Petroleum

Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology

Department of Chemical Engineering
PETROLEUM INDUSTRY
What is Petroleum?
The name petroleum covers both naturally occurring unprocessed crude oil
and petroleum products that are made up of refined crude oil.
History of Petroleum
Petroleum, in one form or another, has been used since ancient times, and
is now important to society, including in economy, politics and technology. The
rise in importance was due to the invention of the combustible engine, the rise in
commercial aviation and the importance of petroleum to industrial organic
chemistry, particularly the synthesis of plastics, fertilizers, solvents, adhesives
and pesticides.
More than 400 years ago, asphalt was used in the construction of the walls
and towers of Babylon; there were oil pits near Babylon, and a pitch spring on
Zacynthus. By 347 AD, oil was produced from bamboo-drilled wells in China.
In 1847, the process to distill kerosene from petroleum was invented by
James Young. The petroleum from which he distilled a light thin oil suitable for
use as a lamp oil, and a thicker oil suitable for lubricating machinery. In 1848,
Young set up a small business refining crude oil. Young found that by slow
distillation he could obtain multiple useful liquids from petroleum, one which he
named paraffinne oil because when congealed it resembles paraffin wax.
In 1851, the first true commercial oil-works in the world was established at
Bathgate by E.W Binney & Co. which was a partnership between Young &
Meldrum and Edward William Binney.
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Edwin Drakes 1859 well near Titusville, Pennsilvania, is popularly

considered the first modern well. Drakes well was singled out because it was
drilled, not dug; because it used a steam engine; because there was a company
associating with it; and because it exploded.
Access to oil was and still is a major factor in several military conflicts of
the twentieth century, including World War II, during which oil facilities were a
major strategic asset and were extensively bombed. The German invasion of the
Soviet Union included the goal to capture the Baku oilfields, as it would provide
much needed oil-supplies for the German military which was suffering from
blockades. Oil exploration in North America during the early 20th century later
led to the US becoming the leading producer by mid-century. As petroleum
production in the US peaked during the 1960s, however, the United States was
surpassed by Saudi Arabia and the Soviet Union.
Today, about 90 percent of vehicular fuel needs are met by oil. Petroleum
also makes up 40 percent of total energy consumption in the United States, but is
responsible for only 1 percent of electricity generation. Petroleum's worth as a
portable, dense energy source powering the vast majority of vehicles and as the
base of many industrial chemicals makes it one of the world's most important
commodities. Viability of the oil commodity is controlled by several key
parameters, number of vehicles in the world competing for fuel, quantity of oil
exported to the world market (Export Land Model), Net Energy Gain (economically
useful energy provided minus energy consumed), political stability of oil exporting
nations and ability to defend oil supply lines.
The top three oil producing countries are Russia, Saudi Arabia and the
United States. About 80 percent of the world's readily accessible reserves are
located in the Middle East, with 62.5 percent coming from the Arab 5: Saudi
Arabia, UAE, Iraq, Qatar and Kuwait. A large portion of the world's total oil exists
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as unconventional sources, such as bitumen in Canada and oil shale in

Venezuela.
What is Crude Oil?
Crude oil is unrefined liquid petroleum, which ranges in color from yellow to
black, and may have a paraffin, asphalt or mixed base. Crude oil is composed of
thousands of different chemical compounds called hydrocarbons, all with
different boiling points1.
Crude oil is generally described as sweet or sour according to its sulfur
content, and heavy or light according to its API Gravity. The API Gravity index is a
relative measure of weight-the lower the number, the heavier the material; the
higher the number, the lighter the material. While there are no exacting
definitions for these types of crudes, a general rule of thumb is:
-
Heavy crude is less than 30API, while light crude is greater than 30API.
If crude contains a sizable amount of sulfur or sulfur compounds, it is called

sour crude; if it has little to no sulfur, it is sweet crude. Sour crude may
contain 1%5% sulfur content, while sweet crudes will have less than 1%
sulfur content.
Sources of Crude Oil
1 For example, a typical crude oil may begin to boil at 104 F to produce petroleum gas
used for heating and making plastics, and finish boiling at greater than 1112 F to
produce residuals such as petroleum coke, asphalt and tar.
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Crude oil is found in geologic formations beneath the earths surface. It is formed
when large quantities of dead organisms 2 are buried underneath sedimentary rock
and subjected to intense heat and pressure.
Petroleum is recovered mostly through oil drilling. This comes after the studies
of structural geology (at the reservoir scale), sedimentary basin analysis, and
reservoir characterization.3
Oil reserves are the amount of technically and economically recoverable oil.
Reserves may be for a well, for a reservoir, for a field, for a nation, or for the world.
Different classifications of reserves are related to their degree of certainty.
The total estimated amount of oil in an oil reservoir, including both producible
and non-producible oil, is called oil in place. However, because of reservoir
characteristics and limitations in petroleum extraction technologies, only a fraction
of this oil can be brought to the surface, and it is only this producible fraction that
is considered to bereserves. The ratio of reserves to the total amount of oil in a
particular reservoir is called the recovery factor. Determining a recovery factor for a
given field depends on several features of the operation, including method of oil
recovery used and technological developments.
Based on data from OPEC4 at the beginning of 2013 the highest proved oil
reserves including non-conventional oil deposits are in Venezuela (20% of global
reserves), Saudi Arabia (18% of global reserves), Canada (13% of global reserves),
and Iran (9%). (OPEC Annual Statistical Bulletin, 2013)
2 Usually zooplankton and algae
3
Mainly in terms of the porosity and permeability of geologic structures.
4 Organization of the Petroleum Exporting Countries is an international organization and economic cartel whose mission is to coordinate the
policies of the oil-producing countries.
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Figure 1: A map of world oil reserves, 2013

Oil Refineries in the Philippines
The Philippines' downstream oil industry is dominated by three companies: Petron;
Pilipinas Shell (Royal Dutch/Shell's Philippine subsidiary); and Caltex (Philippines).
Petron
Petron is the Philippines' largest oil refining and marketing company.
Currently, the Philippine government and Saudi Aramco each own 40% of the
company, with the remaining 20% held by portfolio and institutional investors,
making it the only publicly listed firm amongst the three oil majors. Petron's
Limay, Bataan refinery has a crude processing capacity of 180,000 bbl/d.
Petron's market share as of mid-2004 was around 40%.
Pilipinas Shell
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Pilipinas Shell has a 153,000-bbl/d refinery, one of the largest foreign

investments in the Philippines, and operates some 1,000 Shell gasoline
stations.
Composition of Crude oil

There are four different types of hydrocarbon molecules that appear in crude
oil. The relative percentage of each varies from oil to oil, determining the properties
of each oil. The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and
various aromatic hydrocarbons while the other organic compounds contain nitrogen,
oxygen and sulphur, and trace amounts of metals such as iron, nickel, copper and
vanadium. The exact molecular composition varies widely from formation to
formation but the proportions of chemical elements vary over fairly narrow limits.
Composition by Weight
Hydrocarbo
Range
Average
15 60 %
30 %
30 60 %
49%
Aromatics
3 30 %
15 %
Asphaltics
remainder
6%
n
Alkanes
(paraffins)
Naphthenes
Composition by Weight
Element
Percent Range
Carbon
83 - 85 %
Hydrogen
10 14 %
Nitrogen
0.1 2 %
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Oxygen
Sulfur
Metals
0.05 1.5 %
0.05 6.0 %
< 0.1 %
Process of Extracting Crude Oil

Locating the Oil Field
Geologists use seismic surveys to search for geological structures that
may
form
oil
reservoirs.
The
"classic"
method
includes
making
an
underground explosion nearby and observing the seismic response that

provides information about the geological structures under the ground.
Drilling
The oil well is created by drilling a long hole into the earth with an oil
rig. A steel pipe (casing) is placed in the hole, to provide structural integrity to
the newly drilled well bore. Holes are then made in the base of the well to
enable oil to pass into the bore.Finally a collection of valves called a
"Christmas Tree" is fitted to the top, the valves regulate pressures and control
flow.
Oil Recovery and Extraction (Alboudwarej, 2006)
Primary recovery
During the primary recovery stage, reservoir drive comes from a
number of natural mechanisms. These include: natural water displacing
oil downward into the well, expansion of the natural gas at the top of the
reservoir, expansion of gas initially dissolved in the crude oil, and
gravity drainage resulting from the movement of oil within the reservoir
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from the upper to the lower parts where the wells are located. Recovery
factor during the primary recovery stage is typically 5-15%.
While the underground pressure in the oil reservoir is sufficient to
force the oil to the surface; all that is necessary is to place a complex
arrangement of valves (the Christmas tree) on the well head to connect
the well to a pipeline network for storage and processing. Sometimes
pumps, such as beam pumps and electrical submersible pumps (ESPs),
are used to bring the oil to the surface; these are known as artificial lift
mechanisms.
Secondary recovery
Over the lifetime of the well the pressure will fall, and at some
point there will be insufficient underground pressure to force the oil to
the surface. After natural reservoir drive diminishes, secondary
recovery methods are applied. They rely on the supply of external energy
into the reservoir in the form of injecting fluids to increase reservoir
pressure, hence replacing or increasing the natural reservoir drive with
an artificial drive. Secondary recovery techniques increase the
reservoir's pressure by water injection, natural gas reinjection and gas
lift, which injects air, carbon dioxide or some other gas into the bottom
of an active well, reducing the overall density of fluid in the wellbore.
Typical recovery factor from water-flood operations is about 30%,
depending on the properties of oil and the characteristics of the
reservoir rock. On average, the recovery factor after primary and
secondary oil recovery operations is between 35 and 45%.
Enhanced recovery
Enhanced, or Tertiary oil recovery methods increase the mobility
of the oil in order to increase extraction.
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Thermally enhanced oil recovery methods (TEOR) are tertiary

recovery techniques that heat the oil, thus reducing its viscosity and
making it easier to extract. Steam injection is the most common form of
TEOR, and is often done with a cogeneration plant. In this type of
cogeneration plant, a gas turbine is used to generate electricity and the
waste heat is used to produce steam, which is then injected into the
reservoir. This form of recovery is used extensively to increase oil
extraction in the San Joaquin Valley, which has very heavy oil, yet
accounts for 10% of the United States' oil extraction. Fire flooding (Insitu burning) is another form of TEOR, but instead of steam, some of
the oil is burned to heat the surrounding oil.
Occasionally, surfactants (detergents) are injected to alter the
surface tension between the water and oil in the reservoir, mobilizing oil
which would otherwise remain in the reservoir as residual oil.
Another method to reduce viscosity is carbon dioxide flooding.
Tertiary recovery allows another 5% to 15% of the reservoir's oil to
be recovered. In some California heavy oil fields, steam injection has
doubled or even tripled the oil reserves and ultimate oil recovery. For
example, see Midway-Sunset Oil Field, California's largest oilfield.
Tertiary recovery begins when secondary oil recovery isn't enough
to continue adequate extraction, but only when the oil can still be
extracted profitably. This depends on the cost of the extraction method
and the current price of crude oil. When prices are high, previously
unprofitable wells are brought back into use and when they are low,
extraction is curtailed.
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Figure 2: Steam Injection
Process of Refining Crude Oil

The oil refining process starts with a fractional distillation column.
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The problem with crude oil is that it contains hundreds of different types of
hydrocarbons all mixed together. You 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 temperatures. Each different chain length has a
different property that makes it useful in a different way.
In a refinery, crude is converted into finished products using rigorous
processes involving three types of operations (separation, conversion, upgrading):
Separation processes
The first stage involves separating the molecules through atmospheric
distillation (i.e. normal atmospheric pressure), according to their molecular weight.
This process, also known as topping, consists of heating the oil to 350/400C,
causing it to evaporate at the base of a 60-meter-high distillation tower.
The crude vapors rise inside the tower while the heaviest molecules, or heavy
residue, remain at the bottom without evaporating. As the vapors rise the
temperature progressively drops causing the molecules to condense into liquids, the
heaviest first followed by gases that alone reach the top of the tower, where the
temperature is now only 150C. There are outlets located at different levels to collect
these liquids, which become increasingly light up along the tower. Each outlet
corresponds to a fractional distillation, also known as a petroleum cut, beginning
with bitumen (highly viscous hydrocarbons) all the way to gases.
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The heavy residue from this distillation still contains many mid-density
products. This residue is placed in another tower and distilled again to recover
mid-range products (heavy fuel and diesel).
Conversion processes
After separation, the proportion of heavy hydrocarbons is still too high. To meet
demand for lighter products, these heavy molecules are broken up into two or more
lighter molecules. This conversion process, carried out at 500C, is also known as
catalytic cracking because it uses a catalyst (a substance that accelerates and
facilitates chemical reactions). 75% of heavy products subjected to conversion are
converted into gas, gasoline and diesel this way.
The result can be improved by adding hydrogen (hydrocracking) or using carbon
extraction methods to recover more light molecules (deep conversion). So, all heavy
hydrocarbons can be converted into light hydrocarbons but the more complex the
operation the more it costs and the more energy it uses. The ongoing aim of refiners
is to find a balance between the degree and the cost of the conversion!
Upgrading processes
These involve significantly reducing or eliminating corrosive or environmentally
harmful molecules particularly sulfur. EU sulfur emission standards are strict:
since January 1, 2009, gasoline and diesel containing more than 10 ppm (10
mg/kg) of sulfur may not be used in Europe. The purpose of these measures is to
improve the ambient air quality by optimizing the effectiveness of catalytic exhaust
gas treatment technologies. Diesel is desulfurized at 370C, at a pressure of 60 bars
and in the presence of hydrogen: under these conditions, the sulfur atoms break off
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from the hydrocarbon molecules and combine with hydrogen atoms to form
hydrogen sulfide (H2S). This is then processed to extract sulfur, a substance used in
industry.
Uses of refined petroleum products

Each refined petroleum product made from crude oil is used for a specific
purpose:
-
Petroleum gas - used for heating, cooking, making plastics

o small alkanes (1 to 4 carbon atoms)
o commonly known by the names methane, ethane, propane, butane
o boiling range = less than 104 degrees Fahrenheit / 40 degrees Celsius
o often liquified under pressure to create LPG (liquified petroleum gas)
Naphtha or Ligroin - intermediate that will be further processed to make

gasoline
o mix of 5 to 9 carbon atom alkanes
o boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees
Celsius
Gasoline - motor fuel

o liquid
o mix of alkanes and cycloalkanes (5 to 12 carbon atoms)
Celsius
Kerosene - fuel for jet engines and tractors; starting material for making other
products
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o liquid
o mix of alkanes (10 to 18 carbons) and aromatics
Celsius
Gas oil or Diesel distillate - used for diesel fuel and heating oil; starting
material for making other products
o liquid
o alkanes containing 12 or more carbon atoms
Celsius
Lubricating oil - used for motor oil, grease, other lubricants

o liquid
o long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics
Celsius
Heavy gas or Fuel oil - used for industrial fuel; starting material for making
other products
o liquid
o long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics
Celsius
Residuals - coke, asphalt, tar, waxes; starting material for making other
products
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o solid
o multiple-ringed compounds with 70 or more carbon atoms
o boiling range = greater than 1112 degrees Fahrenheit / 600 degrees
Celsius
Apart from these features and basic uses, each refinery markets its own finished
products, obtained by mixing various products and additives. Oil companies offer
a range of different fuels that are more environmentally-friendly and that ensures
engines work better and have a longer life. (Petroleum)
Figure 3: Oil Distillation

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Processing units used in refineries

Crude Oil Distillation unit: Distills the incoming crude oil into various fractions for
further processing in other units.
Vacuum distillation unit: Further distills the residue oil from the bottom of the crude
oil distillation unit. The vacuum distillation is performed at a pressure well below
atmospheric pressure.
Naphtha hydrotreater unit: Uses hydrogen to desulfurize the naphtha fraction from
the crude oil distillation or other units within the refinery.
Catalytic reforming unit: Converts the desulfurized naphtha molecules into higheroctane molecules to produce reformate, which is a component of the end-product
gasoline or petrol.
Alkylation unit: Converts isobutane and butylenes into alkylate, which is a very highoctane component of the end-product gasoline or petrol.
Isomerisation unit: Converts linear molecules such as normal pentane into higheroctane branched molecules for blending into the end-product gasoline. Also used to
convert linear normal butane into isobutane for use in the alkylation unit.
Distillate hydrotreater unit: Uses hydrogen to desulfurize some of the other distilled
fractions from the crude oil distillation unit (such as diesel oil).
Merox (mercaptan oxidizer) or similar units: Desulfurize LPG, kerosene or jet fuel by
oxidizing undesired mercaptans to organic disulfides.
Amine gas treater, Claus unit, and tail gas treatment for converting hydrogen
sulfide gas from the hydrotreaters into end-product elemental sulfur. The large
majority of the 64,000,000 metric tons of sulfur produced worldwide in 2005 was
byproduct sulfur from petroleum refining and natural gas processing plants.
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Fluid catalytic cracking (FCC) unit: Upgrades the heavier, higher-boiling fractions from
the crude oil distillation by converting them into lighter and lower boiling, more
valuable products.
Hydrocracker unit: Uses hydrogen to upgrade heavier fractions from the crude oil
distillation and the vacuum distillation units into lighter, more valuable products.
Visbreaker unit upgrades heavy residual oils from the vacuum distillation unit by
thermally cracking them into lighter, more valuable reduced viscosity products.
Delayed coking and fluid coker units: Convert very heavy residual oils into endproduct petroleum coke as well as naphtha and diesel oil by-products.
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Figure 4: Refining Process of Petroleum
LIQUEFIED PETROLEUM GAS (LPG)

Introduction:
Petroleum gas a by-product from two sources: natural gas processing and
crude oil refining is a mixture of butane, propane and ethane. The main constituent
of liquefied petroleum gas is, however, propane, propylene, butane, butylene in
various mixtures. These hydrocarbons burn readily, producing a large amount of
heat. This makes petroleum gas a very good fuel.
LPG is synthesized by refining petroleum or wet natural gas, and is usually
derived from fossil fuel sources, being manufactured during the refining of crude oil,
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or extracted from oil or gas streams as they emerge from the ground. It was first
produced in 1910 by Dr. Walter Snelling, and the first commercial products
appeared in 1912. It currently provides about 3% of the energy consumed, and
burns cleanly with no soot and very few sulfur emissions, posing no ground or water
pollution hazards. LPG has a typical specific calorific value of 46.1 MJ/kg compared
with 42.5 MJ/kg for fuel-oil and 43.5 MJ/kg for premium grade petrol (gasoline).
However, its energy density per volume unit of 26 MJ/l is lower than either that of
petrol or fuel-oil.
Large quantities of propane and butane are now available from gas and
petroleum industries. These are often employed as fuel for tractors, trucks, and
buses and mainly as a domestic fuel. They are gases under ordinary pressure.
Because of the low boiling point (-44 to 0C) and high vapor pressure of these gases,
their handling as liquids in pressure cylinders is necessary. Thus, they can be easily
liquefied under pressure. The petroleum gas, which has been liquefied under
pressure is called Liquefied petroleum gas (LPG).
Petroleum gas is supplied in liquid form so that a cylinder of even small
volume may contain an appreciable amount of the gas. A domestic gas cylinder
whose main constituent is butane, contains about 14 kg of LPG. A strong smelling
substance (Ethyl mercaptan C2H5SH) is added to LPG gas cylinders to help in the
detection of gas leakage. The gas used for domestic cooking is called Liquefied
Petroleum Gas (LPG) because it is present in liquid form in the cylinders and is
commonly used for domestic heating purposes.
Owing to demand from industry for butane derivatives, LPG sold as fuel for
automobiles is made up largely of propane. This is because,
LPG compares favorably in cost per mile.

It has a high octane rating making it useful in engines too.
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LPG leaves little or no engine deposit in the cylinders when it burns, a factor
of importance in internal combustion engines.

As it enters the engine as a vapor, it cannot wash down the cylinder walls,
remove lubricant, and increase cylinder-wall piston and piston-ring wear.
Manufacturing Process
Desalting
Crude oil introduced to refinery
processing
contains
undesirable
impurities,
many
such
as
sand, inorganic salts, drilling

mud,
polymer,
byproduct,
etc.
corrosion
The
salt
content in the crude oil varies

depending on source of the
crude oil.
When a mixture
from many crude oil sources is

processed in refinery, the salt
content can vary greatly.
The purpose of desalting is to remove these undesirable impurities, especially salts
and water, from the crude oil prior to distillation.
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The desalting process is completed in following steps:
Dilution water injection and dispersion

Emulsification of diluted water in oil
Distribution of the emulsion in the electrostatic field
Electrostatic coalescence
Water droplet settling
Crude oil passes through the cold preheat train and is then pumped to the desalters
by crude charge pumps. The recycled water from the desalters is injected in the
crude oil containing sediments and produced salty water. This fluid enters in the
static mixer which is a crude/water disperser, maximizing the interfacial surface
area for optimal contact between both liquids.
The wash water shall be injected as near as possible emulsifying device to avoid a
first separation with crude oil. Wash water can come from various sources including
relatively high salt sea water, stripping water, etc. The static mixers are installed
upstream the emulsifying devices to improve the contact between the salt in the
crude oil and the wash water injected in the line.
The oil/water mixture is homogenously emulsified in the emulsifying device. The
emulsifying device (as a valve) is used to emulsify the dilution water injected
upstream in the oil. The emulsification is important for contact between the salty
production water contained in the oil and the wash water. Then the emulsion enters
the Desalters where it separates into two phases by electrostatic coalescence.
The electrostatic coalescence is induced by the polarization effect resulting from an
external electric source. Polarization of water droplets pulls them out from oil-water
emulsion phase. Salt being dissolved in these water droplets, is also separated along
the way. The produced water is discharged to the water treatment system (effluent
water). It can also be used as wash water for mud washing process during operation.
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Gas
Separation
Liquid
fractions are
drawn from
the
trays
and
removed. In
this way the light gases, methane, ethane, propane and
butane pass out the top of the column, petrol is formed in
the top trays, kerosene and gas oils in the middle, and fuel
oils at the bottom.
The atmospheric fractionator normally contains 30 to 50
fractionation trays. Separation of the complex mixtures of crude is relatively easy
and generally 5 to 8 trays are needed for each side stream product plus the same
number above and below the feed plate.
Thus crude oil atmospheric fractionation tower with four liquid sidestream
drawoffs will require some 30 to 42 trays.
Saturate (sat) Gas Plants

Saturate (sat) gas plants separate refinery gas components including butanes
for alkylation, pentanes for gasoline blending, LPG's for fuel, and ethane for
petrochemicals. Because sat gas processes depend on the feedstock and product
demand, each refinery uses different systems, usually absorption-fractionation or
straight fractionation. In Absorption-fractionation, gases and liquids from various
refinery units are fed to an absorber-deethanizer where C2 and lighter fractions are
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separated from heavier fractions by lean oil absorption and removed for use as fuel
gas or petrochemical feed. The heavier fractions are stripped and sent to a
debutanizer, and the lean oil is recycled back to the absorber-deethanizer. C3/C4 is
separated from pentanes in the debutanizer, scrubbed to remove hydrogen sulfide,
and fed to a splitter where propane and butane are separated. In fractionation sat
gas plants, the absorption stage is eliminated.
Polymerization
Polymerization in the petroleum industry is the process of converting light
olefin gases including ethylene, propylene, and butylene into hydrocarbons of higher
molecular weight and higher octane number. Polymerization combines two or more
identical olefin molecules to form a single molecule with the same elements in the
same proportions as the original molecules. Polymerization may be accomplished
thermally or in the presence of a catalyst at lower temperatures.
The olefin feedstock is pretreated to remove sulfur and other undesirable
compounds. In the catalytic process the feedstock is either passed over a solid
phosphoric acid catalyst or comes in contact with liquid phosphoric acid, where an
exothermic polymeric reaction occurs. This reaction requires cooling water and the
injection of cold feedstock into the reactor to control temperatures between 300 and
450 F at pressures from 200 psi to 1,200 psi.
Treating and Blending
The refined gas was treated and blended with merox to form the final product,
the LPG. Merox is an acronym for mercaptan oxidation. It is a proprietary catalytic
chemical process developed by UOP used in oil refineries and natural gas processing
plants to remove mercaptans from LPG.
GASOLINE
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Gasoline is refined from crude oil. It is a refined product of petroleum

consisting of a mixture of hydrocarbons, additives and blending agents. Its
composition varies widely, depending on the crude oil used, the refinery processes
available, the overall balance of product demand, and the product specifications.
According to the International Agency for Research on Cancer in 1989, the
typical composition of gasoline hydrocarbons is as follows: 4-8 % by volume alkanes,
2-5% alkenes, 25-40% isoalkanes, 3-7% cycloalkanes, 1-4% cycloalkenes, and 2050% total aromatics (0.5-2.5% benzene). Additives and blending agents are added to
the hydrocarbon mixture to improve the performance and stability of gasoline. At the
end of the production process, finished gasoline typically contains more than 150
separate compounds.
Gasoline is mainly used as a fuel for internal-combustion engines. It is
sometimes used as a solvent for oils and fats. Gasoline became the preferred
automobile fuel because of its high energy of combustion and its capacity to mix
readily with air in a carburetor.
Gasoline should:
Enable good engine performance - this is achieved by controlling octane

number and volatility.
Allow engines to start and run well in cold or hot weather - this is achieved by
controlling volatility.
Let engines run reliably and efficiently for a long time - this is achieved by
controlling stability and corrosiveness, and the tendency of the gasoline to
form residues and deposits in engines and fuel systems.
Limit evaporative and exhaust emissions for environmental and health

reasons - this is achieved by controlling volatility, total aromatics and olefins,
and by efficient fuel vehicle technology.
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Be removed of unnecessary health risks - this is achieved by limiting benzene

content, blending components like MTBE, and additives like lead or
manganese.
Able to benefit from new engine and emissions control technologies - this is
achieved by limiting sulfur content and controlling octane number and
volatility.
What is Octane Rating

The octane rating of gasoline refers to its resistance to pre-ignition knocking
and pinging. Knocking and pinging are caused by abnormal combustion of the fuel
in the cylinder causing an extreme rise in cylinder pressure. This abnormal chamber
event produces an undesirable and destructive phenomenon also known as
detonation or pre-ignition.
Gasoline is classified by its octane rating. The higher the octane rating
number, the greater resistance to auto-ignition or knock the fuel has. Fuels with an
antiknock index of 87 are regular grade gasoline; 89 are midgrade; and 91 or higher
are high octane gasoline.
History of Gasoline Refinery
In the 19th century, fuels for the automobile were coal tar distillates and the
lighter fractions from the distillation of crude oil. On September 5, 1885, the first
gasoline pump was manufactured by Sylvanus Bowser of Fort Wayne, Indiana and
delivered to Jake Gumper, also of Fort Wayne. The gasoline pump tank had marble
valves and wooden plungers and had a capacity of one barrel. On September 6,
1892, the first gasoline-powered tractor, manufactured by John Froelich of Iowa, was
shipped to Langford, South Dakota, where it was employed in threshing for
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approximately 2 months. It had a vertical single-cylinder gasoline engine mounted

on wooden beams and drove a J. I. Case threshing machine. Froelich formed the
Waterloo Gasoline Tractor Engine Company, which was later acquired by the John
Deere Plow Company.
By the early 20th century, the oil companies were producing gasoline as a
simple distillate from petroleum. During the 1910s, laws prohibited the storage of
gasoline on residential properties. On January 7, 1913, William Meriam Burton
received a patent for his cracking process to convert oil to gasoline. On January 1,
1918, the first U.S. gasoline pipeline began transporting gasoline through a three
inch
pipe
over
40
miles
from
Salt
Creek
to
Casper,
Wyoming.
Charles
Kettering modified an internal combustion engine to run on kerosene. However,

kerosene fueled engine knocked and would crack the cylinder head and pistons.
Thomas Midgley Jr. discovered that the cause of the knocking was from the kerosene
droplets vaporizing on combustion. Anti-knock agents were researched by Midgley,
culminating in tetra ethyl lead being added to fuel. On February 2, 1923, for the first
time in U.S. history ethyl gasoline was marketed. This took place in Dayton, Ohio. In
1923, Almer McDuffie McAfee developed the petroleum industry's first commercially
viable catalytic cracking process, a method that could double or even triple the
gasoline yielded from crude oil by then-standard distillation methods. By the mid1920s, gasolines were 40 - 60 Octanes. By the 1930s, the petroleum industry
stopped using kerosene. Eugene Houdry invented the catalytic cracking of low-grade
fuel into high test gasoline in 1937. During the 1950s, the increase of the
compression ratio and higher octane fuels occurred. Lead levels increased and new
refining processes (hydrocracking) began. In 1960, Charles Plank and Edward
Rosinski patented (U.S. #3,140,249) the first zeolite catalyst commercially useful in
the petroleum industry for catalytic cracking of petroleum into lighter products such
as gasoline. In the 1970s, unleaded fuels were introduced. From 1970 until 1990
Petroleum 2
6

lead was phased out. In 1990, the Clean Air Act created major changes on gasoline,
rightfully intended to eliminate pollution.
Raw Materials
Crude Oil
Additives
Additive
Anti-knocking agents
Anti-oxidants
Metal deactivators
Deposit modifiers
Surfactants
Freezing point
depressants
Function
Example
Improve octane ratings Tetraethyllead,
and
reduce
engine Methylcyclopentadienyl
knocking
manganese
tricarbonyl
(MMT),
Ferrocene,
Toluene, Isooctane
Inhibit gum formation Butylated
and improve stability
hydroxytoluene,
Ethylene diamine, pPhenylenediamine, 2,6Di-tert-butylphenol
Inhibit gum formation N,N-Disalicylidiene-1,2and improve stability
propanediamine,
Benzotriazole
Reduce deposits, spark- Ethylene dichloride,
plug fouling and preignition
Prevent icing, improve Long
chain
of
vaporization,
inhibit alkyldiamines,
deposits, reduce nitrate Alkylsuccinimides
of
emissions
diethylenetriamine
Prevent icing
T-Butanol
Petroleum 2
7

Corrosion inhibitors
Dyes
Prevent
gasoline DCI-4A, DCI-6A
corroding storage tanks
Product color for safety, Solvent Red 24, Solvent
or regulatory purposes
Red 26, Solvent Yellow
124, Solvent Blue 35
Manufacturing Process of Gasoline

1. Distillation
Modern distillation involves pumping oil through pipes in hot furnaces and
separating light hydrocarbon molecules from heavy ones in downstream distillation
towers the tall, narrow columns that give refineries their distinctive skylines.
During this process, the lightest materials, like propane and butane, vaporize
and rise to the top of the first atmospheric column. Medium weight materials,
including gasoline, jet and diesel fuels, condense in the middle. Heavy materials,
called gas oils, condense in the lower portion of the atmospheric column. The
heaviest tar-like material, called residuum, is referred to as the "bottom of the
barrel" because it never really rises.
This distillation process is repeated in many other plants as the oil is further
refined to make various products.
In some cases, distillation columns are operated at less than atmospheric
pressure (vacuum) to lower the temperature at which a hydrocarbon mixture boils.
This "vacuum distillation" (VDU) reduces the chance of thermal decomposition
(cracking) due to overheating the mixture.
Petroleum 2
8

Cracking
Since
the
marketplace
establishes
product value, our competitive edge depends on
efficiently we can convert middle distillate, gas
residuum into the highest value products.
Heat and catalysts are used to convert
heavier oils to lighter products using three
"cracking" methods: fluid catalytic cracking
hydrocracking (Isomax), and coking (or
thermal-cracking).
2.
how
oil and
the
(FCC),
The Fluid Catalytic Cracker (FCC) uses high temperature and catalyst to crack
86,000 barrels (3.6 million gallons) each day of heavy gas oil mostly into gasoline.
Hydrocracking uses catalysts to react gas oil and hydrogen under high pressure and
high temperature to make both jet fuel and gasoline. Also, about 58,000 barrels (2.4
million gallons) of lighter gas oil is converted daily in two Isomax Units, using this
hydrocracking process.
Petroleum 2
9

3. Alkylation
While the cracking processes break most of the gas oil into gasoline and jet
fuel, they also break off some pieces that are lighter than gasoline. This process
takes the small molecules and recombines them in the presence of sulfuric acid
catalyst to convert them into high octane gasoline.
4. Treating (Removing Impurities)

The products from the Crude Units and the feeds to other units contain some
natural impurities, such as sulfur and nitrogen. Using a process called
hydrotreating (a milder version of hydrocracking). these impurities are removed to
reduce air pollution when our fuels are used.
In the RDS Unit's six 1,000-ton reactors, sulfur and nitrogen are removed
from FCC feed stream. The sulfur is converted to hydrogen sulfide and sent to the
Sulfur Unit where it is converted into elemental sulfur. Nitrogen is transformed into
ammonia which is removed from the process by water-washing. Later, the water is
treated to recover the ammonia as a pure product for use in the production of
fertilizer.
The RDS's Unit main product, low sulfur vacuum gas oil, is fed to the FCC
(fluid catalytic cracker) Unit which then cracks it into high value products such as
gasoline and diesel.
Petroleum 3
0

5. Reforming
Octane rating is a key measurement of how well a gasoline performs in an
automobile engine. Much of the gasoline that comes from the Crude Units or from
the Cracking Units does not have enough octane to burn well in cars.
The gasoline process streams in the refinery that have a fairly low octane
rating are sent to a Reforming Unit where their octane levels are boosted. These
reforming units employ precious-metal catalysts - platinum and rhenium and
thereby get the name "rheniformers." In the reforming process, hydrocarbon
molecules are "reformed" into high octane gasoline components. For example, methyl
cyclohexane is reformed into toluene.
The reforming process actually removes hydrogen from low-octane gasoline.

The hydrogen is used throughout the refinery in various cracking (hydrocracking)
and treating (hydrotreating) units.
6. Blending
A final and critical step is the blending of our products. Gasoline, for example,
is blended from treated components made in several processing units. Blending and
Shipping Area operators precisely combine these to ensure that the blend has the
right octane level, vapor pressure rating and other important specifications. All
products are blended in a similar fashion. Among the variables that determine the
Petroleum 3
1

blend are octane level, vapor pressure ratings, and other special considerations,
such as whether the gasoline will be used at high altitudes. Technicians also add
patented performance additives, and dyes to distinguish the various grades of fuel.
KEROSENE
Kerosene, also spelled kerosine, also called paraffin oil or coal oil is a
flammable yellow to colorless oily liquid with a not-unpleasant
smell. While can be extracted from coal or shale, kerosene is
primarily derived from petroleum. It is a distillate of petroleum
with boiling points ranging from 150 to 300 OC (300 to 575OF),
and therefore classified as so-called middle distillates along with
diesel oil. It primarily consists of mixtures of hydrocarbons with
12-15 carbon atoms. Kerosene is used as fuel for lamps,
furnaces, cooking stoves and jet engines, as a solvent for greases and also as an
insecticide.
History
1846 A Canadian geologist and doctor named Abraham Gesner first

discovered a liquid that gives a beautiful flame by extraction from shale oil
that he named kerosene, contraction of the Greek word keroselaion meaning
wax oil.
1848 James Young, a Scottish chemist who experimented and discovered dry
distillation of boghead oil that produces various products including the one he
called the paraffin oil.

1850 Young patented his process and build a his own commercial oil-works
in Bathgate in 1851.
1851 Samuel Martin Kier began selling kerosene to local miners, under the
name of Carbon Oil.
Petroleum 3
2

Mid 1850s Kerosene was used as a fuel for lamps but kerosene was then a
very expensive commodity was only used in many public venues and homes of
wealthy.
1860 Oil wells were discovered in Northwestern Pennsylvania and
Southwestern Ontario and that began the mass production of kerosene that
makes it inexpensive and available for many people.

Mid-19th Century Kerosene was used in almost every establishment
including hospitals, stores, homes, offices, factories, etc. as a fuel for lamps
and furnaces.
Late 1890s and early 1900s Kerosene became the most important refinery
product.
1920 Kerosene surpassed gasoline as a fuel for internal combustion engine.
Raw Materials
Petroleum/ Crude Oil
Kerosene is extracted from petroleum chemicals found deep within the earth.
This mixture of petroleum chemicals is consists of oil, rocks, water and other
subterranean contaminants in the reservoir of sandstone and carbonate rocks. The
oil itself (crude oil) is come from decayed organisms of buried along with the
sediments of prehistoric eras. Over ten millions of years, organic residues came from
these organisms were converted into petroleum by means of chemical processes
called diagenesis and catagenesis. Diagenesis occurs on temperature below 122 OF
(50OC) that involves both microbial activity and chemical reactions such as
dehydration, condensation, cyclization and polymerization. Catagenesis occurs with
temperature
between
122OF
and
393OF
(50OC
and
200OC)
that
involves
thermocatalyctic cracking, decarboxylation and hydrogen disproportion.

Caustic Soda (Sodium Hydroxide)
Petroleum 3
3

Sodium hydroxide is a white, deliquescent, brittle strong solid alkali used in

many industrial productions including soap and paper manufacturing. In kerosene
production, it is used as a sweetening or detoxification agent of the said petroleum
product.
Manufacturing Process
Preparation of Raw Materials
Crude Oil Recovery

The first step in kerosene production
is to collect the crude oil. Since crude
oil found beneath the earth surface,
there
are
three
ways
of
drilling
operations that bring the oil to the

surface. One method is the cabletooled drilling that uses jackhammer
chisel that dislodge the rocks and dirt to create tunnel to the oil well. Second
process, rotary drilling that digs deeper to the oil reservoir by sinking a drill
pipe with rotating steel bits to pulverize rocks. The third is the off-shore
drilling that uses large ocean-borne platform that lowers the shaft to the
ocean floor.
Flushing
Once the drilling process breaks the reservoir, crude oil erupts from the
ground by the force of hydrocarbon gas. Flushing is done to have more to have
more oil recovery from beneath by pumping water into the well to push the oil
out. Addition of surfactant to the water will create higher recovery of oil. Water
is separated from oil after washing.
The oil obtained are now stored in tanks then delivered to refinery.
Petroleum 3
4

Separation
Distillation
Distillation is a process of separation of components of
crude oil by means of the difference of boiling points
among the components. The stream of crude oil is sent
to the bottom of the distillation column where it is
heated to vapor. Lighter hydrocarbons rise to the top of
the column and most of the high-boiling point
fractions are left at the bottom. The fraction condensed
and collected having the boiling points 302OF to 482OF
(150OC to 200OC) is the kerosene. To achieve higher
purity, refluxing or recycling of kerosene multiple times is done.
Petroleum 3
5

Purification
Merox (Mercaptan Oxidation)

Merox, the contraction of mercaptan oxidation, or in less technical term, the
sweetening is a catalytic chemical process to purify kerosene by removal of
sulfurous contaminants including H2S and mercaptan (thiol) by reaction of
Petroleum 3
6

kerosene
containing
in
an
caustic
alkaline
soda
environment,
(NaOH).
This
process was invented and developed by UOP

(Universal Oil Products), a multi-national
company developing oil refining and gas
processing and petroleum production.
1. Prewashing
The process operation starts with the water coalescence or the formation of
drain water layer from the aggregation of natural water droplets from
Petroleum 3
7

kerosene. Kerosene will then undergo caustic prewashing or the addition of

NaOH to disintegrate hydrogen sulfide.
2. Oxidation
The washed kerosene is now fed to the Merox reactor together with
compressed air. This is where the mercaptan oxidation occurs as the
mercaptan percolates over the catalyst bed consists of carbon granules
impregnated with UOP proprietary catalyst. The resulting product of the
reaction will now flow to the caustic settler where it forms the bottom layer of
caustic solution and the top layer of sweetened oil. Caustic solution remains
at the bottom and then returned back to the reactor to maintain alkaline
environment.
3. Post-Treatment
The water-insoluble product will now go to the water wash tank to remove
remaining caustic traces and other water-soluble contaminants, next is the
flowing of oil to the salt bed to eliminate entrained water and finally through a
clay bed to remove oil-soluble impurities, organometallic compounds and
particulates.
Final Processing
Packaging
Once the kerosene is fully refined, they are now placed in metal drums, tanks
or opaque plastic container and are now ready for shipment. Careful handling
is very necessary since the kerosene is highly flammable.
Quality Control
Testing the amount of unwanted components or hydrocarbons is conducted.
The result of the analysis of kerosene tells the efficiency of extraction and
distillation. Refluxing or repeated recycle of kerosene fraction helps to maximize the
Petroleum 3
8

yield of kerosene from distillation. Recycling of petroleum waste in the reaction in

distillation can optimize production.
REFERENCES
Alboudwarej.
(2006).
Highlighting
Heavy
Oil.
Retrieved
from
http://www.slb.com/~/media/Files/resources/oilfield_review/ors06/sum06/heavy_
oil.ashx
OPEC Annual Statistical Bulletin. (2013). Retrieved September 11, 2014, from OPEC
website: http://www.opec.org/opec_web/en/data_graphs/330.htm
Petroleum.
(n.d.).
Retrieved
September
http://en.wikipedia.org/wiki/Petroleum
Osha.
(2006).
Polymerization
in
11,
petroleum
2014,
refining.
from
Wikipedia:
Retrieved
from
http://www.eoearth.org/view/article/155306/
Binod Shrestha. (2005). Hydrocarbon from petroleum. Retrieved from http://chemguide.blogspot.com/2010/04/hydrocarbon-from-petroleum.html
Jrank.
(2003).
Kerosene.
Retrieved
from
http://www.madehow.com/Volume-
7/Kerosene.html.
Ali, M., et al. (2005). Handbook of industrial chemistry. USA: McGraw-Hills
Companies Inc.
Austin, G. (1984). Shreve's chemical process industries. USA: McGraw-Hills
Companies Inc.
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9

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Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology

Pamantasan ng Lungsod ng Maynila

Edwin Drakes 1859 well near Titusville, Pennsilvania, is popularly

Pamantasan ng Lungsod ng Maynila

as unconventional sources, such as bitumen in Canada and oil shale in

If crude contains a sizable amount of sulfur or sulfur compounds, it is called

Sources of Crude Oil

Pamantasan ng Lungsod ng Maynila

Mainly in terms of the porosity and permeability of geologic structures.

Pamantasan ng Lungsod ng Maynila

Figure 1: A map of world oil reserves, 2013

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Pilipinas Shell has a 153,000-bbl/d refinery, one of the largest foreign

Composition of Crude oil

Pamantasan ng Lungsod ng Maynila

Process of Extracting Crude Oil

underground explosion nearby and observing the seismic response that

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

Thermally enhanced oil recovery methods (TEOR) are tertiary

Pamantasan ng Lungsod ng Maynila

Figure 2: Steam Injection

Process of Refining Crude Oil

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

Uses of refined petroleum products

Petroleum gas - used for heating, cooking, making plastics

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

Gasoline - motor fuel

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Lubricating oil - used for motor oil, grease, other lubricants

Pamantasan ng Lungsod ng Maynila

Figure 3: Oil Distillation

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Processing units used in refineries

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Figure 4: Refining Process of Petroleum

LIQUEFIED PETROLEUM GAS (LPG)

Pamantasan ng Lungsod ng Maynila

LPG compares favorably in cost per mile.

Pamantasan ng Lungsod ng Maynila

of importance in internal combustion engines.

sand, inorganic salts, drilling

content in the crude oil varies

from many crude oil sources is

Pamantasan ng Lungsod ng Maynila

The desalting process is completed in following steps:

Dilution water injection and dispersion

Pamantasan ng Lungsod ng Maynila

Saturate (sat) Gas Plants

Pamantasan ng Lungsod ng Maynila

Pamantasan ng Lungsod ng Maynila

Gasoline is refined from crude oil. It is a refined product of petroleum

Enable good engine performance - this is achieved by controlling octane

Limit evaporative and exhaust emissions for environmental and health

Pamantasan ng Lungsod ng Maynila

Be removed of unnecessary health risks - this is achieved by limiting benzene

What is Octane Rating

Pamantasan ng Lungsod ng Maynila

approximately 2 months. It had a vertical single-cylinder gasoline engine mounted