Fundamental of

Petroleum

Diah Agustina Puspitasari, ST., MT

Chemical Engineering Department
Engineering Faculty
Brawijaya University

Indonesians Energy

Composition of Crude Oil

Oil and gas are made of a mixture of different
hydrocarbons (C : 85-90%; H : 10-14%)
Non hydrocarbon element : 0.2-3 %
Nitrogen : < 0.1-2 %
Oxygen : 1-1.5 %
As the name suggests these are large molecules made
up of hydrogen atoms attached to a backbone of carbon.

Hydrocarbon Group
Paraffin is a compound where all four bonds of a
carbon atom are linked to four separate atoms.
They carry out substitution reactions slowly with
chlorine in sunlight and with bromine in the
presence of a catalyst.
Paraffins are available both as normal and isoparaffin. Normal paraffins are straight chain
compounds and iso-paraffins are branched
compounds.
Iso-paraffins are more reactive than normal
paraffins and are desirable in motor spirit.

 Olefins are unsaturated

hydrocarbons, the double
bond is present between the
two carbon atoms in the
formula.
Olefins are not present in
crude oil, but they are
produced by thermal and
catalytic decomposition or
dehydrogenation of normal
paraffins.

 Naphthenes are cyclic saturated

hydrocarbons with the general
formula (CnH2n) also known as
cyclo-alkanes.
They are relatively inactive, like
paraffins.
Naphthenes
are
desirable compounds for the
production of aromatics and
good quality lube oil base
stocks.

 Crude oil also contains a large number of

hydrocarbons that do not fall into the category of
paraffins, olefins, naphthenes, or aromatics, but may
be the combined group of any two or more groups of
paraffins, naphthenes, or aromatic hydrocarbons.

Non Hydrocarbon or Hetero Atomic

Compound
Hydrogen sulfide (H2S) gas is associated with crude oil
in dissolved form and is released when heated. H2S is
corrosive at high temperatures and in the presence of
moisture.
Crude oil that contains large amounts of H 2S is called
sour crude. H2S can be removed from gases by
absorption in an amine solution
Sulfur present in petroleum fuel products also forms
various oxides of sulfur (SOx) during combustion, which
are strong environmental pollutants.

 Nitrogen compounds in hydrocarbons are usually found

in the heavier parts of the crude oil.
These are responsible for colour and colour instability
and poisoning of certain catalysts.
Nitrogen in petroleum fuels causes the generation of
oxides of nitrogen (NOx).
Nitrogen can be eliminated from petroleum products by
catalytic hydrogenation.

 Oxygen compounds: crude oil may contain oxygen

containing compounds, such as naphthenic acids,
phenols, and cresols, which are responsible for
corrosive activities.
Oxygen also acts as a poison for many catalysts.
This can be removed by catalytic hydrogenation.
Excess oxygen compounds may even lead to
explosion.

Physical Properties of Crude Oil

API gravity is expressed as the relation developed by the
American Petroleum Institute, as

where s is the specific gravity of oil measured with

respect to water, both at 60F (15.5C).
Oil is lighter than water, API gravity is always greater
than 10. The lighter the oil, the larger the API gravity.

Petroleum Components are

Needed to Make Many Products

Petroleum Components are

Needed to Make Many Products
Chemistry; An Environmental Perspective; Buelll, Phyllis and Girard, James; Prentice Hall 1994, p443

Distillation Separates the Components

of Crude Oil Mixture
As the number of carbons in
petroleum
substance
increase;
boiling
point
increases
Distillation
separates
petroleum
mixture
by
different boiling points

Fig.04.15

Petroleum Components
Fraction

# Cs in
Molecule

Boiling
Pt,C

Use

Gas

1-4

-160 to 30

Gaseous
Fuel

Gasoline

5-12

30 to 200

Motor fuel

Kerosene

12-18

180 to 400

Diesel fuel,
furnace fuel

Lubricants

>17

350 and up

Lubricants

Paraffins

>20

Low melting candles

solids

Asphalt

>36

Gummy
residue

Surfacing
roads

Petroleoum Product
Liquefied
petroleum
gas,
commonly called LPG, is also
known by the names of its
principal generic components,
propane and butane.
LPG as a liquid is colorless, and
in vapor form it cannot be seen.
The calorific value of LPG on a
volume basis is significantly
higher (propane, 95 MJ/m3;
butane, 121 MJ/m3) compared
with that of natural gas (38
MJ/m3).

 Pure LPG has no smell, but for safety reasons an

odoring agent (mercaptant).
LPG is a mixture of propane and butane in liquified
format a pressure of about 1015 atm.
LPG is the most versatile fuel used in domestic
applications. It is used like natural gas and can do
everything that natural gas can do.

 LPG is tested for its quality as required by its use as

a domestic cooking gas. One of the simplest tests of
LPG quality is the weathering test
If the temperature < 0 C,
then the proportion of propane
in the mixture is more.
if it is temperature 0-2C,
then the proportion of butane
will be more.
For domestic use, the
maximum : 2C

Petroleum Fuel
Gasoline

Gasoline may be defined as the fuel

derived from crude oil, in the boiling
range of 100 to 400F.
It is estimated that production of
gasoline world wide in 2007 was
approximately 1150 million tons.
Composition : Hydrocarbon

Gasoline Engine
The gasoline engine (spark ignition
engine) is used widely as the power
source of automobiles.
In the SI engines, fuel is burnt directly by
introducing an electrical spark into the
mixture of air and vapour of MS through
the carburettor (a mixing device of air
and vapour of fuel) of the engine. Power
is developed due to the volumetric
expansion of burnt gases (flue gas) in
the engine cylinder during the expansion
stroke (forward stroke) and exhausted to
the atmosphere in the compression
stroke (return stroke) in a repeated cycle.

1. Octane Number
The octane number is a relative measure of
knocking, or the tendency to self-ignition of a fuel in
a spark-ignited internal combustion engine.
If fuel has too low an octane number, it caused
Preignition and will damage the engine.
The antiknock quality of motor gasoline is
expressed in terms of octane numbers.

 If an engine runs with 100% pure iso-octane, the

power rating is 100% (knock free).
If the engine is run with n-heptane, the octane
number is taken as zero.
The octane number falls with the increase in speed
Aircrafts using gasoline require very high RON fuel
as necessary with the cruising speed.

Items that Increase Octane Rating

1.

Branches in Molecule
Cracking and Catalytic Combination
increase branching
2. Oxygen in Molecule
3. Octane Enhancers
Lead before 1975
Fuels with OR>100 (methanol, ethanol,
MTBE)

Increasing the Amount of Gasoline

from Petroleum Mixture
Cracking Reactions : Cracking Kerosene Molecules to
Form Gasoline- sized Molecules

C16H34
C8H18

C8H16

 Catalytic reaction : combination joins smaller

molecules to form a gasoline sized molecule

C2H4 + C2H4

+ C2H4

C8H16

+ C2H4

Octane Rating Describe the Amount of

Knocking a Fuel Undergoes When it is Burned

Gasoline Blend Component

A. MTBE (Methyl tertiary-butyl ether)

MTBE is most suited as a gasoline blend component, and it being

used in gasoline blending to partly replace aromatics.
MTBE can be used up to 11 vol % in the blend, and it gives an
oxygen content of 2 wt % (percentage by weight) to gasoline blend.
A negative effect of MTBE use in gasoline is ground and surface
water pollution, which can occur through leaking underground
storage tanks, pipeline, spills, and emissions from marine engines.

C. Tetraethyl Lead (TEL)

Tetraethyl is an organometallic compound with the
formula (C2H5)4 Pb.
Lead is a poisonous metal that has neurotoxic effects
on humans even at very low levels.
Lead in automotive engine exhaust can be deposited
on the catalyst in the converter and thus permanently
deactivate the catalyst.

2. Reid Vapor Pressure

A gasoline engine needs a fuel that is sufficiently
volatile to allow easy formation of the fuel vapor-air
mixture required for combustion.
If fuel vaporizes too much, it will not flow to the
engine due to vapor lock. If fuel is less volatile, it will
not evaporate and will remain in liquid form.
The Reid Vapor Pressure (RVP) is vapor pressure of
gasoline at 100F.
The RVP of various gasoline grades varies between
35 and 84 kPa.

Distillation

Gasolines tendency to vaporize is also characterized by

determining a series of temperatures at which various
percentages (10, 50, 90 %) of the fuel have evaporated as
described in ASTM D 86.
The 10 % evaporated temperature : 70 0C (easy cold starting)
The 50 % evaporated temperature : 125 0C (low enough to
provide good warm up and cool weather)
The 90 % (FBP) : 180 0C (low enough to minimize crankcase
and combustion chamber deposits, spark plug fouling, and
dilution of engine oil.)

Distillation Analysis

Gasoline Specification

Diesel Fuel
Pure air is drawn into the
cylinder
The air is compressed to
high
temperature
and
pressure
Around TDC fuel is injected,
which self-ignites and burns,
further increasing pressure
and therby forcing the piston
down.
The hot gas is released to
the surrounding.

Diesel Fuels Specifications

Viscosity

Flash
point

Diesel
fuels

Pour point

Sulphur

1. Viscosity
Viscosity is a measure of resistance to flow, and it
decreases as the temperature increases.
The viscosity of the fuel must be low enough toballow
free flow at its lowest operating temperature but high
enough to provide lubrication to the moving parts of
finely machined injectors.
Diesel fuel viscosity typically lies between 1.5 and 6
cSt at 100F. A viscosity of 4 cSt at 100 F is considered
optimum for atomization, lubrication, and good
penetration into the combustion chamber.

2. Flash Point
Flash Point (ASTM D 93).
The flash point is defined as
the temperature of the oil at
which it momentarily flashes in
the presence of air and the
igniting source.

3. Pour Point
The pour point is the temperature at which there is no
movement of a chilled sample in a test jar. However,
the fuel may still flow under static head at pour point
(e.g., from storage tank to pump suction). In a
temperate climate, the diesel pour point generally
varies between 6 and -6 0C.

4. Sulphur
Sulfur has a definite effect on the wear of
compression-ignited engine components such as
piston rings.
Fuel sulfur contributes to deposits in the combustion
chamber and in the injection system.
Sulfur specification was reduced from 1 wt %
(percent by weight) a decade ago to 500 to 15 ppm in
2007, in most developed countries of the world.

5. Distillation
This test measures at what
maximum temperature would
the B-100 product completely
be vaporized under a reduced
pressure .
Data is collected of the initial
and final boiling temperature
point as well as the boiling
curve (the volume per cent
distilled
over
different
temperature increments).

6. Cetana Number
The cetane number of diesel fuel is a rating to
indicate how quickly a fuel will ignite in a diesel
engine.
A diesel engine if run on a fuel with a lower cetane
number than what it was designed for will be harder
to start and noisier, and it will have higher exhaust
emissions.
Ignition quality is compared with a mixture of cetane
or n-hexadecane (C16H34) and alpha methyl
naphthalene or 1-methyl naphthalene (C11H10).
Cetane ignites quickly and is arbitrarily given a
cetane number of 100.

Diesel Fuels Spesification

Gasoline is Available in
87, 89, and 92 Octane

Octane Rating Scale is Based on Heptane

(OR-0) and Iso-octane (OR=100)
CH3

CH2

CH2

CH2

CH2

CH2

heptane
CH3
CH3

CH3
CH2

CH3
Isooctane

CH

CH3

CH3

Angka Oktan
Angka oktan suatu bahan bakar dinyatakan dengan
besar prosen volume iso-oktana dalam campuran yang
terdiri dari iso-oktana dan n hepatana.
Angka oktan yang merupakan salah satu faktor utama
untuk mengetahui kualitas bensin adalah nilai ketahanan
suatu bahan bakar bersama dengan udara terhadap
terjadinya penyalaan disaat langkah kompresi atau
disebut dengan kemampuan anti-ketukan.

 Uji angka oktan digunakan motor

khusus yang bersilinder tunggal
dimana
perbandingan
kompresinya dappat diubahubah,
yang disebut dengan motor CFR
(Cooperative Fuel Research).
Research Octane Number (RON)
(CFR F-1)
Motor Octane Number (MON)
(CFR F-2)

Cooperative Fuel Research (CFR)

Pengaruh MTBE Terhadap Angka Oktan

Pengaruh Putaran Motor Terhadap Daya Motor

Konsentrasi MTBE 20%

menghasilkan
daya
optimum pada putaran
2500 Rpm.
Konsentrasi MTBE 25%
menghasilkan
daya
optimum yang lebih
kecil.

Aviation fuel
Kerosene

Jet Fuel
(Jet-A, JP-8)

Increased Performance, Reliability & Safety

Gasoline

Avgas
(100 LL)

High performance aviation engines were made possible

because of the concurrent development of high performance
aviation fuels
Aviation fuels are specifically designed for
Increased engine performance
Increased reliability

This is true for both piston and turbine aviation engines and
fuels