Petroleum Chemistry

(Chem. 441)
For B. Sc. Students
By
Prof. Dr. Ahmad M. Farag

Professor of Organic Chemistry

Faculty of Science
Cairo University

Prof. Dr. Ahmad M. Farag 1

 Contents
• Introduction
• Origin and Occurrence of petroleum
• Petroleum Products
• Terms and definitions
• Classification of Crude Oils
• Chemical and Physical Determinations
of Crude Oil Quality

Prof. Dr. Ahmad M. Farag 2

• Chemical Composition of Crude Oils
• Raw Materials for Petrochemicals
• Natural Gas
• Refinery Processes:
• Thermal Cracking
• Catalytic Conversions
• Petrochemicals:
•From Methane
•From Synthesis Gas
•From Methanol
Prof. Dr. Ahmad M. Farag 3
 Petroleum (Crude Oil)
Introduction:
The term petroleum comes from the Latin stems
petra, "rock," and oleum, "oil."
It is used to describe a broad range of
hydrocarbons that are found as gases, liquids, or
solids beneath the surface of the earth.
The two most common forms are natural gas and
crude oil.
Petroleum is an oily, viscous liquid which has
many impurities like water, salt and sand. It is also
a complex mixture of many hydrocarbon
compounds.
Oil deposits are found with water, dust particles,
rocks, salt and sand.
Prof. Dr. Ahmad M. Farag 4
Origin and Occurrence of Petroleum

• Petroleum (including heavy oil and

bitumen), natural gas, and oil shale
produced by the decay of plant remains
over geological time.
• There are two theories on the origin of
petroleum: the Abiogenic theory and
the Biogenic theory.

Prof. Dr. Ahmad M. Farag 5

• Abiogenic Origin:
• Crude oil constituents were produced from
acetylene.
CaCO3 + alkali metal → CaC2 (calcium carbide)
CaC2 + H2O → acetylene + petroleum
The action of dilute acids or hot water on mixed
iron and manganese carbides produces a mixture
of hydrocarbons from which petroleum evolved is
another theory in which acetylene is considered to
be the basic material:

Fe3C + H2O + H+ → hydrocarbons + petroleum

Mn3C + H2O + H+ → hydrocarbons + petroleum

Prof. Dr. Ahmad M. Farag 6

• Biogenic Origin
• Hydrocarbons that are synthesized by
living organisms usually account for
less than 20% of the petroleum. The
remainder of the hydrocarbons in
petroleum is produced by a variety of
processes that convert other organic
material to hydrocarbons as part of the
maturation processes.

Prof. Dr. Ahmad M. Farag 7

Evidence Supporting Biogenic Theory
• Presence of brine (sea water) together
with petroleum.
• Presence of optically active
compounds.
• Presence of compounds containing N,
S, and chlorophyll.
• Presence of fossils in petroleum areas.
• Presence of resins (vegetable origin).

Prof. Dr. Ahmad M. Farag 8

• Nature of Source Materials
• Hydrocarbons: considered as a source of paraffinic
and naphthenic crudes. Thermal alteration of
polyterpene (β-carotene) and amino acid
(phenylalanine) can be natural precursors of alkyl
aromatics (alkylbenzenes and alkylnaphthalenes).

Lycopene

β-Carotene

Prof. Dr. Ahmad M. Farag 9

• Fatty Acids:
• They are converted to hydrocarbons by simple
elimination of CO2

RCOOH RH + CO2

Acid Structure Natural source

Butyric CH3CH2CH2COOH Cow butterfat

Hexanoic CH3(CH2)4COOH Goat butterfat

Palmitic CH3(CH2)14COOH Palm oil

Oleic CH3(CH2)7CH=CH(CH2)7COOH Olive oil

Linoleic CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH Cottonseed oil

Eleostearic CH3(CH2)3(CH=CH)3(CH2)7COOH Tung oil

Prof. Dr. Ahmad M. Farag 10

• Fats:
• Which are mixtures of various glycerides.

CH2OCOC15H31 CHOCOC17H35 CH2OCOC17H35 CH2OCOC17H35

CHOCOC15H31 CHOCOC15H35 CHOCOC 17H35 CH2OCOC17H35
CH2OCOC15H31 CH2OCOC17H35 CH2OCOC15H31 CH2OCOC17H33

Tripalmitin Tristearin Palmitodistearin Oleodistearin

Prof. Dr. Ahmad M. Farag 11

• Carbohydrates: Important parts of all
plants and contribute to the total organic
content of the sediments.

• Proteins: highly complex component of all

living matter. They are polymeric
substances composed of one or more of
some 25 amino acids linked together
through pepited linkage.

Prof. Dr. Ahmad M. Farag 12

 • Lignin: a mixture of complex, high molecular weight,
amorphous substances and forms the cell structure of plants,
particularly those of woody type
• Sterols: saturated, condensed ring structure which distributed
in animals and plants and are also believed to source material
for petroleum.

OH

O HO
HO
Testosterone Cholesterol Vitamin D

Prof. Dr. Ahmad M. Farag 13

• Porphyrins: Complex derivatives of the
basic material porphine. They are among the
nitrogen-containing constituents of crude oil.
• They are recognized as the degradation
products of the chlorophyll.

NH
HN

NH
HN

Prof. Dr. Ahmad M. Farag 14

 Petroleum can be extracted from oil wells by
drilling. Wherever natural gas is found,
petroleum well close by is a possibility.

Diagram to show the occurrence of petroleum under the surface of earth

Prof. Dr. Ahmad M. Farag 15
The first oil well was found in Pennsylvania
in the USA in the year 1859. In India the first
oil well was found in 1867.
These days oil wells are generally found
under the sea and therefore off shore oil
wells have to be dug by building platforms
at sea.
The process whereby the petroleum is
separated into its components along with
the separation of impurities is called
“Refining of petroleum”.
Prof. Dr. Ahmad M. Farag 16
Refinery Processes can be divided into three major
steps:
1- Separation: is the division of the crude oil into
various steams (or fractions) depending on the
nature of the crude material.
2- Conversion: is the production of salable materials
from the crude oil.
3- Finishing: is the purification of the various
fractions by several processes to remove
impurities from the product.
The refining is done by fractional distillation.
Each hydrocarbon component with its own boiling
point separates out neatly when the petroleum is
heated. Prof. Dr. Ahmad M. Farag 17
The Figure below shows the fractional
distillation of petroleum.

Prof. Dr. Ahmad M. Farag 18

 Petroleum-based Products
• Fuel (89%)
– Gasoline
– Diesel
– Jet Fuel
– House fuel oil
• New substances (7%)
– Plastics
– Medications
• Lubricants, road paving materials and
misc.(4%)

Prof. Dr. Ahmad M. Farag 19

 Petroleum Products
Nomenclature:
Terms used for petroleum and its products:
• L. P. G.: Liquefied Petroleum Gas:
Light hydrocarbons (propane and butanes)
which are gaseous at atmospheric pressure
and temperature. It can sometimes be
liquefied and maintained in the liquid state
under pressure to facilitate storage, handling
and transport.
Commercial L. P. G. is principally composed
of butanes and propane (Butagas).
Prof. Dr. Ahmad M. Farag 20
• Crude oil: The material obtained directly
from the well.
• Sour Crude: it is the crude containing H2S,
RSH in great amounts.
• Gasoline: Liquid petroleum product boiling
blew 200°C [American and British usage].
In Britain “Motor spirit” and “petrol” are also
used.
The corresponding French term is “essence”
while most other European countries use
“benzine”, a word which should not be
confused with “benzene”, the name of the
pure aromatic hydrocarbon.
Prof. Dr. Ahmad M. Farag 21
• Aviation Gasoline: A special type of gasoline
used for aircrafts.
• Naphtha: In U.S.A. the term is used for the higher
boiling fractions up to 220°C (heavy gasoline).
• Special Boiling Point Spirits:
These are relatively narrow boiling fractions within
the overall range of gasoline, which are used as
solvents and cleaning fluids. Of these is “white
spirit” which is used as a solvent and paint
thinner. This term is international, but mineral
turpentine is sometimes used in certain countries.
Prof. Dr. Ahmad M. Farag 22
 The fractions within the low boiling range of
gasoline are:
• Petroleum ether:
40-60 °C
60-80 °C
80-100°C
Ligroin: 100-120°C
• Kerosine or Kerosene: It is the illuminating oil
fraction, also used in stoves and heaters.
• Paraffin Wax: It is a mixture of solid
hydrocarbons obtained from waxy distillates
(starting from heptadecane upwards, (C17H36).
Prof. Dr. Ahmad M. Farag 23
• Petrolatum or Petroleum Jelly:
It is a microcrystalline wax + some lubricating
oil. It is sometimes called mineral jelly or
Vaseline.
• Medicinal Oil ( liquid paraffin):
It is a lubricating oil fraction, refined so as to be
(water white), tasteless and odorless.
• Diesel Oil:
This term may indicate either fuel or a lubricant
for Diesel engines. Diesel lubricant: the
lubricating oil used for lubrication of diesel
engine.
Prof. Dr. Ahmad M. Farag 24
• Lubricating Oils (Lube Oils):
• Lubricating Grease:
• Gas Oil (Solar): It is described as distilled
fuel oil. It should be noticed that diesel fuel
is heavy gas oil.
• Fuel Oil (Furnace Oil):
These fuel oils are the undistilled type.
Sometimes are called “residual fuel oils”
and are obtained from atmospheric
distillation of some crude oils, which are of
asphaltic type. It is also called topped crude
oil.
Prof. Dr. Ahmad M. Farag 25
• Asphaltic Bitumen:
The dark semisolid residual product obtained from
petroleum by distillation under reduced pressure.
The word is abbreviated to Bitumen.
• Asphalt:
A mixture of natural bitumen + minerals (as found
in Trinidad, Bolivia (which is famous by Pitch
Lake) or it is a mixture of artificial bitumen
(asphaltic bitumen) + minerals.
• A Fraction:
Is a cut of distillation collected through certain
boiling range.
• A Product:
Is a fraction after treatment and refining so that it
acquires the properties needed in its
specifications. Prof. Dr. Ahmad M. Farag 26
 Classification of Crude Oils
Crude oils are generally characterized as
belonging to one of four types depending
upon the relative amounts of waxes and
asphalts present. The wax content shows the
degree to which the crude is paraffinic. The
presence of asphalts indicates an aromatic
crude.
1. Light paraffinic: Crudes with a relatively low
wax content.
2. Paraffinic: Crudes with a high wax content
and relatively low asphalt content in the
residue.
3. Naphthenic or asphaltic: Crudes with trace
amounts of waxes and high asphalt content
in the residue.
4. Aromatic: Crudes with high aromatic
content.
• The term "mixed crude" is used when the
crude has average properties between
paraffinic and naphthenic
Prof. Dr. Ahmad M. Farag
types. 28
 Chemical and Physical Determinations of
Crude Oil Quality
Specific gravity (sp. gr):

sp. gr. t1/t2= Density of liquid at t1

Density of H2O at t2
• The temperatures t1 and t2 must be stated,
we say for e.g.: sp. gravity 60°/60° F
means that both densities were measured
at 60°F. The density of liquid is the mass
of unit volume at a stated temperature.
Prof. Dr. Ahmad M. Farag 29
• American Petroleum Institute (A.P.I.)
A.P.I. gravity is used instead of sp.
gravity or density. A.P.I. gravity degrees
are found in tables corresponding to sp.
gravity, but it can be also calculated.
Sp. gravity and density are converted
into API degrees, if the tables are
unavailable, as follows:
API degrees = 141.5 -131.5
sp. gr. 60/60°F
= 141.36 -131.5
d (60°F)
Prof. Dr. Ahmad M. Farag 30
• Pour Point:
• The pour point of a crude oil or a product
is the lowest temperature at which an oil
is observed to flow under the conditions
of the test. The importance of pour point
data is that it is an indication of the
amount of waxes present in crude oils.
The test is also important for diesel fuels
and lubricating oils used in cold areas.
Specified pour points for these products
should be below the lowest temperature
reached in these areas.
Prof. Dr. Ahmad M. Farag 31
• Sulfur content:
Determination of sulfur in crudes is important
since it gives the refiner an indication of the
amount of sulfur compounds in the products
and whether the crude oil needs further
treatment.
• Carbon Residue:
Carbon residue is an indication of the tendency
of a crude oil to form carbonaceous and metal
residues which do not burn or evaporate easily
at the conditions of the test. Carbon residue
determination is an important test for diesel
fuels, lubricants and fuel oil.
Prof. Dr. Ahmad M. Farag 32
• Ash Content:
Tests for ash content show the amount of
ash left after burning all the liquid and
volatile material in a crude oil or a
product.

• Aniline point:
It is the lowest temperature at which the
oil is completely miscible with an equal
volume of aniline.

Prof. Dr. Ahmad M. Farag 33

 Aniline point is useful for:
Characterization of crude oil and petroleum
products.
• For oils of a given type, it increases rapidly
with paraffinisty. As a consequence it is one
of the first properties used for the
determination of aromatics and naphthens
content in oils or fuels.
• Calculation of Diesel index:
Diesel Index=
[Aniline point (°F) × API gravity] ÷ 100
Prof. Dr. Ahmad M. Farag 34
 Composition of Crude Oils
The crude oil mixture is composed of the following
groups:
1. Hydrocarbon compounds.
2. Non-hydrocarbon compounds.
3. Organometallic compounds and inorganic salts
(metallic compounds).
• Hydrocarbon Compounds:
The principal constituents of most crude oils are
hydrocarbon compounds. All hydrocarbon classes are
present in the crude mixture, except alkenes and
alkynes. This may indicate that crude oils originated
under a reducing atmosphere.

Prof. Dr. Ahmad M. Farag 35

The following are the different hydrocarbon
classes found in all crude oils:
Alkanes (Paraffins):
Alkanes are saturated hydrocarbons having the
general formula CnH2n+2. The simplest alkane,
methane (CH4) is the principal constituent of
natural gas. Methane, ethane, propane, and
butane are gaseous hydrocarbons at ambient
temperatures and atmospheric pressure.
They are usually found associated with crude
oils in a dissolved state.
Prof. Dr. Ahmad M. Farag 36
As the molecular weight of the hydrocarbon
increases, the number of isomers also
increases. e.g. hexane (C6H14) has the following
isomers:

Prof. Dr. Ahmad M. Farag 37

Cycloparaffins (Naphthenes)

Prof. Dr. Ahmad M. Farag 38

 Aromatic compounds
CH3
CH3

CH3
Benzene Toluene p-Xylene

Naphthalene Tetralin
1,2-Benzopyrene
Prof. Dr. Ahmad M. Farag 39
Non-hydrocarbon Compounds
Sulfur compounds:
Acidic Sulfur compounds:
CH 3SH
Methyl mercaptan (Methanethiole)
SH SH

Phenyl mercaptan Cyclohexyl mercaptan

(Benzenethiol) (Cyclohexanethiol)
Prof. Dr. Ahmad M. Farag 40
Non-acidic Sulfur compounds

CH3SCH3
Dimethyl sulphide

S S S
Thiophene Thiopyran Benzothiophene

Prof. Dr. Ahmad M. Farag 41

Nitrogen compounds
Basic nitrogen compounds:

N N
Pyridine Quinoline

N
N
Isoquinoline Acridine
Prof. Dr. Ahmad M. Farag 42
Non-basic nitrogen compounds

N N
H H
Pyrrole Indole

N
H N
H
Carbazole Benzocarbazole
Prof. Dr. Ahmad M. Farag 43
 Oxygen compounds
Acidic Oxygen compounds
COOH

CH3(CH2)n-COOH

Aliphatic carboxylic Cyclohexane carboxylic

acid acid
OH OH

R COOH R
Aromatic carboxylic Phenol Cresylic acides
acid
Prof. Dr. Ahmad M. Farag 44
Non-acidic Oxygen compounds

R-COOR' R-CONHR' R-CO-R'

Esters Amides Ketones

O O
Furan Benzofuran
Prof. Dr. Ahmad M. Farag 45
 Raw Materials for Petrochemicals

• Primary raw materials are naturally

occurring substances that have not been
subjected to chemical changes.
• Natural gas and crude oils are the basic raw
materials for the manufacture of
petrochemicals.
• Secondary raw materials, or intermediates,
are obtained from natural gas and crude oils
through different processing schemes.
Prof. Dr. Ahmad M. Farag 46
 Natural Gas
• Associated gas: is present in contact with and/or
dissolved in crude oil and is co-produced with it.
• Non-associated natural gas: is found in
reservoirs containing no oil (dry wells).
• The principal component of most natural gases
is methane. Higher molecular weight paraffinic
hydrocarbons (C2-C7) are usually present in
smaller amounts with the natural gas mixture.
• Non-associated gas: contains a higher methane
ratio than associated gas, while associated gas
contains a higher ratio of heavier hydrocarbons.
Prof. Dr. Ahmad M. Farag 47
• Non-hydrocarbon constituents in natural gas are
weak acids, such as H2S and CO2 or inert, such
as N2, He and Ar.
• Higher molecular weight hydrocarbons present
in natural are recovered as Natural Gas Liquids
(NGL).
• Propane and butane are recovered from natural
gas and sold as Liquefied Petroleum Gas (LPG).
• Before natural gas is used it must be processed
to remove the impurities and to recover the
heavier hydrocarbons (heavier than methane).

Prof. Dr. Ahmad M. Farag 48

 Natural Gas Treatment
• Acid Gas Treatment:
1. Physical absorption using a selective absorption
solvent e.g. Selexol (dimethyl ether of ethylene
glycol)
2. Physical adsorption using a solid adsorbent
(e.g. zeolites).
3. Chemical absorption (chemisorption) using
solvent capable of reacting reversibly with the
acid gases (e.g. weak base such as mono- &
diethanolamines or strong basic solutions such
as NaOH).

Prof. Dr. Ahmad M. Farag 49

Strong basic solutions are also used for
acid gases (e.g. NaOH is used to remove
H2S and CO2).

In the Merox Process a caustic solvent

containing a catalyst such as Co,
which is capable of converting
mercaptans (RSH) to caustic insoluble
disulfides (RSSR) is used for streams
rich in mercaptans.
Prof. Dr. Ahmad M. Farag 50
 Water Removal
• Moisture must be removed from natural
gas to reduce corrosion problems and to
prevent hydrate formation
• Ethylene glycol (EG), diethylene glycol
(DEG) and triethylene glycol (TEG) are
typical solvents for water removal.
• Water can also be reduced or removed
from natural gas by using solid
adsorbents such as molecular sieves or
silica gel.
Prof. Dr. Ahmad M. Farag 51
• Molecular sieves are crystalline
aluminosilicates having a three dimensional
interconnecting network of silica and alumina.
• They demonstrated utility in synthetic organic
procedures allowing isolation of desired
products from condensation reactions that are
governed by unfavorable equilibria.
• These synthetic zeolites have been shown to
remove water (their drying capacity even to
90°C), alcohols (including methanol & ethanol),
and HCl from such systems as ketimine and
enamine syntheses and ester condensations.
Prof. Dr. Ahmad M. Farag 52
Condensable Hydrocarbon Recovery
• Hydrocarbons heavier than methane
present in natural gases can be recovered
by lean oil extraction.
• Lean oil absorption is a process in which
the NGL's are removed by contacting the
natural gas with a liquid hydrocarbon
solvent (oil).
• Lean oil absorbs the NGL's in an absorber
column, the resulting rich oil is subjected
to a distillation process to separate NGL's
for sale and recycling the regenerated
lean oil to the absorber column.
Prof. Dr. Ahmad M. Farag 53
• Another way to recover NGL is
through cryogenic cooling to very
low temperatures (-150 to -180°F),
which are achieved by adiabatic
expansion of the inlet gas.
• Further cooling of the gas is
accomplished through turbo
expanders, and the gas is sent to a
demethanizer to separate methane
from NGL.

Prof. Dr. Ahmad M. Farag 54

 Natural Gas Liquids (NGL)
• NGLs are those hydrocarbons heavier than
methane that are recovered from natural gas.
• A high percentage is normally expected from
associated gas.
• NGLs are fractionated to separate them into three
streams:
1. Ethane-rich stream, which is used for producing
ethylene.
2. Liquefied Petroleum Gas (LPG) which is a
propane-butane mixture which is mainly used as a
fuel or a chemical feedstock.
LPG is an important feedstock for olefin
production.
3. Natural Gasoline (NG) is mainly constituted of
C5+ hydrocarbons and is added to gasoline to raise
its vapor pressure. Natural gasoline is usually sold
according to its vapor pressure.
Prof. Dr. Ahmad M. Farag 55