refinery
engineers to develop innovative solutions to these problems.

The environmental impacts of fuel preparation and consumption

will require that a significant shift take place in product distribution
(i.e., less conventional gasoline and more reformulated and
alternative fuels).
This will have a major effect on refinery processing operations and
will place a burden on refinery construction in addition to the need
to provide increased capacity for high sulfur and heavier crude oils.

Petroleum Refineries Block

Flow Diagram

Implementation of Technologies

Oil Refining

Crude oil contains many compounds; not homogenous. It may vary in

appearance and composition from one oil field to another.

Refining separates the various compounds by evaporation temperature

(fractional distillation).

Conversion causes chemical changes to make a different product by

recombining the molecular chains.

The refining process uses chemicals, catalyst, heat and pressure to

separate and combine the basic type of HC molecules naturally found in
crude oil into group of similar molecules.

Octane rating is percentage of Octane mixed with Heptane and

determines pre-ignition point in a standard engine (knocking is bad for
the engine).

The oil refining process starts with a fractional distillation column.

The problem with crude oil is that it contains hundreds of different HC

We have to separate the different types of hydrocarbons to have anything
useful. Fortunately there is an easy way to separate things, and this is what
oil refining is all about.

Different hydrocarbon chain lengths all have progressively higher boiling

points, so they can all be separated by distillation.

This is what happens in an oil refinery - in one part of the process, crude oil
is heated and the different chains are pulled out by their vaporization
Each different chain length has a different property that makes it useful in a
different way.
To understand the diversity contained in crude oil, and to understand why
refining crude oil is so important in our society, look through the following
list of products that come from crude oil:

Petroleum gas - used for heating, cooking, making plastics

small alkanes (1 to 4 carbon atoms)
commonly known by the names methane, ethane, propane, butane
boiling range = less than 104 degrees Fahrenheit / 40 degrees Celsius
often liquefied under pressure to create LPG (liquefied petroleum gas)

Naphtha or Ligroin - intermediate that will be further processed to make

mix of 5 to 9 carbon atom alkanes

boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees Celsius

Gasoline - motor fuel-liquid

mix of alkanes and cycloalkanes (5 to 12 carbon atoms)

boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees Celsius

Kerosene - fuel for jet engines and tractors; starting material for making other
mix of alkanes (10 to 18 carbons) and aromatics
boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees Celsius
Gas oil or Diesel distillate - used for diesel fuel and heating oil; starting material
for making other products-liquid
alkanes containing 12 or more carbon atoms
boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius
Lubricating oil - used for motor oil, grease, other lubricants liquid
long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics
boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius

Heavy gas or Fuel oil - used for industrial fuel; starting material for
making other products liquid

long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics

boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees
Residuals - coke, asphalt, tar, waxes; starting material for making
other products

multiple-ringed compounds with 70 or more carbon atoms

boiling range = greater than 1112 degrees Fahrenheit / 600 degrees
You may have noticed that all of these products have different sizes
and boiling ranges. Chemists take advantage of these properties
when refining oil.

Crude Oil is A Complex Mixture!

Crude oil range in consistency from water to
tar-like solids, and in colour from clear to
A general crude oil may contains of 84% C,
14% H, 1-3% S and N, O, metals and salts
@ <1%.
Crude oils are classified as paraffinic,
naphthenic and aromatic, based on the
predominant proportion of similar HC
Crude oils are defined @ API (American
Petroleum Institute) gravity. API, lighter
the crude and higher the value.
Crude with less sulfur Sweet. Other than
that called as sour crude.

Heavier crude contains more polycyclic aromatics

Lead to carbonaceous deposits called coke

Some crudes contain a lot of sulfur, which leads to

processing considerations.

Classification of Petroleum
The first crude oil classification is by the types of hydrocarbons
(paraffinic, naphthenic, and aromatics). This rating is important to the
refinery since the value
of the crude oil decreases
from classification 1 to 6.

Refinery Products

Knowledge of the physical and chemical properties of the petroleum products

is necessary for an understanding of the need for the various refinery processes.
Major hydrocarbons in crude oil:

Paraffin: series of HC compound having general formula CnH2n+2, i.e. straight

chains or branched chains. Paraffins from C1 to C40 usually appear in crude oil
and represent up to 20% of crude by volume.
Since Paraffins are fully saturated (no double bond), they are stable and remain
unchanged over long periods of geological time.
Examples: methane, ethane, butane, isobutane

Aromatics: unsaturated ring type (cyclic) compounds. Naphthalenes are

double-ring aromatic compounds. >3 aromatic ring are found in heavier
fractions of crude oil.

Some of the common aromatics found in petroleum and crude oils are benzene
and its derivatives with attached methyl, ethyl, propyl, or higher alkyl groups.

Examples: benzene, methylbenzene

Naphthenes: saturated hydrocarbon groupings (CnH2n), arranged in the

form of closed ring (cyclic).
Can found in all fractions of crude oil except the very lightest one.
Thermodynamic studies show that naphthene rings with five and six
carbon atoms are the most stable naphthenic hydrocarbons.

CnH2n , ringed structures with one or more
rings contain only single bonds between the
carbon atoms. Examples: cyclohexane, methyl

Low-boiling products

The compounds which are in the gas phase at ambient temperatures and
C1 is usually used as a refinery fuel, but can be used as a feedstock for hydrogen
production by pyrolytic cracking and reaction with steam.

C2 can be used as refinery fuel or as a feedstock to produce hydrogen or

ethylene, which are used in petrochemical processes.
C3 is frequently used as a refinery fuel but is also sold as a liquefied petroleum
gas (LPG).

C4 in crude oils and produced by refinery processes are used as components of

gasoline and in refinery processing as well as in LPG. nC4 has a lower vapor
pressure than iC4, and is usually preferred for blending into gasoline to regulate
its vapor pressure and promote better starting in cold weather.

On a volume basis, gasoline has a higher sales value than that of LPG, thus, it is
desirable from an economic viewpoint to blend as much normal butane as
possible into gasoline.

Most refiners produce gasoline in two or three grades, unleaded regular,
premium, and super-premium, and in addition supply a regular gasoline to
meet the needs of farm equipment and pre-1972.
The principal difference between the regular and premium fuels is the
antiknock performance.
Gasolines are complex mixtures of hydrocarbons having typical boiling
ranges from 100 to 400F (38 to 205C) as determined by the ASTM method
Components are blended to promote high antiknock quality, ease of starting,
quick warm-up, low tendency to vapor lock, and low engine deposits.

Refinery Feedstocks
The basic raw material for refineries is petroleum or crude oil,
even though in some areas synthetic crude oils from other sources
(Gilsonite, tar sands, etc.) and natural gas liquids are included in
the refinery feedstocks. The elementary composition of crude oil
usually falls within the following ranges.

The U.S. Bureau of Mines has developed a system which classifies

the crude according to two key fractions obtained in distillation:
No. 1 482 to 527F (250 to 275C) at atmospheric pressure and
No. 2 from 527 to 572F (275 to 300C) at 40 mmHg pressure.

Petroleum Standards
There are a number of international standard organizations that
recommend specific characteristics or standard measuring techniques for
various petroleum products. Some of these organizations are as follows:
1. ASTM (American Society for Testing and Materials) in the United
2. ISO (International Organization for Standardization), which is at the
international level
3. IP (Institute of Petroleum) in the United Kingdom

4. API (American Petroleum Institute) in the United States

API Gravity
Specific gravity and API gravity refer to the weight per unit volume (density) of
crude oil at 60F and 1 atm as compared to water at 60F and 1 atm. In general,
API is a measure of how heavy or light a petroleum liquid is compared to water.
Crude oil gravity may range from less than 10API to over 50API but most
crudes fall in the 20 to 45API range.
Generally, a crude with the API gravity of less than 20-22 is called heavy crude
and with API gravity of greater than 33-40 is called light crude. Similarly, if the
sulfur content of a crude is less than 0.5 wt% it is called a sweet oil.

The equation to calculate API gravity from Specific Gravity (SG) is given by:

Calculate API of a heavy oil with a specific gravity of 1.0 (i.e., with the same density as pure
water at 60 F and 1 atm, pure water density is 999.017 kg/m3)
131.5 = 10
The specific gravity is defined by the following equation:
( )
() =
2 ( )

Calculating the approximate number of barrels per metric ton for a given crude oil based on its
API gravity is given by:
Barrels of crude oil per metric ton=


For example, a metric ton of West Texas Intermediate (39.6 API) has a volume of about 7.6

Sulfur Content, wt%

Sulfur content and API gravity are two properties which have had the greatest influence
on the value of crude oil. 0.1% < S <5%.
Sour crude (>0.5%) require more extensive processing.
Pour Point, F (C)
The pour point of a liquid is the temperature at which it becomes semi solid and loses its
flow characteristics.

The pour point of the crude oil, in F or C, is a rough indicator of the relative
paraffinicity and aromaticity of the crude.

The lower the pour point, the lower the paraffin content and the greater the content of

Pour point represents the lowest temperature at which an oil can be stored and still
capable of flowing under gravity. When temperature is less than pour point of a
petroleum product it cannot be stored or transferred through a pipeline.
Carbon Residue, wt%
Carbon residue is determined by distillation to a coke residue in the absence of air.

Related to the asphalt content of the crude and to the quantity of the lubricating oil
fraction that can be recovered. In most cases the lower the carbon residue, the more
valuable the crude.

Salt Content, lb/1000 bbl

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

If the salt is not removed, severe corrosion problems may be encountered. If residue
are processed catalytically, desalting is desirable at even lower salt contents of the
Metals Content, ppm

The metals content of crude oils can vary from a few parts per million to more than
1000 ppm and, in spite of their relatively low concentrations, are of considerable

Nitrogen Content, wt%

A high nitrogen content is undesirable in crude oils because organic
nitrogen compounds cause severe poisoning of catalysts used in
processing and cause corrosion problems such as hydrogen blistering.
Crudes containing nitrogen in amounts above 0.25% by weight require
special processing to remove the nitrogen.

Cloud point is the lowest temperature at which wax crystals begin to form by a
gradual cooling under standard conditions. At this temperature the oil becomes
cloudy and the first particles of wax crystals are observed.

Low cloud point products are desirable under low-temperature conditions. Wax
crystals can plug the fuel system lines and filters, which could lead to stalling
aircraft and diesel engines under cold conditions.

Cloud points are measured for oils that contain paraffins in the form of wax and
therefore for light fractions (naphtha or gasoline) no cloud point data are
Characterization Factors

The K factor or characterization factor is a systematic way of classifying a crude

oil according to is paraffinic, naphthenic, intermediate or aromatic nature.

Reid vapor pressure (RVP)

Is the absolute pressure exerted by a mixture at 100 oF (37.8 C) as

determined by the test method ASTM-D-323 and a vapor-to-liquid
volume ratio of 4. The RVP is one of the important properties of gasolines
and jet fuels.

Distillation Range

The boiling range of the

crude gives an indication
of the quantities of the
various products present.

Distillation Data
Distillation curve
A-True Boiling Point (TBP)
A plot of the boiling point of crude oil
B- ASTM: standard test
1) D-86 for light fractions atmospheric pressure
2) D-1160 for heavier fractions (> 500oF) carried out in vacuum
C-Equilibrium Flash Vaporization (EFV)
Temperature versus the volume percent boiled off . The temperature at which a product
(or cut or fraction) begins to boil is called the initial boiling point (IBP). The
temperature at which it is 100% vaporized is the end point (EP). So every cut has two
cut points the IBP and EP.

Octane number is a parameter defined to characterize antiknock

characteristic of a fuel (gasoline and jet fuel) for spark ignition engines.
Octane number is a measure of fuel's ability to resist auto-ignition during
compression and prior to ignition. Higher octane number fuels have
better engine performance.
The octane number of a fuel is measured based on two reference
hydrocarbons of n-heptane with an assigned octane number of zero and
isooctane (2,2,4-trimethylpentane) with assigned octane number of 100.

There are two methods of measuring octane number of a fuel in the

laboratory; motor octane number (MON) and research octane number
(RON). The MON is indicative of high-speed performance (900 rpm)
and is measured under heavy road conditions (ASTM D 357). The RON
is indicative of normal road performance under low engine speed (600
rpm) city driving conditions (ASTM D 908). The arithmetic average
value of RON and MON is known as posted octane number (PON) or
Anti-Knock Index (AKI).
Isoparaffins and aromatics have high octane numbers while n-paraffins
and olefins have low octane numbers.

Generally there are three kinds of gasolines: regular, intermediate, and premium
with PON of 87, 88-90, and 91-94, respectively. Improving the octane number
of fuel would result in reducing power loss of the engine, improving fuel
economy, and a reduction in environmental pollutants and engine damage.
There are a number of additives that can improve octane number of gasoline or
jet fuels. These additives are tetra-ethyl lead (TEL), alcohols, and ethers.

For diesel engines, the fuel must have a characteristic that favors auto-ignition. The
ignition delay period can be evaluated by the fuel characterization factor called cetane
number (CN). The shorter the ignition delay period the higher CN value.

Crude Oil Assay

Distillation Analysis
Indicates the quality of the crude oil feedstock.
Based on the amount of material that boils in a particular
temperature range.
Represents expected products from crude & vacuum distillation.
Amount of data depends on laboratory analysis.

Quality Measures
Gravity, API
Characterization factor
Sulfur content, wt%
Pour point, F (C)
Carbon residue, wt%
Salt content, lb/1000 bbl
Nitrogen content, wt%
Metal content, ppm

Importance of Crude Oil Characterization

Crude grades vary considerably from each other - in yield and
properties. Crude characterization is essential to estimate feedstock
properties for refinery units, produce an optimal amount of finished
products, meet product quality specifications and to provide an
economic assessment for crude oils.
- to determine the economic
viability of new
fields / discoveries
- to assign crude value for
individual grades
- to schedule crude receipts
and determine
product yields
- to optimize refinery crude
Model Engineers
Research &
- to design equipment and
process planning

Crude Oil Distillation

Ref: R. Smith, Chemical Process Design and Integration, Wiley, 2005.

In the first stage of processing crude oil, it is distilled under conditions

slightly above atmospheric pressure. A range of petroleum fractions are
taken from the crude oil distillation.

Designs are normally thermally coupled. Most configurations follow the

thermally coupled indirect sequence as shown in Figure (a). However, rather
than build the configuration in Figure (a), the configuration of Figure (b) is
the one normally constructed. Notice that the two arrangements are


Crude Oil Distillation

Crude Oil Distillation

Unfortunately, a practical crude oil distillation cannot be operated in quite
the way shown in Figure (b), because:

Extremely high temperature sources of heat would be required. Steam

is usually not distributed for process heating at such high temperatures.

High temperatures in the reboilers would result in significant fouling

of the reboilers from decomposition of the hydrocarbons to form coke.

Therefore, in practice, some or all of the reboiling is substituted by the

direct injection of steam into the distillation. The steam is condensed in
the overhead and is separated in a decanter from the hydrocarbons.

Crude Oil Distillation

Another problem with the arrangement in
Figure (b) is that as the vapor rises up the
main column, its flow rate increases
This problem can be solved by removing
heat from the main column at intermediate
points by pumparound. This corresponds
with introducing some condensation of the
vapor at the top of intermediate columns.

Crude Oil Distillation

In a pumparound, liquid is taken from the column, sub cooled and
returned to the column at a higher point.
By choosing the most appropriate flow rate and temperature for the
pumparound, the heat load to be removed can be adjusted to whatever is
The trays between the liquid draw and return in a pumparound have more
to do with heat transfer than mass transfer. In addition to returning a sub
cooled liquid to the column, mixing occurs as material is introduced to a
higher point in the column.

Crude Oil Distillation

The crude oil entering the main column needs to be preheated to around 400
C. This is done by a furnace (fired heater). Note that this temperature is
higher than decomposition limit, but a high temperature can be tolerated in
the furnace if it is only for a short residence time.
All of the material that needs to leave as product above the feed point must
vaporize as it enters the column. In addition to this, some extra vapor over
and above this flow rate must be created that will be condensed and flow
back down through the column as reflux. This extra vaporization to create
reflux is known as overflash.

Crude Oil Distillation

The distillation of crude oil under conditions slightly above
atmospheric pressure is limited by the maximum temperature that can
be tolerated by the materials being distilled, otherwise there would be
The residue from the atmospheric crude oil distillation is usually
reheated to a temperature around 400C or slightly higher and fed to a
vacuum column, which operates under a high vacuum (about 50
mmHg) to allow further recovery of material from the atmospheric
residue, as shown in the next Figure.

Crude Oil Distillation