Menoufia University

Faculty of Science
Chemistry Department

THE CHEMISTRY OF PETROLEUM AND

ITS PRODUCTS (CH3616)
Prof. Adel Abdel-Hady Nassar
Prof. of Organic Chemistry
Dean of Faculty of Science
Menoufia University

2021/2022 (Second Term)

 Course specification
44. Chemistry of Petroleum and its products CH3616
2020-2021

Program (s) on which the course is given: Ch, Ch.&G.,

Major or Minor element of programs: Minor
Department offering the program: Chemistry
Department offering the course: Chemistry
Academic year / Level: Fourth ↑102
Date of specification approval: 2021
1- Basic Information
Title: Chemistry of Petroleum and its products Code:
CH3616
Credit Hours: 2h Lecture:-1.5h
Tutorial: 1 Practicals:0 Total:2h

2- Professional Information
Overall aims of course:
- Upon successful completion of this course, the student will achieve a basic
understanding of what occurs inside a modern petroleum refinery.
Furthermore, the student will learn how the most common refinery fuels
processes accomplish the refining of crude oils into the fuels specification
products that the markets demand.
- Gain knowledge about the synthesis and industrial applications of
petrochemical, starting from saturated and unsaturated hydrocarbons.
- Provide a brief overview of the function and interrelationship of the
petroleum refinery fuels processes most commonly found in modern
petroleum refineries.
- Having knowledge on the processes of refining petroleum crude oils into the
literally hundreds of specification petroleum products, many of which we
use on a daily basis.
A – Intended Learning Outcomes of Course (ILOs)
a- Knowledge and Understanding:
After completing the course the student should be able to
a1. Discuss the basic information of petroleum and petrochemicals.
a2. Identify natural gas, mainly methane, and petroleum as sources of energy
a3. Illustrate petroleum as a mixture of hydrocarbons and its separation into
useful fractions by fractional distillation
a4. Discuss the following fractions and state their uses
(i) petrol (gasoline) as a fuel in cars

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 (ii) naphtha as feedstock for the chemical industry
(iii) paraffin (kerosene) as a fuel for heating and cooking and for
aircraft engines.
(iv) diesel as a fuel for diesel engines
(v) lubricating oils as lubricants and as a sources of polishes and
waxes
(vi) bitumen for making road surfaces
a.5 Explain that the naphtha fraction from crude oil is the main source of
hydrocarbons used as the feedstock for the production of a wide range of
organic compounds
a.6. Discuss the issues relating to the competing uses of oil as an energy
source and as a chemical feedstock
b. Intellectual Skills:
On completing this course, students will be able to:
b1- Deduce different classes of natural products.

b2- Differentiate between suitable methods to synthesize petrochemicals.

b3- Differentiate between petroleum products and petrochemicals.
c. Professional and Practical Skills
On completing this course, students will be able to:
c1-Apply the students to work in petro-chemical industry.
c2- Apply the students to be familiar with instruments and
different chemical reactions.
d. General and Transferable Skills:
On completing this course, students will be able to:
d1- Able to Work effectively both in a team, and independently on solving
chemistry problems.
d2- work effectively both in a team, and independently on collecting
information on a required topic.
d3- Communicate effectively with his teacher and colleagues.
d4- - Use E-learning University platform melc.menofia.edu.eg
3. Course content
No. of No. of Tutorial/
Topics Lecture
weeks hours Practical
An introduction to petroleum and 1 2 1.5 1
its importance in our daily life
The origin of petroleum and natural 2,3 4 3 2
gas.
Composition of Petroleum and its 4 2 1.5 1
refinery.

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Hydrocarbons and 5,6 4 3 2
nonhydrocarbons contents in
petroleum.
Mid term exam 7 2
Types of petroleum processes 8,9 4 3 2
Thermal and Catalytic cracking of 10,11 4 3 2
crude oils.
Octane number and octane rating 12,13 4 3 2
mechanism of thermal and catalytic
cracking in petroleum process
Types of petroleum reforming an
transformations and Petrochemicals
and Biofuels
Final term exam 14 2

4– Teaching and Learning Methods

Course ILO Covered by Method (By ILO Code)
Teaching/Learning
Method K&U S. I/C S. P&P S. G&T S.

Lectures a1…a5 b1…b3 c2 d1, d2

Discussion (Brain
b2, b3 c1, c2 d1, d2
Storming)
Practical / Tutorials b1, b2, c1, c2, d1, d4
Reading Materials a1,a2 b2, b3, c1, c2, d1,d2
Research &
a3, a4,a6 b3, d2
Reporting
Problem Solving-
a1, a2, a4, b1, b2, b3, c2, d1,d2,d3
based Learning
Individual Work a1, a4 b1, b2, b3 c1
Group Work c2, d2,d4
E-learning a1,a5,a6 b1 c1 d4

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5- Student Assessment Methods
Course ILOs Covered by Method
(By ILO Code) Assessment
Assessment Week
Weight /
Method P&P G&T No.
K&U I/C S. Percentage
S. S.
Midterm d2
a1,a2 b1,b2 c1,c2 (20 %) 7
Exam
Final Exam a1,a2,a3 b1…b3 c1…c2 d1.. d4 (60 %) 14
Quizzes a1…a4 b1…b3 c1,c2 d1…d4 6, 11
Course 3, 10,
a1,a2 b1..b3 c1 d1…d4
Work 12
(20 %)
Oral
11..a5 b1..b2 c2 d2 14
Assessment
Practical a2…a5 b1, b3 c1,c2 d2
Online
a1,a5,a6 b1 c1 d4
assignment

6- List of References:
6.1: Recommended Textbooks

The Chemistry and Technology of Petroleum by James G.

Speight, Third edition, 2008.
6.2: Websites on the internet that are relevant to the topics of the course:
http://en.wikipedia.org/wiki/Petroleum
2- http://www.mawsoah.net/maogen.asp
3- http://www.rasgharib.net/index.php
://www.faisalbughdadi.com/teach/
6.3 Sample preparation procedure for the determination of polycyclic aromatic
hydrocarbons in petroleum vacuum residue and bitumenThis paper describes a novel
method of sample preparation for the determination of trace concentrations of
polycyclic aromatic hydrocarbons (PAHs) in high-boiling petroleum products. Limits
of quantitation of ...Ewelina Gilgenast, Grzegorz Boczkaj… in Analytical and
Bioanalytical Chemistry (2011)

6.4 Scanning calorimetry and thermogravimetry in analysis of

petroleum systems. Determination of the component composition
The possibility of qualitative analysis of heavy hydrocarbon mixtures
by differential scanning calorimetry (DSC) and quantitative analysis
combined with thermogravimetry (TG) was demonstrated. In
experimental ...
Yu. L. Shishkin in Chemistry and Technology of Fuels and Oils (2006)
-6-
7- Facilities Required for Teaching and Learning
- Suitable lecturing hall
- Data show, screen, and laptop computer.
- White board and colored pens

8- ILO’S contents
P&
K&U S. I/C S.
G&T S.
P S.
Course contents a a a a a a b b b c c d d d d
1 2 3 4 5 6 1 2 3 1 2 1 2 3 4
An introduction to √ √ √ √ √
petroleum and its
importance in our
daily life
The origin of √ √ √ √ √
petroleum and
natural gas.
Composition of √ √
Petroleum and its
refinery.
Hydrocarbons and
nonhydrocarbons
Types of petroleum √ √ √ √
processes
Thermal and
Catalytic cracking of
crude oils.
Octane number and √ √ √
octane rating
Mechanism of √ √ √
thermal and catalytic
cracking in
petroleum process
Types of petroleum √ √ √ √
reforming and
transformations
Course Coordinator: Prof. Dr. Adel Nassar
Head of Department: Prof. Dr. Ebrahim Tantawy
Date: / /2021

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 CONTENTS

Page Subject
9 Part One: The Chemistry of Petroleum
and Its Derivatives
Chapter I:
The Chemistry of Petroleum
25 Petroleum as Primary Raw Materials for
Petrochemicals
45 Crude Oil Processing and Production of
Hydrocarbon Intermediates
85 Part Two
Petroleum Derivatives:
Chapter I: Petrochemicals
96 Chapter II: Detergents
110 Chapter III: Lubricating Oils Chemistry
138 General Bank of Questions
168 List of References

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 THE CHEMISTRY OF PETROLEUM
AND ITS PRODUCTS
PART ONE
PETROLEUM CHEMISTRY
CHAPTER I

The Chemistry of Petroleum

Aim:
The course aims to provide an understanding of
the chemical composition and properties of petroleum
(oil and gas), and provide knowledge of petroleum
products and alternative fuels.
What is petroleum?
Petroleum comes from the Latin words petr-
(rock) and oleum (oil). Petroleum is the term for a
complex mixture of hydrocarbons and lesser quantities
of other organic molecules containing sulphur (S),
oxygen (O), nitrogen (N) and some metals.
Hydrocarbons are compounds that contain only
hydrogen (H) and carbon (C) atoms and the number of
carbon atoms in a compound determines its physical
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properties. For example, simple compounds such as
methane (CH4), ethane (C2H6), propane (C3H8) and
butane (C4H10) all have boiling temperatures below
0 °C and are therefore gases under ambient (surface
temperature and pressure) conditions. Larger, more
complex hydrocarbon compounds ranging from
pentane (C5H12) to hexadecane (C16H34) are liquids
under ambient conditions, whilst even larger
compounds with a high molecular weight form waxy
solids. The molecular arrangement of hydrocarbon
compounds is highly variable. The most commonly
occurring forms are chemically stable, so-called
saturated compounds known collectively as paraffins
and cycloparaffins. A second group, in which the
bonding arrangement is more complex and potentially
less chemically stable, comprises unsaturated
compounds called aromatics and alkenes. Aromatic
compounds such as toluene (C6H5CH3) rarely amount
to more than 15% of petroleum but they may impart a
pleasant odour, hence their name. Petroleum occurs
naturally in several forms: natural gas – mainly
gaseous hydrocarbons but also containing variable

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amounts of carbon dioxide; a liquid, called crude oil,
that typically contains a very wide range of
hydrocarbon compounds; and solid bitumen. Bitumen
contains the heaviest (in the sense of high molecular
weight) and most complex hydrocarbon compounds
found in petroleum, and they are relatively enriched in
oxygen, sulphur and nitrogen. The composition of
typical petroleum samples are shown in Table 1. Note
that oxygen is a significant impurity in bitumen, but is
commonly found only in trace amounts in crude oil and
natural gas. In contrast, nitrogen is negligible in
bitumen and crude oil, but may constitute up to 15% in
natural gas.

(C) NATURAL GAS

(B) CRUDE OIL

(A) GROUND WATER

Fossils into fuels:

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 Crude oil, natural gas and coal are fossil fuels.
Fossil fuels are very precious resources because they
are non-renewable (once they're used, that's it!). We
can also make lots of organic chemicals from them,
needed to make products such as paints, detergents,
polymers (including plastics), cosmetics and some
medicines. Fossil fuels were formed from the fossillized
remains of dead plants and animals that once lived
millions of years ago. Oil and natural gas are the
products of the deep burial and decomposition of dead
plants and animals. Heat and pressure, in the absence
of oxygen, transform the decomposed material into tiny
pockets of gas and crude oil. The oil and gas then
migrates through the pores in the rocks to eventually
collect in reservoirs. Coal comes mainly from dead
plants which have been buried and compacted beneath
sediments. Most coal originated as peat in ancient
swamps created many millions of years ago.
What is crude oil?
Crude oil is a complex mixture of hydrocarbons
with small amounts of other chemicals such as sulphur.
The crude oil is useless as a mixture and must be sent
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to an oil refinery to be separated. Crude oils from
different parts of the world, or even from different
depths in the same oilfield, contain different mixtures of
hydrocarbons and other compounds. This is why they
vary from light colored volatile liquids to thick, dark oils.
What is natural gas?
Natural gas is a mixture of hydrocarbons with
small molecules. These molecules are carbon and
hydrogen. For example, natural gas used in the home
is mainly methane.
What is a hydrocarbon?
Hydrocarbons only contain hydrogen and carbon
atoms. There are two main chemical families of
hydrocarbons - the alkanes and the alkenes.
Thousands of synthetic products can be manufactured
from hydrocarbons with many different properties such
as polymers and plastics.
Oil refineries:
A refinery is a factory. A refinery takes a raw
material (crude oil) and transforms it into petrol and
hundreds of other useful products. A refinery breaks

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crude oil down into its various components, which then
are selectively changed into new products. This
process takes place inside a maze of pipes and
vessels. The refinery is operated from a highly
automated control room. All refineries perform three
basic steps:
 Separation (fractional distillation)
 Conversion (cracking and rearranging the
molecules)
 Treatment

Fractional distillation: is the separation of a mixture

into its component parts, or fractions, such as in
separating chemical compounds by their boiling point
by heating them to a temperature at which several
fractions of the compound will evaporate. It is a special
type of distillation. Generally the component parts boil
at less than 25 °C from each other under a pressure of
one atmosphere (atm). If the difference in boiling points
is greater than 25 °C,
Separation: fractional distillation: Modern separation
involves piping crude oil through hot furnaces. The

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resulting liquids and vapours are passed into distillation
towers:

 It is important to realize that the column is hot at the

bottom and cool at the top.
 The crude oil separates into fractions according to
weight and boiling point.
 The lightest fractions, including petrol and liquid
petroleum gas (LPG), vapourise and rise to the top
of the tower.
 Kerosine (aviation fuel) and diesel oil, stay in the
middle of the tower
 Heavier liquids separate lower down.
 The heaviest fractions with the highest boiling points
settle at the very bottom.
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Trends as we up and down the column:
The following table shows how the behaviour of
the hydrocarbon molecules alters.

The fractions are now ready for piping to the next

areas within the refinery. Some fractions require very
little additional processing. However, most molecules
require much more processing to become high-value
products.
Conversion: cracking and rearranging molecules:
Some fractions from the distillation towers need
to be transformed into new components . This is where
a refinery makes money, because the low-value
fractions that aren't in great demand can be converted
to petrol and other useful chemicals. The most widely
used conversion method is called cracking because it
uses heat and pressure to "crack" heavy hydrocarbon
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molecules into lighter ones. A cracking unit consists of
one or more tall, thick-walled, reactors and a network
of furnaces, heat exchangers and other vessels.
Catalytic cracking, or "cat cracking," is the basic petrol-
making process. Using intense heat (about 600°C), low
pressure and a powdered catalyst (a substance that
speeds up a chemical reaction), the cat cracker can
convert most of the heavy fractions into smaller more
useful molecules. Some refineries also have cokers,
which use heat and moderate pressure to turn the
really heavy fractions into lighter products and a hard,
coal like substance that is used as an industrial fuel.
Cracking and coking are not the only forms of
conversion. Other refinery processes, instead of
splitting molecules, rearrange them to add value.
Alkylation makes petrol components by combining
some of the gaseous byproducts of cracking. The
process, which essentially is cracking in reverse, takes
place in a series of large, horizontal vessels.
Reforming uses heat, moderate pressure and catalysts
to turn naphtha into high-octane petrol.

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Naphtha:
Naphtha is a generic term normally used in the
petroleum refining industry for the overhead liquid
fraction obtained from atmospheric distillation units.
The approximate boiling range of light straight-run
naphtha (LSR) is 35–90°C, while it is about 80–200°C
for heavy straight-run naphtha (HSR) .Naphtha is also
obtained from other refinery processing units such as
catalytic cracking, hydrocracking, and coking units. The
composition of naphtha, which varies appreciably,
depends mainly on the crude type and whether it is
obtained from atmospheric distillation or other
processing units. Naphtha from atmospheric distillation
is characterized by an absence of olefinic compounds.
Its main constituents are straight and branchedchain
paraffins, cycloparaffins (naphthenes), and aromatics,
and the ratios of these components are mainly a
function of the crude origin. Naphthas obtained from
cracking units generally contain variable amounts of
olefins, higher ratios of aromatics, and branched
paraffins. Due to presence of unsaturated compounds,
they are less stable than straight-run naphthas. On the
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other hand, the absence of olefins increases the
stability of naphthas produced by hydrocracking units.
In refining operations, however, it is customary to blend
one type of naphtha with another to obtain a required
product or feedstock. Selecting the naphtha type can
be an important processing procedure. For example,
paraffinic-base naphtha is a better feedstock for steam
cracking units because paraffins are cracked at
relatively lower temperatures than cycloparaffins.
Alternately, a naphtha rich in cycloparaffins would be a
better feedstock to catalytic reforming units because
cycloparaffins are easily dehydrogenated to aromatic
compounds. The main use of naphtha in the petroleum
industry is in gasoline production. Light naphtha is
normally blended with reformed gasoline (from catalytic
reforming units) to increase its volatility and to reduce
the aromatic content of the product gasoline. Heavy
naphtha from atmospheric distillation units or
hydrocracking units has a low octane rating, and it is
used as a feedstock to catalytic reforming units.
Catalytic reforming is a process of upgrading low
octane naphtha to a high-octane reformate by enriching

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it with aromatics and branched paraffins. The octane
rating of gasoline fuels is a property related to the
spontaneous ignition of unburned gases before the
flame front and causes a high pressure. Afuel with a
low octane rating produces a strong knock, while a fuel
with a high octane rating burns smoothly without
detonation. Octane rating is measured by an arbitrary
scale in which isooctane (2,2,4-trimethylpentane) is
given a value of 100 and n-heptane a value of zero. A
fuel’s octane number equals the percentage of
isooctane in a blend with n-heptane.The octane number
is measured using a single-cylinder engine (CFR
engine) with a variable compression ratio. The octane
number of a fuel is a function of the different
hydrocarbon constituents present. In general, aromatics
and branched paraffins have higher octane ratings than
straight-chain paraffins and cycloparaffins. Reformates
are the main source for extracting C6-C8 aromatics
used for petrochemicals. Naphtha is also a major
feedstock to steam cracking units for the production of
olefins.

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Kerosine:
Kerosine, a distillate fraction heavier than
naphtha, is normally a product from distilling crude oils
under atmospheric pressures. It may also be obtained
as a product from thermal and catalytic cracking or
hydrocracking units. Kerosines from cracking units are
usually less stable than those produced from
atmospheric distillation and hydrocracking units due to
presence of variable amounts of olefinic constituents.
Kerosine is usually a clear colorless liquid which does
not stop flowing except at very low temperature
(normally below –30°C). However, kerosine containing
high olefin and nitrogen contents may develop some
color (pale yellow) after being produced. The main
constituents of kerosines obtained from atmospheric
and hydrocracking units are paraffins, cycloparaffins,
and aromatics. Kerosines with a high normal-paraffin
content are suitable feedstocks for extracting C12-C14
n-paraffins, which are used for producing
biodegradable detergents. Currently, kerosine is mainly
used to produce jet fuels, after it is treated to adjust its
burning quality and freezing point. Before the
- 21 -
widespread use of electricity, kerosine was extensively
used to fuel lamps, and is still used for this purpose in
remote areas. It is also used as a fuel for heating
purposes.

What is the gasoline octane number?

The octane number of gasoline is a measure of
its resistance to knock. The octane number is
determined by comparing the characteristics of a
gasoline to isooctane (2,2,4-trimethylpentane) and
heptane. Isooctane is assigned an octane number of
100. It is a highly branched compound that burns
smoothly, with little knock. On the other hand, heptane
is given an octane rating of zero. It is an unbranched
compound and knocks badly. Straight-run gasoline has
an octane number of about 70. In other words, straight-
run gasoline has the same knocking properties as a
mixture of 70% isooctane and 30% heptane. Cracking,
isomerization, and other processes can be used to
increase the octane rating of gasoline to about 90. Anti-
knock agents may be added to further increase the
octane rating. Tetraethyl lead, Pb(C2H5)4, was one such
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agent, which was added to gas at the rate of up to 2.4
grams per gallon of gasoline. The switch to unleaded
gasoline has required the addition of more expensive
compounds, such as aromatics and highly branched
alkanes, to maintain high octane numbers. Gasoline
pumps typically post octane numbers as an average of
two different values. Often you may see the octane
rating quoted as (R+M)/2. One value is the research
octane number (RON), which is determined with a test
engine running at a low speed of 600 rpm. The other
value is the motor octane number (MON), which is
determined with a test engine running at a higher speed
of 900 rpm. If, for example, a gasoline has an RON of
98 and a MON of 90, then the posted octane number
would be the average of the two values or 94. High
octane gasoline does not outperform regular octane
gasoline in preventing engine deposits from forming, in
removing them, or in cleaning the engine. Consumers
should select the lowest octane grade at which the
car's engine runs without knocking. Occasional light
knocking or pinging won't harm the engine, and doesn't
indicate a need for higher octane. On the other hand, a

- 23 -
heavy or persistent knock may result in engine
damage.Octane is a measure of a gasoline's antiknock
performance, in other words, its ability to resist
"knocking" which is a metallic rattling or pinging sound
that results from uncontrolled combustion in the
engine's cylinders.

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 CHAPTER II

Petroleum as Primary Raw Materials for

Petrochemicals
In general, primary raw materials are naturally
occurring substances that have not been subjected to
chemical changes after being recovered. Natural gas
and crude oils are the basic raw materials for the
manufacture of petrochemicals. The first part of this
chapter deals with natural gas. The second part
discusses crude oils and their properties. Secondary
raw materials, or intermediates, are obtained from
natural gas and crude oils through different processing
schemes. The intermediates may be light hydrocarbon
compounds such as methane and ethane, or heavier
hydrocarbon mixtures such as naphtha or gas oil. Both
naphtha and gas oil are crude oil fractions with different
boiling ranges. Coal, oil shale, and tar sand are
complex carbonaceous raw materials and possible
future energy and chemical sources. However, they
must undergo lengthy and extensive processing before
they yield fuels and chemicals similar to those
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produced from crude oils (substitute natural gas (SNG)
and synthetic crudes from coal, tar sand and oil shale).
Natural gas (Non-associated and Associated
Natural Gases):
Natural gas is a naturally occurring mixture of
light hydrocarbons accompanied by some non-
hydrocarbon compounds. Non-associated natural gas
is found in reservoirs containing no oil (dry wells).
Associated gas, on the other hand, is present in contact
with and/or dissolved in crude oil and is coproduced
with it. The principal component of most natural gases
is methane.

Higher molecular weight paraffinic hydrocarbons

(C2-C7) are usually present in smaller amounts with the

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natural gas mixture, and their ratios vary considerably
from one gas field to another. Non-associated gas
normally contains a higher methane ratio than
associated gas, while the latter contains a higher ratio
of heavier hydrocarbons. Table 1-1 shows the analyses
of some selected non-associated and associated
gases.1 In our discussion, both non-associated and
associated gases will be referred to as natural gas.
However, important differences will be noted.The non-
hydrocarbon constituents in natural gas vary
appreciably from one gas field to another. Some of
these compounds are weak acids, such as hydrogen
sulfide and carbon dioxide. Others are inert, such as
nitrogen, helium and argon. Some natural gas
reservoirs contain enough helium for commercial
production.Higher molecular weight hydrocarbons
present in natural gases are important fuels as well as
chemical feedstocks and are normally recovered as
natural gas liquids. For example, ethane may be
separated for use as a feedstock for steam cracking for
the production of ethylene. Propane and butane are
recovered from natural gas and sold as liquefied

- 27 -
petroleum gas (LPG). Before natural gas is used it must
be processed or treated to remove the impurities and to
recover the heavier hydrocarbons (heavier than
methane). The 1998 U.S. gas consumption was
approximately 22.5 trillion ft3.
Properties of natural gas:
Treated natural gas consists mainly of methane;
the properties of both gases (natural gas and methane)
are nearly similar. However, natural gas is not pure
methane, and its properties are modified by the
presence of impurities, such as N2 and CO2 and small
amounts of unrecovered heavier hydrocarbons. An
important property of natural gas is its heating value.
Relatively high amounts of nitrogen and/or carbon
dioxide reduce the heating value of the gas. Pure
methane has a heating value of 1,009 Btu/ft3. This
value is reduced to approximately 900 Btu/ft3 if the gas
contains about 10% N2 and CO2. (The heating value of
either nitrogen or carbon dioxide is zero.) On the other
hand, the heating value of natural gas could exceed
methane’s due to the presence of higher-molecular
weight hydrocarbons, which have higher heating
- 28 -
values. For example, ethane’s heating value is 1,800
Btu/ft3, compared to 1,009 Btu/ft3 for methane. Heating
values of hydrocarbons normally present in natural gas
are shown in Table 1-4. Natural gas is usually sold
according to its heating values. The heating value of a
product gas is a function of the constituents present in
the mixture. In the natural gas trade, a heating value of
one million Btu is approximately equivalent to 1,000 ft3
of natural gas.
Crude oils:
Crude oil (petroleum) is a naturally occurring
brown to black flammable liquid. Crude oils are
principally found in oil reservoirs associated with
sedimentary rocks beneath the earth’s surface.
Although exactly how crude oils originated is not
established, it is generally agreed that crude oils
derived from marine animal and plant debris subjected
to high temperatures and pressures. It is also
suspected that the transformation may have been
catalyzed by rock constituents. Regardless of their
origins, Primary Raw Materials for Petrochemicals.

- 29 -
 Table 1: Heating values of methane and heavier
hydrocarbons present in natural gas:

All crude oils are mainly constituted of

hydrocarbons mixed with variable amounts of sulfur,
nitrogen, and oxygen compounds. Metals in the forms
of inorganic salts or organometallic compounds are
present in the crude mixture in trace amounts. The ratio
of the different constituents in crude oils, however,
varies appreciably from one reservoir to another.
Normally, crude oils are not used directly as fuels or as
feedstock's for the production of chemicals. This is due
to the complex nature of the crude oil mixture and the
presence of some impurities that are corrosive or
poisonous to processing catalysts. Crude oils are
refined to separate the mixture into simpler fractions
- 30 -
that can be used as fuels, lubricants, or as intermediate
feedstock to the petrochemical industries. A general
knowledge of this composite mixture is essential for
establishing a processing strategy.

Composition of crude oils:

The crude oil mixture is composed of the following
groups:
1. Hydrocarbon compounds (compounds made of
carbon and hydrogen).
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.

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The following is a brief description of 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. Normal
alkanes (n-alkanes, n-paraffins) are straight-chain
hydrocarbons having no branches. Branched alkanes
are saturated hydrocarbons with an alkyl substituent or
a side branch from the main chain. Abranched alkane
with the same number of carbons and hydrogens as an
n-alkane is called an isomer. For example, butane
(C4H10) has two isomers, n-butane and 2-methyl
propane (isobutane). As the molecular weight of the
hydrocarbon increases, the number of isomers also
increases. Pentane (C5C12) has three isomers; hexane
(C6H14) has five. The following shows the isomers of
hexane:
- 32 -
 An isoparaffin is an isomer having a methyl group
branching from carbon number 2 of the main chain.
Crude oils contain many short, medium, and long-chain
normal and branched paraffins. A naphtha fraction
(obtained as a light liquid stream from crude
fractionation) with a narrow boiling range may contain a
limited but still large number of isomers.
Cycloparaffins (Naphthenes):
Saturated cyclic hydrocarbons, normally known
as naphthenes, are also part of the hydrocarbon
constituents of crude oils. Their ratio, however,
depends on the crude type. The lower members of
naphthenes are cyclopentane, cyclohexane, and their
mono-substituted compounds. They are normally
present in the light and the heavy naphtha fractions.

- 33 -
Cyclohexanes, substituted cyclopentanes, and
substituted cyclohexanes are important precursors for
aromatic hydrocarbons

Only a few aromatic-cycloparaffin compounds

have been isolated and identified. Tetralin is an
example of this class.
Non-hydrocarbon Compounds:
Various types of non-hydrocarbon compounds
occur in crude oils and refinery streams. The most
important are the organic sulfur, nitrogen, and oxygen
compounds. Traces of metallic compounds are also
found in all crudes. The presence of these impurities is
harmful and may cause problems to certain catalytic
processes. Fuels having high sulfur and nitrogen levels
cause pollution problems in addition to the corrosive
nature of their oxidization products.

- 34 -
Sulfur Compounds
Sulfur in crude oils is mainly present in the form of
organosulfur compounds. Hydrogen sulfide is the only
important inorganic sulfur compound found in crude oil.
Its presence, however, is harmful because of its
corrosive nature. Organosulfur compounds may
generally be classified as acidic and non-acidic. Acidic
sulfur compounds are the thiols (mercaptans).
Thiophene, sulfides, and disulfides are examples of
non-acidic sulfur compounds found in crude fractions.
Extensive research has been carried out to identify
some sulfur compounds in a narrow light petroleum
fraction. Examples of some sulfur compounds from the
two types are

Acidic Sulfur Compounds:

- 35 -
Non-acidic Sulfur Compounds:

Sour crudes contain a high percentage of

hydrogen sulfide. Because many organic sulfur
compounds are not thermally stable, hydrogen sulfide
is often produced during crude processing. High-sulfur
crudes are less desirable because treating the different
refinery streams for acidic hydrogen sulfide increases
production costs. Most sulfur compounds can be
removed from petroleum streams through
hydrotreatment processes, where hydrogen sulfide is
produced and the corresponding hydrocarbon released.
Hydrogen sulfide is then absorbed in a suitable
absorbent and recovered as sulfur (Chapter 4).
Nitrogen Compounds:
Organic nitrogen compounds occur in crude oils
either in a simple heterocyclic form as in pyridine
- 36 -
(C5H5N) and pyrrole (C4H5N), or in a complex structure
as in porphyrin. The nitrogen content in most crudes is
very low and does not exceed 0.1 wt%. In some heavy
crudes, however, the nitrogen content may reach up to
0.9 wt %. Nitrogen compounds are more thermally
stable than sulfur compounds and accordingly are
concentrated in heavier petroleum fractions and
residues. Light petroleum streams may contain trace
amounts of nitrogen compounds, which should be
removed because they poison many processing
catalysts. During hydrotreatment of petroleum fractions,
nitrogen compounds are hydrodenitrogenated to
ammonia and the corresponding hydrocarbon. For
example, pyridine is denitrogenated to ammonia and
pentane:

Nitrogen compounds in crudes may generally be

classified into basic and non-basic categories. Basic
nitrogen compounds are mainly those having a pyridine
ring, and the non-basic compounds have a pyrrole
- 37 -
structure. Both pyridine and pyrrole are stable
compounds due to their aromatic nature. The following
are examples of organic nitrogen compounds.
Basic Nitrogen Compounds:

Non-Basic Nitrogen Compounds:

Oxygen Compounds:
Oxygen compounds in crude oils are more
complex than the sulfur types. However, their presence
in petroleum streams is not poisonous to processing
catalysts. Many of the oxygen compounds found in
crude oils are weakly acidic. They are carboxylic acids,
cresylic acid, phenol, and naphthenic acid. Naphthenic
acids are mainly cyclopentane and cyclohexane
derivatives having a carboxyalkyl side chain.
- 38 -
Naphthenic acids in the naphtha fraction have a
special commercial importance and can be extracted
by using dilute caustic solutions. The total acid content
of most crudes is generally low, but may reach as
much as 3%, as in some California crudes. Non-acidic
oxygen compounds such as esters, ketones, and
amides are less abundant than acidic compounds.
They are of no commercial value. The following shows
some of the oxygen compounds commonly found in
crude oils:
Acidic Oxygen Compounds:

- 39 -
Non-Acidic Oxygen Compounds

Metallic Compounds:
Many metals occur in crude oils. Some of the
more abundant are sodium, calcium, magnesium,
aluminium, iron, vanadium, and nickel. They are
present either as inorganic salts, such as sodium and
magnesium chlorides, or in the form of organometallic
compounds, such as those of nickel and vanadium (as
in porphyrins). Calcium and magnesium can form salts
or soaps with carboxylic acids. These compounds act
as emulsifiers, and their presence is undesirable.
Although metals in crudes are found in trace amounts,
their presence is harmful and should be removed.
When crude oil is processed, sodium and magnesium
chlorides produce hydrochloric acid, which is very
corrosive. Desalting crude oils is a necessary step to
- 40 -
reduce these salts. Vanadium and nickel are poisons to
many catalysts and should be reduced to very low
levels. Most of the vanadium and nickel compounds are
concentrated in the heavy residues. Solvent extraction
processes are used to reduce the concentration of
heavy metals in petroleum residues

PROPERTIES OF CRUDE OILS:

Crude oils differ appreciably in their properties
according to origin and the ratio of the different
components in the mixture. Lighter crudes generally
yield more valuable light and middle distillates and are
sold at higher prices. Crudes containing a high percent
of impurities, such as sulfur compounds, are less
desirable than low-sulfur crudes because of their
corrosivity and the extra treating cost. Corrosivity of
crude oils is a function of many parameters among
which are the type of sulfur compounds and their
decomposition temperatures, the total acid number, the
type of carboxylic and naphthenic acids in the crude
and their decomposition temperatures. It was found that
naphthenic acids begin to decompose at 600°F.
- 41 -
Refinery experience has shown that above 750°F there
is no naphthenic acid corrosion. The subject has been
reviewed by Kane and Cayard.20 For a refiner, it is
necessary to establish certain criteria to relate one
crude to another to be able to assess crude quality and
choose the best processing scheme. The following are
some of the important tests used to determine the
properties of crude oils.
Salt Content:
The salt content expressed in milligrams of
sodium chloride per liter oil (or in pounds/barrel)
indicates the amount of salt dissolved in water. Water in
crudes is mainly present in an emulsified form. A high
salt content in a crude oil presents serious corrosion
problems during the refining process. In addition, high
salt content is a major cause of plugging heat
exchangers and heater pipes. A salt content higher
than 10 lb/1,000 barrels (expressed as NaCl) requires
desalting.
Sulfur Content:
Determining the sulfur content in crudes is
important because the amount of sulfur indicates the
- 42 -
type of treatment required for the distillates. To
determine sulfur content, a weighed crude sample (or
fraction) is burned in an air stream. All sulfur
compounds are oxidized to sulfur dioxide, which is
further oxidized to sulfur trioxide and finally titrated with
a standard alkali. Identifying sulfur compounds in
crude oils and their products is of little use to a refiner
because all sulfur compounds can easily be
hydrodesulfurized to hydrogen sulfide and the
corresponding hydrocarbon.
The sulfur content of crudes, however, is important and
is usually considered when determining commercial
values.
CRUDE OIL CLASSIFICATION:
Appreciable property differences appear between
crude oils as a result
of the variable ratios of the crude oil components. For a
refiner dealing with crudes of different origins, a simple
criterion may be established to group crudes with
similar characteristics. Crude oils can be arbitrarily
classified into three or four groups depending on the
relative ratio of the hydrocarbon classes that
- 43 -
predominate in the mixture. The following describes
three types of crudes:
1. Paraffinic—the ratio of paraffinic hydrocarbons is
high compared to aromatics and naphthenes.
2. Naphthenic—the ratios of naphthenic and aromatic
hydrocarbons are relatively higher than in paraffinic
crudes.
3. Asphaltic—contain relatively a large amount of
polynuclear aromatics, a high asphaltene content,
and relatively less paraffins than paraffinic crudes.

- 44 -
 CHAPTER III
Crude Oil Processing and Production of
Hydrocarbon Intermediates

The hydrocarbon intermediates referred to in the

previous chapter are produced by subjecting crude oils
to various processing schemes. These include a
primary distillation step to separate the crude oil
complex mixture into simpler fractions. These fractions
are primarily used as fuels. However, a small
percentage of these streams are used as secondary
raw materials or intermediates for obtaining olefins,
diolefins, and aromatics for petrochemicals production.
Further processing of these fractions may be required
to change their chemical composition to the required
products. These new products may also be used as
fuels of improved qualities or as chemical feedstocks.
For example, reforming a naphtha fraction catalytically
produces a reformate rich in aromatics. The major use
of the reformate is to supplement the gasoline pool due
to its high octane rating. However, the reformate is also
used to extract the aromatics for petrochemicals use. At
- 45 -
this point, the production of intermediates for
petrochemicals is not separable from the production of
fuels. In this part, the production of hydrocarbon
intermediates is discussed in conjunction with different
crude oil processing schemes. These include physical
separation techniques and chemical conversion
processes. The production of olefins is also discussed
in the last section.
PHYSICAL SEPARATION PROCESSES
Physical separation techniques separate a
mixture such as a crude oil without changing the
chemical characteristics of the components. The
separation is based on differences of certain physical
properties of the constituents such as the boiling and
melting points, adsorption affinities on a certain solid,
and diffusion through certain membranes.

CONVERSION PROCESSES
Conversion processes in the petroleum industry are
generally used to:

- 46 -
1. Upgrade lower-value materials such as heavy
residues to more valuable products such as naphtha
and LPG. Naphtha is mainly used to supplement the
gasoline pool, while LPG is used as a fuel or as a
petrochemical feedstock
2. Improve the characteristics of a fuel. For example, a
lower octane naphtha fraction is reformed to a higher
octane reformate product. The reformate is mainly
blended with naphtha for gasoline formulation or
extracted for obtaining aromatics needed for
petrochemicals production.
3. Reduce harmful impurities in petroleum fractions and
residues to control pollution and to avoid poisoning
certain processing catalysts. For example,
hydrotreatment of naphtha feeds to catalytic
reformers is essential because sulfur and nitrogen
impurities poison the catalyst. Conversion processes
are either thermal, where only heat is used to effect
the required change, or catalytic, where a catalyst
lowers the reaction activation energy. The catalyst
also directs the reaction toward a desired product or
products (selective catalyst).
- 47 -
THERMAL CONVERSION PROCESSES
Thermal cracking was the first process used to
increase gasoline production. After the development of
catalytic cracking, which improved yields and product
quality, thermal cracking was given other roles in
refinery operations. The three important thermal
cracking techniques are coking, viscosity breaking, and
steam cracking. Steam cracking is of special
importance as a major process designed specifically for
producing light olefins.
Coking Processes
Coking is a severe thermal cracking process
designed to handle heavy residues with high
asphaltene and metal contents. These residues cannot
be fed to catalytic cracking units because their
impurities deactivate and poison the catalysts. Products
from coking processes vary considerably with feed type
and process conditions. These products are
hydrocarbon gases, cracked naphtha, middle distillates,
and coke. The gas and liquid products are
characterized by a high percentage of unsaturation.
Hydrotreatment is usually required to saturate olefinic
- 48 -
compounds and to desulfurize products from coking
units.
Thermal Cracking Reactions
The first step in cracking is the thermal
decomposition of hydrocarbon molecules to two free
radical fragments. This initiation step can occur by a
homolytic carbon-carbon bond scission at any position
along the hydrocarbon chain. The following represents
the initiation reaction: RCH2CH2CH2Rv r RCH2C˙ H2 +
RvC˙ H2. The radicals may further crack, yielding an
olefin and a new free radical. Cracking usually occurs
at a bond beta to the carbon carrying the unpaired
electron. RCH2C˙ H2 r R˙ + CH2=CH2 Further bond
scission of the new free radical R˙ can continue to
produce ethylene until the radical is terminated. Free
radicals may also react with a hydrocarbon molecule
from the feed by abstracting a hydrogen atom. In this
case the attacking radical is terminated, and a new free
radical is formed. Abstraction of a hydrogen atom can
occur at any position along the chain. However, the rate
of hydrogen abstraction is faster from a tertiary position

- 49 -
than from a secondary, which is faster than from a
primary position.

The secondary free radical can crack on either

side of the carbon carrying the unpaired electron
according to the beta scission rule, and a terminal olefin
is produced.

Free radicals, unlike carbocations, do not

normally undergo isomerization by methyl or hydrogen
migration. However, hydrogen transfer (chain transfer)
occurs when a free radical reacts with other
hydrocarbons. There are two major commercial
thermal cracking processes, delayed coking and fluid
coking. Flexicoking is a fluid coking process in which
the coke is gasified with air and steam. The resulting
gas mixture partially provides process heat

- 50 -
CATALYTIC CONVERSION PROCESSES:
Catalytic conversion processes include naphtha
catalytic reforming, catalytic cracking, hydrocracking,
hydrodealkylation, isomerization, alkylation, and
polymerization. In these processes, one or more
catalyst is used. A common factor among these
processes is that most of the reactions are initiated by
an acid-type catalyst that promotes carbonium ion
formation. Other important catalytic processes are
those directed toward improving the product quality
through hydrotreatment. These processes use
heterogeneous hydrogenation catalysts.
Catalytic Reforming:
The aim of this process is to improve the octane
number of a naphtha feedstock by changing its
chemical composition. Hydrocarbon compounds differ
greatly in their octane ratings due to differences in
structure. In general, aromatics have higher octane
ratings than paraffins and cycloparaffins. Similar to
aromatics, branched paraffins have high octane ratings.
The octane number of a hydrocarbon mixture is a
function of the octane numbers of the different
- 51 -
components and their ratio in the mixture. Increasing
the octane number of a low-octane naphtha fraction is
achieved by changing the molecular structure of the low
octane number components. Many reactions are
responsible for this change, such as the
dehydrogenation of naphthenes and the
dehydrocyclization of paraffins to aromatics. Catalytic
reforming is considered the key process for obtaining
benzene, toluene, and xylenes (BTX). These aromatics
are important intermediates for the production of many
chemicals.

Reformer Feeds:
The feed to a catalytic reformer is normally a heavy
naphtha fraction produced from atmospheric distillation
units. Naphtha from other sources such as those
produced from cracking and delayed coking may also
be used. Before using naphtha as feed for a catalytic
reforming unit, it must be hydrotreated to saturate the
olefins and to hydrodesulfurize and hydrodenitrogenate
sulfur and nitrogen compounds. Olefinic compounds
are undesirable because they are precursors for coke,
- 52 -
which deactivates the catalyst. Sulfur and nitrogen
compounds poison the reforming catalyst. The reducing
atmosphere in catalytic reforming promotes forming of
hydrogen sulfide and ammonia. Ammonia reduces the
acid sites of the catalyst, while platinum becomes
sulfided with H2S. Types of hydrocarbons in the feed
have significant effects on the operation severity. Feeds
with a high naphthene content are easier to aromatize
than feeds with a high ratio of paraffins (see “Reforming
reactions”). The boiling range of the feeds is also an
effective parameter. Feeds with higher end points
(≈200°C) are favorable because some of the long-chain
molecules are hydrocracked to molecules in the
gasoline range. These molecules can isomerize and
dehydrocyclize to branched paraffins and to aromatics,
respectively.
Reforming Catalysts:
The catalysts generally used in catalytic reforming
are dual functional to provide two types of catalytic
sites, hydrogenation-dehydrogenation sites and acid
sites. The former sites are provided by platinum, which
is the best known hydrogenation-dehydrogenation
- 53 -
catalyst and the latter (acid sites) promote carbonium
ion formation and are provided by an alumina carrier.
The two types of sites are necessary for aromatization
and isomerization reactions. Bimetallic catalysts such
as Pt/Re were found to have better stability, increased
catalyst activity, and selectivity. Trimetallic catalysts of
noble metal alloys are also used for the same purpose.
The increased stability of these catalysts allowed
operation at lower pressures. A review of reforming
catalysts by Al-Kabbani manifests the effect of the ratio
of the metallic components of the catalyst. A ratio of 0.5
or less for Pt/Re in the new generation catalysts versus
1.0 for the older ones can tolerate much higher coke
levels. Reforming units can perform similarly with
higher coke levels (20–25% versus 15–20%). These
catalysts can tolerate higher sulfer naphtha feeds (>1
ppm). Higher profitability may be realized by increasing
the cycle length.13
Reforming Reactions
Many reactions occur in the reactor under
reforming conditions. These are aromatization
reactions, which produce aromatics; isomerization
- 54 -
reactions, which produce branched paraffins; and other
reactions which are not directly involved in aromatics
formation (hydrocracking and hydrodealkylation).
Aromatization. The two reactions directly responsible
for enriching naphtha with aromatics are the
dehydrogenation of naphthenes and the
dehydrocyclization of paraffins. The first reaction can
be represented by the dehydrogenation of cyclohexane
to benzene.

This reaction is fast; it reaches equilibrium

quickly. The reaction is also reversible, highly
endothermic, and the equilibrium constant is quite
large.
It is evident that the yield of aromatics (benzene)
is favored at higher temperatures and lower pressures.
The effect of decreasing H2 partial pressure is even
more pronounced in shifting the equilibrium to the right.
The second aromatization reaction is the
- 55 -
dehydrocyclization of paraffins to aromatics. For
example, if n-hexane represents this reaction, the first
step would be to dehydrogenate the hexane molecule
over the platinum surface, giving 1-hexene (2- or 3-
hexenes are also possible isomers,
but cyclization to a cyclohexane ring may occur
through a different mechanism). Cyclohexane then
dehydrogenates to benzene

Isomerization
Reactions leading to skeletal rearrangement of
paraffins and cycloparaffins in a catalytic reactor are
also important in raising the octane number of the
reformate product. Isomerization reactions may occur
on the platinum catalyst surface or on the acid catalyst
sites. In the former case, the reaction is slow. Most
isomerization reactions, however, occur through
formation of a carbocation. The formed carbocation
could rearrange through a hydride-methide shift that

- 56 -
would lead to branched isomers. The following example
illustrates the steps for the isomerization
of n-heptane to 2-methylhexane through 1,2-methide-
hydride shifts: Carbocation Formation:

Hydride Abstraction:

Isomerization of alkylcyclopentanes may also

occur on the platinum catalyst surface or on the
silica/alumina. For example, methylcyclopentane
isomerizes to cyclohexane.

- 57 -
 The formed cyclohexane can dehydrogenate to
benzene. Hydrocracking. Hydrocracking is a
hydrogen-consuming reaction that leads to higher gas
production and lower liquid yield. This reaction is
favored at high temperatures and high hydrogen partial
pressure. The following represents a hydrocracking
reaction

Bond breaking can occur at any position along

the hydrocarbon chain. Because the aromatization
reactions mentioned earlier produce hydrogen and are
favored at high temperatures, some hydrocracking
occurs also under these conditions. However,
hydrocracking long-chain molecules can produce C6,
C7, and C8 hydrocarbons that are suitable for
hydrodecyclization to aromatics. For more aromatics
yield, the end point of the feed may be raised to include
- 58 -
higher molecular weight hydrocarbons in favor of
hydrocracking and dehydrocyclization. However,
excessive hydrocracking is not desirable because it
lowers liquid yields.
Hydrodealkylation
Hydrodealkylation is a cracking reaction of an
aromatic side chain in presence of hydrogen. Like
hydrocracking, the reaction consumes hydrogen and is
favored at a higher hydrogen partial pressure. This
reaction is particularly important for increasing benzene
yield when methylbenzenes and ethylbenzene are
dealkylated. Although the overall reaction is slightly
exothermic, the cracking step is favored at higher
temperatures.

Hydrodealkylation may be represented by the

reaction of toluene and hydrogen. As in hydrocracking,
this reaction increases the gas yield and changes the

- 59 -
relative distribution of the aromatics in favor of
benzene.
Catalytic Cracking:
Catalytic cracking (Cat-cracking) is a remarkably
versatile and flexible process. Its principal aim is to
crack lower-value stocks and produce higher-value light
and middle distillates. The process also produces light
hydrocarbon gases, which are important feedstocks for
petrochemicals. Catalytic cracking produces more
gasoline of higher octane than thermal cracking. This is
due to the effect of the catalyst, which promotes
isomerization and dehydrocyclization reactions.
Products from catalytic cracking units are also more
stable due to a lower olefin content in the liquid
products. This reflects a higher hydrogen transfer
activity, which leads to more saturated hydrocarbons
than in thermally cracked products from delayed coking
units, for example. The feeds to catalytic cracking units
vary from gas oils to crude residues. Heavier feeds
contain higher concentrations of basic and polar
molecules as well as asphaltenes. Examples are basic
nitrogen compounds, which are readily adsorbed on the
- 60 -
catalyst acid sites and lead to instantaneous albeit
temporary deactivation. Polycyclic aromatics and
asphaltenes contribute strongly to coke formation. FCC
(fluid catalytic cracking) catalyst deactivation in resid
processing have been reviewed by O’Connor et al.17
and Occelli.18 These feedstocks are often pretreated to
decrease the metallic and asphaltene contents.
Hydrotreatment, solvent extraction, and propane
deasphalting are important treatment processes.
Excessive asphaltene and aromatics in the feed are
precursors to carbon formation on the catalyst surface,
which substantially reduces its activity and produces
gasolines of lower quality. Residium fluid catalytic
cracking (RFCC) has gained wide acceptance due to a
larger production of gasoline with only small amounts of
lowvalue products. Pretreating the feed in a low-
severity residue desulfurization (RDS) increased the
gasoline yield by 7.4%.19 Table 3-8 compares the
effect of RDS pretreatment on product yields from
RFCC (with and without RDS).19 Other resid treatment
approaches to passivate heavy metals in catalytic

- 61 -
cracking feeds are noted in the following
section“Cracking Catalysts.”
Cracking Catalysts
Acid-treated clays were the first catalysts used in
catalytic cracking processes, but have been replaced
by synthetic amorphous silica-alumina, which is more
active and stable. Incorporating zeolites (crystalline
alumina- silica) with the silica/alumina catalyst improves
selectivity towards aromatics. These catalysts have
both Lewis and Bronsted acid sites that promote
carbonium ion formation. An important structural
feature of zeolites is the presence of holes in the crystal
lattice, which are formed by the silica-alumina
tetrahedra. Each tetrahedron is made of four oxygen
anions with either an aluminum or a silicon cation in the
center. Each oxygen anion with a –2 oxidation state is
shared between either two silicon, two aluminum, or an
aluminum and a silicon cation. The four oxygen anions
in the tetrahedron are balanced by the +4 oxidation
state of the silicon cation, while the four oxygen anions
connecting the aluminum cation are not balanced. This
results in –1 net charge, which should be balanced.
- 62 -
Metal cations such as Na+, Mg2+, or protons (H+)
balance the charge of the alumina tetrahedra. A two-
dimensional representation of an H-zeolite tetrahedra is
shown:

Bronsted acid sites in HY-zeolites mainly

originate from protons that neutralize the alumina
tetrahedra. When HY-zeolite (X- and Y-zeolites are
cracking catalysts ) is heated to temperatures in the
range of 400–500°C, Lewis acid sites are formed
Zeolites as cracking catalysts are characterized by
higher activity and better selectivity toward middle
distillates than amorphous silica-alumina catalysts. This
is attributed to a greater acid sites density and a higher
adsorption power for the reactants on the catalyst
surface. The higher selectivity of zeolites is attributed to
its smaller pores, which allow diffusion of only smaller
molecules through their pores, and to the higher rate of
- 63 -
hydrogen transfer reactions. However, the silicaalumina
matrix has the ability to crack larger molecules.
Hayward and Winkler have recently demonstrated the
importance of the interaction of the zeolite with the
silica-alumina matrix. In a set of experiments using gas
oil and rare earth zeolite/silica-alumina, the yield of
gasoline increased when the matrix was used before
the zeolite. This was explained by the mechanism of
initial matrix cracking of large feedstock molecules to
smaller ones and subsequent zeolite cracking of the
smaller molecules to products. Aluminum distribution in
zeolites is also important to the catalytic activity. An
inbalance in charge between the silicon atoms in the
zeolite framework creates active sites, which determine
the predominant reactivity and selectivity of FCC
catalyst. Selectivity and octane performance are
correlated with unit cell size, which in turn can be
correlated with the number of aluminum atoms in the
zeolite framework. Deactivation of zeolite catalysts
occurs due to coke formation and to poisoning by
heavy metals. In general, there are two types of
catalyst deactivation that occur in a FCC system,

- 64 -
reversible and irreversible. Reversible deactivation
occurs due to coke deposition. This is reversed by
burning coke in the regenerator. Irreversible
deactivation results as a combination of four separate
but interrelated mechanisms: zeolite dealumination,
zeolite decomposition, matrix surface collapse, and
contamination by metals such as vanadium and
sodium.22 Pretreating the feedstocks with hydrogen is
not always effective in reducing heavy metals, and it is
expensive. Other means that proved successful are
modifying the composition and the microporous
structure of the catalyst or adding metals like Sb, Bi or
Sn, or Sb-Sn combination.23 Antimony organics have
been shown to reduce by 50% gas formation due to
metal contaminants, especially nickel.
Cracking Reactions
Amajor difference between thermal and
catalytic cracking is that reactions through catalytic
cracking occur via carbocation intermediate,
compared to the free radical intermediate in thermal
cracking. Carbocations are longer lived and
accordingly more selective than free radicals. Acid
- 65 -
catalysts such as amorphous silica-alumina and
crystalline zeolites promote the formation of
carbocations. The following illustrates the different
ways by which carbocations may be generated in the
reactor. Abstraction of a hydride ion by a Lewis acid
site from a hydrocarbon

2. Reaction between a Bronsted acid site (H+) and an

olefin

3. Reaction of a carbonium ion formed from step 1 or

2 with another hydrocarbon by abstraction of a
hydride ion

- 66 -
 Abstraction of a hydride ion from a tertiary carbon
is easier than from a secondary, which is easier than
from a primary position. The formed carbocation can
rearrange through a methide-hydride shift similar to
what has been explained in catalytic reforming. This
isomerization reaction is responsible for a high ratio of
branched isomers in the products. The most important
cracking reaction, however, is the carbon-carbon beta
bond scission. A bond at a position beta to the
positively-charged carbon breaks heterolytically,
yielding an olefin and another carbocation. This can be
represented by the following example:

The new carbocation may experience another

beta scission, rearrange to a more stable carbonium
ion, or react with a hydrocarbon molecule in the mixture
and produce a paraffin. The carbon-carbon beta
scission may occur on either side of the carbocation,
with the smallest fragment usually containing at least
three carbon atoms. For example, cracking a

- 67 -
secondary carbocation formed from a long chain
paraffin could be represented as follows:

If R = H in the above example, then according to the

beta scission rule (an empirical rule) only route b
becomes possible, and propylene would be a
product:

The propene may be protonated to an isopropyl

carbocation:

An isopropyl carbocation cannot experience a

beta fission (no C-C bond beta to the carbon with the
positive charge).25 It may either abstract a hydride ion
from another hydrocarbon, yielding propane, or revert
back to propene by eliminating a proton. This could
- 68 -
explain the relatively higher yield of propene from
catalytic cracking units than from thermal cracking
units. Aromatization of paraffins can occur through a
dehydrocyclization reaction. Olefinic compounds
formed by the beta scission can form a carbocation
intermediate with the configuration conducive to
cyclization. For example, if a carbocation such as that
shown below is formed (by any of the methods
mentioned earlier), cyclization is likely to occur.

Once cyclization has occurred, the formed

carbocation can lose a proton, and a cyclohexene
derivative is obtained. This reaction is aided by the
presence of an olefin in the vicinity (R–CH=CH2).

- 69 -
 The next step is the abstraction of a hydride ion
by a Lewis acid site from the zeolite surface to form the
more stable allylic carbocation. This is again followed
by a proton elimination to form a cyclohexadiene
intermediate. The same sequence is followed until the
ring is completely aromatized.

During the cracking process, fragmentation of

complex polynuclear cyclic compounds may occur,
leading to formation of simple cycloparaffins. These
compounds can be a source of C6, C7, and C8
aromatics through isomerization and hydrogen transfer
reactions. Coke formed on the catalyst surface is
thought to be due to polycondensation of aromatic
nuclei. The reaction can also occur through a
carbonium ion intermediate of the benzene ring. The
polynuclear aromatic structure has a high C/H ratio.

Hydrocracking Process
- 70 -
 Hydrocracking is essentially catalytic cracking in
the presence of hydrogen. It is one of the most versatile
petroleum refining schemes adapted to process low
value stocks. Generally, the feedstocks are not suitable
for catalytic cracking because of their high metal, sulfur,
nitrogen, and asphaltene contents. The process can
also use feeds with high aromatic content. Products
from hydrocracking processes lack olefinic
hydrocarbons. The product slate ranges from light
hydrocarbon gases to gasolines to residues. Depending
on the operation variables, the process could be
adapted for maximizing gasoline, jet fuel, or diesel
production.
Hydrocracking Catalysts and Reactions
The dual-function catalysts used in hydrocracking
provide high surface area cracking sites and
hydrogenation-dehydrogenation sites. Amorphous
silica-alumina, zeolites, or a mixture of them promote
carbonium ion formation. Catalysts with strong acidic
activity promote isomerization, leading to a high
iso/normal ratios.30 The hydrogenation-
dehydrogenation activity, on the other hand, is provided
- 71 -
by catalysts such as cobalt, molybdenum, tungsten,
vanadium, palladium, or rare earth elements. As with
catalytic cracking, the main reactions occur by
carbonium ion and beta scission, yielding two
fragments that could be hydrogenated on the catalyst
surface. The main hydro-cracking reaction could be
illustrated by the first-step formation of a carbocation
over the catalyst surface

The carbocation may rearrange, eliminate a

proton to produce an olefin, or crack at a beta
position to yield an olefin and a new carbocation.
Under an atmosphere of hydrogen and in the
presence of a catalyst with hydrogenation-
dehydrogenation activity, the olefins are
hydrogenated to paraffinic compounds. This reaction
sequence could be represented as follows:

- 72 -
 As can be anticipated, most products from
hydrocracking are saturated. For this reason, gasolines
from hydrocracking units have lower octane ratings
than those produced by catalytic cracking units; they
have a lower aromatic content due to high
hydrogenation activity. Products from hydrocracking
units are suitable for jet fuel use. Hydrocracking also
produces light hydrocarbon gases (LPG) suitable as
Petrochemical feedstocks.
Hydrodealkylation Process
This process is designed to hydrodealkylate
methylbenzenes, ethylbenzene and C9 + aromatics to
benzene. The petrochemical demand for benzene is
greater than for toluene and xylenes. After separating
benzene from the reformate, the higher aromatics are
charged to a hydrodealkylation unit. The reaction is a
hydrocracking one, where the alkyl side chain breaks
- 73 -
and is simultaneously hydrogenated. For example,
toluene dealkylates to methane and benzene, while
ethylbenzene produces ethane and benzene. In each
case one mole of H2 is consumed:

Consuming hydrogen is mainly a function of the

number of benzene substituents. Dealkylation of
polysubstituted benzene increases hydrogen
consumption and gas production (methane). For
example, dealkylating one mole xylene mixture
produces two methane moles and one mole of
benzene; it consumes two moles of hydrogen.

Unconverted toluene and xylenes are recycled.

- 74 -
Hydrotreatment Processes
Hydrotreating is a hydrogen-consuming process
primarily used to reduce or remove impurities such as
sulfur, nitrogen, and some trace metals from the feeds.
It also stabilizes the feed by saturating olefinic
compounds. Feeds to hydrotreatment units vary widely;
they could be any petroleum fraction, from naphtha to
crude residues. The process is relatively simple:
choosing the desulfurization process depends largely
on the feed type, the level of impurities present, and the
extent of treatment needed to suit the market
requirement. In this process, the feed is mixed with
hydrogen, heated to the proper temperature, and
introduced to the reactor containing the catalyst. The
conditions are usually adjusted to minimize
hydrocracking. Typical reactor temperatures range from
260 to 425°C. Hydrogen partial pressure and space
velocity are important process variables. Increasing the
temperature and hydrogen partial pressure increases
the hydrogenation and hydrodesulfurization reactions.
Lower space velocities are used with feeds rich in
polyaromatics. Total pressure varies widely—from 100
- 75 -
to 3,000 psi—depending on the type of feed, level of
impurities, and the extent of hydrotreatment required.
Figure 3-9 shows an Exxon hydrotreatment unit.
Reactions occurring in hydrotreatment units are mainly
hydrodesulfurization and hydrodenitrogenation of sulfur
and nitrogen compounds. In the first case H2S is
produced along with the hydrocarbon. In the latter case,
ammonia is released. The following examples are
hydrodesulfurization reactions of some representative
sulfur compounds present in petroleum fractions and
coal liquids.

Examples of hydrodonitrogenation of two types of

nitrogen compounds normally present in some light and
middle crude distillates are shown as follows:

- 76 -
 More complex sulfur and nitrogen compounds are
present in heavy residues. These are hyrodesulfurized
and hydrodenitrogenated, but under more severe
conditions than normally used for lighter distillates. For
example, for light petroleum distillates the approximate
temperature and pressure ranges of 300–400°C and
35–70 atm. are used, versus 340–425°C and 55–170
atm. for heavy petroleum residua. Liquid hourly space
velocities (LHSV) in the range of 2–10 hr–1 are used
for light products, while it is 0.2–10 hr–1 for heavy
residues.33
Alkylation Process
Alkylation in petroleum processing produces
larger hydrocarbon molecules in the gasoline range
from smaller molecules. The products are branched

- 77 -
hydrocarbons having high octane ratings. The term
alkylation generally is applied to the acid catalyzed
reaction between isobutane and various light olefins,
and the product is known as the alkylate. Alkylates are
the best of all possible motor fuels, having both
excellent stability and a high octane number. Either
concentrated sulfuric acid or anhydrous hydrofluoric
acid is used as a catalyst for the alkylation reaction.
These acid catalysts are capable of providing a proton,
which reacts with the olefin to form a carbocation. For
example, when propene is used with isobutane, a
mixture of C5 isomers is produced. The following
represents the reaction steps:

The formed carbocation from the last step may

abstract a hydride ion from an isobutane molecule and
- 78 -
produce 2,2-dimethylpentane, or it may rearrange to
another carbocation through a hydride shift.

The new carbocation can rearrange again

through a methide/hydride shift as shown in the
following equation:

The rearranged carbocation finally reacts with

isobutane to form 2,2,3-trimethylbutane.

- 79 -
 The final product contains approximately 60–80%
2,2-dimethylpentane and varying amounts of 2,2,3-
trimethylbutane and 2-methylhexane. The primary
process variables affecting the economics of sulfuric
acid alkylation are the reaction temperature, isobutane
recycle rate, reactor space velocity, and spent acid
strength. To control fresh acid makeup, spent acid
could be monitored by continuously measuring its
density, the flow rate, and its temperature. This can
reduce the acid usage in alkylation units.
Isomerization Process
Isomerization is a small-volume but important
refinery process. Like alkylation, it is acid catalyzed and
intended to produce highly-branched hydrocarbon
mixtures. The low octane C5/C6 fraction obtained from
natural gasoline or from a light naphtha fraction may be
isomerized to a high octane product. Dual-function
catalysts activated by either inorganic or organic
chlorides are the preferred isomerization catalysts. A
typical catalyst is platinum with a zeolite base. These
catalysts serve the dual purpose of promoting
carbonium ion formation and hydrogenation-
- 80 -
dehydrogenation reactions. The reaction may start by
forming a carbocation via abstraction of a hydride ion
by a catalyst acid site. Alternatively, an olefin formed on
the catalyst surface could be protonated to form the
carbocation. The carbocation isomerizes by a 1,2-
hydride/methide shift as mentioned earlier.
Oligomerization of Olefins (Dimerization)
This process produces polymer gasoline with a
high octane. Dimerization was first used (1935) to
dimerize isobutylene to diisobutylene, constituted of
2,4,4-trimethyl-1-pentene (80%) and 2,4,4-trimethyl-2-
pentene (20%). Both phosphoric and sulfuric acid were
used as catalysts. At present, the feedstock is either a
propylene-propane mixture or propylene-butane
mixture where propane and butane are diluents. The
product is an olefin having a high octane number.
When propylene is used, a trimer or a tetramer is
formed. The polymerization reaction is highly
exothermic, so the temperature has to be controlled.
The presence of propane and butane in the mixture
acts as a heat sink to absorb part of the reaction heat.
Typical reaction conditions are 170–250°C and 25–100
- 81 -
atm. The polymerization reaction starts by protonating
the olefin and forming a carbocation. For example,
protonating propene gives isopropyl carbocation. The
proton is provided by the ionization of phosphoric acid:

The next step is the reaction of the carbocation

with the olefin (propene or butene).

The newly-formed carbocation either eliminates a

proton and forms a dimer or attacks another propene
molecule and eliminates a proton, giving the trimer.

- 82 -
 Further protonation of the trimer produces a C9
carbocation which may further react with another
propene molecule and eventually produce propylene
tetramer. The product is a mixture of dimers, trimers,
tetramers, and pentamers having an average RON
(Research Octane Number) = 95. Petrochemicals
satisfy fundamental needs of modern life. Hardly a day
goes by where we do not use or encounter some
product derived from petrochemicals: the carpeting on
which we walk, the plastic soda bottles from which we
drink, the clothing we wear, the fertilizer that grows our
crops, the tires we rely on for transportation, the paints
we use to brighten our surroundings, the
pharmaceuticals we need to remain healthy, the
cosmetics women use to enhance their beauty.
Petrochemical products are made from hydrocarbon
feedstocks through numerous processes and
transformations: Crude oil and natural gas serve as the
feedstocks for petrochemical building blocks; These
building blocks, in turn, are converted into a wide array
of chemical products known as intermediates; The
intermediates are processed into plastics and resins

- 83 -
which, when molded, shaped and/or reformed end up
as consumer products.

- 84 -
 PART TWO
PETROLEUM DERIVATIVES
CHAPTER I
Petrochemicals
Petrochemicals are chemical products made from
raw materials of petroleum or other hydrocarbon origin.
Although some of the chemical compounds that
originate from petroleum may also be derived from coal
and natural gas, petroleum is the major source. Primary
petrochemicals are divided into three groups depending
on their chemical structure: Olefins - include ethylene,
propylene, and butadiene. Ethylene and propylene are
important sources of industrial chemicals and plastics
products. Butadiene is used in making synthetic rubber.
Aromatic Petrochemicals - include benzene, toluene,
and xylenes. Benzene is used in the manufacture of
dyes and synthetic detergents. Toluene is used in
making explosives. Manufacturers use xylenes in
making plastics and synthetic fibres. Synthesis gas - is
a mixture of carbon monoxide and hydrogen, and is
used to make the petrochemicals ammonia and
methanol. Ammonia is used in making fertilizers and
- 85 -
explosives whereas methanol serves as a source for
other chemicals. The synthetic polymer industry
represents the major end use of many petrochemical
monomers such as ethylene, styrene, and vinyl
chloride. Synthetic polymers have greatly affected our
lifestyle. Many articles that were previously made from
naturally occurring materials such as wood, cotton,
wool, iron, aluminum, and glass are being replaced or
partially substituted by synthetic polymers. Clothes
made from polyester, nylon, and acrylic fibers or their
blends with natural fibers currently dominate the
apparel market. Plastics are replacing many articles
previously made of iron, wood, porcelain, or paper in
thousands of diversified applications. Polymerization
could now be tailored to synthesize materials stronger
than steel.l For example, polyethylene fibers with a
molecular weight of one million can be treated to be 10
times stronger than steel! However, its melting point is
148°C. A recently announced thermotropic liquid crystal
polymer based on p-hydroxybenzoic acid, terephthalic
acid, and p, pv-biphenol has a high melting point of
420°C and does not decompose up to 560°C. This

- 86 -
polymer has an initial stress of 106 kg/mm2, even after
6,000 hours of testing The polymer field is versatile and
fast growing, and many new polymers are continually
being produced or improved. The basic chemistry
principles involved in polymer synthesis have not
changed much since the beginning of polymer
production. Major changes in the last 70 years have
occurred in the catalyst field and in process
development. These improvements have a great impact
on the economy. In the elastomer field, for example,
improvements influenced the automobile industry and
also related fields such as mechanical goods and wire
and cable insulation.

OLEFINIC HYDROCARBONS:
The most important olefins used for the
production of petrochemicals are ethylene, propylene,
the butylenes, and isoprene. These olefins are usually
coproduced with ethylene by steam cracking ethane,
liquid petroleum fractions, and residues. Olefins are
characterized by their higher reactivities compared to
paraffinic hydrocarbons. They can easily react with
- 87 -
inexpensive reagents such as water, oxygen,
hydrochloric acid, and chlorine to form valuable
chemicals. Olefins can even add to themselves to
produce important polymers such as polyethylene and
polypropylene. Ethylene is the most important olefin for
producing petrochemicals, and therefore, many sources
have been sought for its production. The following
discusses briefly, the properties of these olefinic
intermediates.
Primary Raw Materials for Petrochemicals:
In general, primary raw materials are naturally
occurring substances that have not been subjected to
chemical changes after being recovered. Natural gas
and crude oils are the basic raw materials for the
manufacture of petrochemicals.
Selective Examples:
Ethylene (CH2=CH2)
Ethylene (ethene), the first member of the
alkenes, is a colorless gas with a sweet odor. It is
slightly soluble in water and alcohol. It is a highly active
compound that reacts easily by addition to many
chemical reagents. For example, ethylene with water
- 88 -
forms ethyl alcohol. Addition of chlorine to ethylene
produces ethylene dichloride (1,2-dichloroethane),
which is cracked to vinyl chloride. Vinyl chloride is an
important plastic precursor. Ethylene is also an active
alkylating agent. Alkylation of benzene with ethylene
produces ethyl benzene, which is dehydrogenated to
styrene. Styrene is a monomer used in the manufacture
of many commercial polymers and copolymers.
Ethylene can be polymerized to different grades of
polyethylenes or copolymerized with other
olefins.Catalytic oxidation of ethylene produces
ethylene oxide, which is hydrolyzed to ethylene glycol.
Ethylene glycol is a monomer for the production of
synthetic fibers. Ethylene is a constituent of refinery
gases, especially those produced from catalytic
cracking units. The main source for ethylene is the
steamcracking of hydrocarbons.
PROPYLENE (CH3CH=CH2):
Like ethylene, propylene (propene) is a reactive
alkene that can be obtained from refinery gas streams,
especially those from cracking processes. The main
source of propylene, however, is steam cracking of
- 89 -
hydrocarbons, where it is coproduced with ethylene.
There is no special process for propylene production
except the dehydrogenation of propane.

Propylene can be polymerized alone or

copolymerized with other monomers such as ethylene.
Many important chemicals are based on propylene
such as isopropanol, allyl alcohol, glycerol, and
acrylonitrile.
BUTYLENES (C4H8):
Butylenes (butenes) are by-products of refinery
cracking processes and steam cracking units for
ethylene production. Dehydrogenation of butanes is a
second source of butenes. However, this source is
becoming more important because isobutylene (a
butane isomer) is currently highly demanded for the
production of oxygenates as gasoline additives. There
are four butene isomers: three unbranched, “normal”
butenes (n-butenes) and a branched isobutene (2-
methylpropene). The three n-butenes are 1-butene and
- 90 -
cis- and trans- 2-butene. The following shows the four
butylene isomers:

The industrial reactions involving cis- and trans-2-

butene are the same and produce the same products.
There are also addition reactions where both l-butene
and 2-butene give the same product. For this reason, it
is economically feasible to isomerize 1-butene to 2-
butene (cis and trans) and then separate the mixture.
The isomerization reaction yields two streams, one of
2-butene and the other of isobutene, which are
separated by fractional distillation, each with a purity of
80–90%. The following table shows the boiling points of
the different butene isomers.

- 91 -
Structure and boiling points of C4 olefins

Double bonds are separated by only one single

bond, the compound is a conjugated diene (conjugated
diolefin). Nonconjugated diolefins have the double
bonds separated (isolated) by more than one single
bond. This latter class is of little industrial importance.
Each double bond in the compound behaves
independently and reacts as if the other is not present.
8 Examples of nonconjugated dienes are 1,4-
pentadiene and 1,4- cyclohexadiene. Examples of
conjugated dienes are 1,3-butadiene and 1,3-
cyclohexadiene.

- 92 -
 An important difference between conjugated and
nonconjugated dienes is that the former compounds
can react with reagents such as chlorine, yielding 1,2-
and 1,4-addition products. For example, the reaction
between chlorine and 1,3-butadiene produces a
mixture of 1,4-dichloro-2-butene and 3,4-dichloro- 1-
butene

When polymerizing dienes for synthetic rubber

production, coordination catalysts are used to direct
the reaction to yield predominantly 1,4-addition
polymers.

- 93 -
BUTADIENE (CH2=CH-CH=CH2)
Butadiene is by far the most important monomer
for synthetic rubber production. It can be polymerized
to polybutadiene or copolymerized with styrene to
styrene-butadiene rubber (SBR). Butadiene is an
important intermediate for the synthesis of many
chemicals such as hexamethylenediamine and adipic
acid. Both are monomers for producing nylon.
Chloroprene is another butadiene derivative for the
synthesis of neoprene rubber. The unique role of
butadiene among other conjugated diolefins lies in its
high reactivity as well as its low cost. Butadiene is
obtained mainly as a coproduct with other light olefins
from steam cracking units for ethylene production.
Other sources of butadiene are the catalytic
dehydrogenation of butanes and butenes, and
dehydration of 1,4-butanediol. Butadiene is a colorless
gas with a mild aromatic odor.

- 94 -
 Isoprene (2-methyl-1,3-butadiene) is a colorless
liquid, soluble in alcohol but not in water. Its boiling
temperature is 34.1°C. Isoprene is the second
important conjugated diene for synthetic rubber
production. The main source for isoprene is the
dehydrogenation of C5 olefins (tertiary amylenes)
obtained by the extraction of a C5 fraction from catalytic
cracking units. It can also be produced through several
synthetic routes using reactive chemicals such as
isobutene, formaldehyde, and propene. The main use
of isoprene is the production of polyisoprene. It is also a
comonomer with isobutene for butyl rubber production.

- 95 -
 CHAPTER TWO

DETERGENTS

The Detergency Process:

It could be defined as ‘the act of cleaning the

surface of a soiled material in a liquid bath in which a
solute (or solutes) which aids this cleaning (detergents)
are dissolved’. Many widely different processes
contribute to the cleaning, and their relative importance
depends very greatly on the nature of the substrate, the
nature of the dirt to be removed, and the cleaning
conditions (detergent concentration, temperature,
degree of agitation).

Most important detergency systems use water as

solvent and, for simplicity, the discussion is restricted to
detergents designed for use in water.

Any successful detergent system must do two

things:

1. It must detach the dirt from the surface to be

cleaned.

- 96 -
2. It must disperse or dissolve the dirt in the wash
liquor in such a way that the cleaned substrate
can be separated from the wash liquor without the
dirt being redeposited on it.

The key to both these requirements is:

The nature of the interfaces between the

substrate, the dirt, and the wash liquor. A fully
formulated detergent system functions by modifying the
properties of these interfaces, thus changing the energy
of the interactions between the dirt and the substrate.
To do this, the detergent formulation must contain
materials that are adsorbed at these interfaces, i.e. it
must contain surface-active material (surfactants).

Surfactants:

Surfactants can be represented by a general

formula RX where R is a hydrophobic tail group, in
almost all cases a hydrocarbon residue, and X is a
hydrophilic head group such as —COO–.

Depending on the nature of R and X, such

molecules may be either water-soluble or oil-soluble
and the balance between the hydrophilic and the
- 97 -
hydrophobic groups largely determines the detergent
properties.

The hydrocarbon chain of a water-soluble

surfactant is not entirely comfortable in bulk aqueous
solution. This is not because of repulsion between the
hydrocarbon chain and water. In fact, the van der
Waals attraction of water for the hydrocarbon chain is
slightly greater than the attraction between paraffin
chains but both these attractions are much lower than
the water—water attraction (H-Bond).

Liquid water consists of a three-dimensional

hydrogen-bonded network of water molecules, the
hydrogen bonds being continually broken and formed.
A paraffin chain modifies the interactions of the water
molecules near it so as to give a different kind of
structure. Under most circumstances there is a
tendency to restore the bulk water structure, and the
surfactant molecule always tends to take up a position
in which its chain is at least partially removed from the
bulk solution. The most obvious way for it to effect this
is for surfactant molecules to congregate at the
interface between its aqueous solution and air, and also
- 98 -
at interfaces with oil and with certain solids if these are
present in the system. This adsorption at the interfaces
has a quite drastic effect on the interfacial properties,
particularly interfacial tensions, which are considerably
lowered.

Synthetic Surfactants:

Surfactants are usually classified, according to the

charge carried by their head group, into:

1. Anionic surfactants, e.g. CH3(CH2)11OSO3–Na+

2. Non-ionic surfactants, e.g.

CH3(CH2)11(OCH2CH2)8OH

3. Cationic surfactants, e.g.

[CH3(CH2)17]2N+(CH3)2Cl–

There are very many examples within each class and

only materials of actual or potential industrial
importance are considered in this book.

1. Anionic Surfactants:

The anionics are by far the most important

surfactants and its structure contain C10-15 saturated
hydrocarbon chains attached directly or indirectly to

- 99 -
sulphonate or sulphate groups, and the major uses are
in domestic fabric washing and dishwashing products:-

a- Biologically Hard Branched-chain

Alkylbenzenesulphonate. The first synthetic anionic
surfactants to be commercially exploited on a large
scale were based on alkylbenzenes produced by
tetramerizing propylene and adding the resultant
mixture of highly branched dodecenes to benzene.

H3PO4 catalyst CH3 CH3 CH3

4 CH3CH=CH2 CH3-C=C-CH-CH-CH3
Tetramization step
Propylene CH2CH2CH3

HF or AlCl3

CH3 CH3 CH3 CH3 CH3 CH3

1) SO3
CH3-C-C-CH-CH-CH3 CH3-C-C-CH-CH-CH3
CH2CH2CH3 2)NaOH CH CH CH
2 2 3

Dodecyl benzene
SO3Na

Both the propylene tetramerization and the

Friedel—Crafts alkylation involves intermediates with
carbonium ion character in which carbon-skeletal
rearrangements and hydride shifts can occur. The
above formula simply gives structures representative of
- 100 -
the numerous highly branched propylene tetramers and
dodecyl benzenes formed.

These dodecylbenzenes can be converted into

sodium dodecyl benzenesulphonate in very high yield.
This is a good surfactant with excellent foaming
properties and, since it is derived from cheap and
readily available raw materials.

As its calcium salt is much more soluble than

calcium soap, it requires a builder to be effective when
used for fabric washing in hard water. Sodium
triphosphate (Na5P3O10) is an efficient cheap builder.
Propylene-tetramer-based materials have one very
important defect. They are biologically ‘hard’, i.e. they
degrade biologically rather slowly. This meant that a
significant proportion of the sodium
alkylbenzenesulphonate entering domestic drains
survived “sewage treatment and was discharged into
rivers and lakes. This resulted in unpleasant foams
during sewage treatment and on rivers. These foams
were not only aesthetically undesirable; they interfered
severely with the sewage treatment and also inhibited
the normal uptake of oxygen by natural waters.
- 101 -
Consequently these biologically hard surfactants had to
be withdrawn in densely populated areas.

b- Biologically Soft Straight-Chain

Alkylbenzenesulphonates. The slow rate of
biodegradation of propylene-tetramer-based
alkylbenzenesulphonates is caused by the highly
branched alkyl group which they contain. Sodium
alkylbenzenesulphonates with straight-chain alkyl
groups are much more rapidly biodegraded, i.e. they
are biologically ‘soft’. The long straight-chain alkyl
group in these soft alkylbenzenesulphonates is derived
either from n-paraffins in the C10-15 range or from
paraffin waxes (C15-35). The n-paraffins are isolated
from kerosene petroleum fractions by molecular-sieve
(MS) techniques or urea-clathration methods; both
methods give straight-chain paraffins of greater than
90% purity. The paraffins are converted either into
monochiloroparaffins or into non-terminal olefins which
are then used to alkylate benzene under Friedel—
Crafts conditions. Paraffin waxes are cracked to give a
range of terminal olefins of widely different chain length;
this mixture is fractionated to give the fraction which is
- 102 -
used to alkylate benzene. The linear alkyl benzene can
be converted into the corresponding straight-chain
sodium alkyl benzenesulphonates. Its properties
depend both on the chain length of the alkyl chain. Alkyl
benzenes with low 2-phenyl isomer contents are
generally considered best and a number of companies
have developed their individual approaches for
controlling the isomerizations so as to minimize 2-
phenyl content.
MS n-Paraffins Cl2 Mixed sec-Mono-
Kerosine chloroparaffins
in C10-15 range

Catalytic
Dehydrogenation

AlCl3

Mixed non-terminal
CH3(CH2)mCH(CH2)nCH3
Olefins

Benzene
AlCl3 Soft Linear Alkyl Benzene
(LAB)

Cracking Terminal 1) SO3

Paraffin Wax 2) NaOH
Olifins

CH3(CH2)mCH(CH2)nCH3

SO3Na

- 103 -
c- Other Synthetic Anionic Surfactants. From the point
of view of surfactancy, the benzene ring in
alkylbenzenesulphonates is not strictly necessary. It is
really present in the molecule to provide a convenient
means of attaching the hydrophilic sulphonate group to
a hydrophobic alkyl chain. A number of other methods
for attaching long alkyl chains to anionic groups have
been developed and are detailed below. Most of the
anionic surfactants produced by these methods could
give performance comparable to that of
alkylbenzenesulphonates in fabric washing and/or other
detergency applications, and each of them has its own
technical and economic advantages and
disadvantages. In the future, some of these alternative
surfactants may well displace part of the alkyl
benzenesulphonate now used.

i- Olefin-Sulphonates: By telomerization route, reaction

of ethylene with triethylaluminum at moderate
temperature and high pressure.

CH3CH2CH2CH2
(CH3CH2)3Al + CH2=CH2 CH3CH2CH2CH2 Al
CH3CH2CH2CH2
- 104 -
 The reaction conditions then changed, either by
increasing the temperature or by introducing a catalyst
such as colloidal nickel, to give a displacement
reaction.

CH3CH2CH2CH2 CH3CH2CH2CH2CH=CH2 +
CH3CH2CH2CH2 Al + 6 CH2=CH2 CH3CH2CH2CH2CH=CH2 +
CH3CH2CH2CH2 CH3CH2CH2CH2CH=CH2 +

(CH3CH2)3Al

Olefins are sulphonated with sulphur trioxide

(SO3) to give alkenesulphonic acids which react again
with (SO3) to give alkenedisulphonic acids and sultons.

R-CH2CH2CH=CH2 + SO3 [ R-CH2CH2CHCH2SO3]

[ R-CH2CH2CH----CH2]
R-CH2CH=CHCH2SO3H
O SO2
SO3
R
R-CH2CH-CH2-CH2 Sultone-Sulphonic
O Acids
O SO2
SO2

- 105 -
 This complex mixture of sulphonates produced
from these reactions, termed α-olefin sulphonate, is
rapidly biodegradable and is an excellent surfactant.

ii- Alkyl Sulphonates. These were amongst the first

synthetic surfactants to be used in detergent products
and were originally prepared by sulphating long-chain
alcohols produced by hydrogenation of esters of fatty
acids.

H2
CH3(CH2)16COOR CH3(CH2)16CH2-OH + R-OH
Cu Chromite
1) SO3
2) NaOH
CH3(CH2)16CH2-OSO3Na

Secondary alkyl sulphates are prepared by

treating long-chain olefins with 90—95% sulphuric acid.

H2SO4
CH3(CH2)9CH=CH2 CH 3(CH 2)9CH-OSO 3H

CH 3

NaOH
CH3(CH2)9CH-OSO3Na

CH3

- 106 -
2. Non-ionic Surfactants:

Non-ionic surfactants are composed of a long

hydrophobic alky group connected to a highly polar
neutral group. The polar group must be sufficiently
hydrophilic to take the hydrophobic group into aqueous
solution. Sugar units such as glucose can do this and
for example, n-dodecyl β-glucoside (A) functions as a
non-ionic surfactant.

HO
O (A)
HO
O
HO (CH2)11CH3
OH

Some industrially produced non-ionic surfactants

are in fact based on sugars and related polyols, but by
far the most important class are those represented by
the general structure (B) in which the hydrophilic group
is a polyoxyethylene chain, R contains a long
hydrocarbon chain and X is a linking group such as —
O— or —COO—. These are produced by treating a
substrate RXH with ethylene oxide. Such reactions of
materials with different numbers of oxyethylene (-
OCH2CH2O-) groups attached to the hydrophobic R
- 107 -
group; n in formula (B) represents the average number
of oxyethylene groups attached to the hydrophobe.

RXH + n CH2 CH2 RX[CH2CH2O]nH

O (B)

These surfactants also show unusual solubility

characteristics. If the temperature of an aqueous
solution of a polyoxyethylene non-ionic surfactant is
raised, a temperature termed the cloud point is reached
at which the solution becomes turbid.

3. Cationic Surfactants:

Cationic surfactants are composed of a

hydrophobic alkyl group attached to a positively
charged hydrophilic group. All the industrially important
materials of this class are based on quaternary nitrogen
compounds or amines.

The most widely used route to them, termed the

fatty route, starts from long-chain fatty acids. These are
converted by NH3 at 200—300°C into nitriles which are
hydrogenated either to the corresponding primary
amines or to amines containing two long-chain alkyl

- 108 -
groups. The primary amine, obtained by using Raney
nickel at 100—150°C. The secondary amine is obtained
by change of conditions to >200°C.

n-C17H35CH2-NH2

n-C17H35COOH n-C17H35CN
(n-C17H35)2NH

The amines are converted into a number of

derivatives that are used technically, the most important
being quaternary compounds, e.g. (I), amine acetate
(II) and the so-called ‘fatty diamines’ (III). Their
production is outlined in the above reactions, where R
is usually a mixture of long-chain alkyl groups derived
from tallow fatty acids.

CH3Cl
R2NH (CH3)2NR2Cl (I)
NaOH

CH3Cl (CH3)2NR2Cl (I)

NaOH

CH3COOH
R-NH2 NH3ROOCCH3 (II)

CH2=CHCN
RNHCH2CH2CN
H2

RNHCH2CH2CH2NH2 (III)

- 109 -
 CHAPTER THREE

Lubricating Oils Chemistry

Background

Since the Roman era, many liquids, including water,

have been used as lubricants to minimize the friction,
heat and wear between mechanical parts in contact
with each other. Today, lubricating oil, or lube oil, is the
most commonly used lubricant because of its wide
range of possible applications.

The term ''lubricating oils'' is generally used to

include all the classes of lubricating materials that are
applied as fluids. Lubricating oils are composed of base
oils plus additives to enhance specific characteristics.
The term ''base stock'' replaces ''base oil''; the two are
synonymous (similar in meaning).

Lubricating base stock is made from the more

viscous portion of the crude oil, which remains after
removal by distillation of the gas oil and lighter
fractions. They have been prepared from crude oils
obtained from most parts of the world.

- 110 -
Lubrication and Lubricants

a- Purpose of lubrication

The primary purpose of lubrication is to reduce wear

and heat between contacting surfaces in relative
motion. While wear and heat cannot be completely
eliminated, they can be reduced to negligible or
acceptable levels. Because heat and wear are
associated with friction, both effects can reduce the
coefficient of friction between the contacting surfaces.
Lubrication is also used to reduce oxidation and
prevent rust; to provide insulation in transformer
applications; to transmit mechanical power in hydraulic
fluid power applications; and to seal against dust, dirt,
and water.

a- Lubricants.

Reduced wear and heat are achieved by inserting a

lower---viscosity (shear strength) material between
wearing surfaces that have a relatively high coefficient
of friction. In effect, the wearing surfaces are replaced
by a material with a more desirable coefficient of
friction. Any material used to reduce friction in this way
- 111 -
is a lubricant. Lubricants are available in liquid, solid,
and gaseous forms.

Oil Refining

Most lubricating oils are currently obtained from

distillation of crude petroleum. Due to the wide variety
of Petroleum constituents, it is necessary to separate
petroleum into portions (fractions) with roughly the
same Qualities.

a- Separation into fractions.

Separation is accomplished by a two-stage process:

crude distillation and residuum distillation.

(1) Crude distillation.

In the first stage the crude petroleum is mixed with

water to dissolve any salt. The resulting brine is
separated by settling (Sedimentation). The remaining
oil is pumped through a tubular furnace where it is
partially vaporized. The components that have a low
number of carbon atoms vaporize and pass into a
fractionating column or tower. As the vapors rise in the
column, cooling causes condensation. By controlling

- 112 -
the temperature, the volatile components may be
separated into fractions that fall within particular boiling
point ranges. In general, compounds with the lowest
boiling points have the fewest carbon atoms and
compounds with the highest boiling points have the
greatest number of carbon atoms. This process
reduces the number of compounds within each fraction
and provides different qualities. The final products
derived from this first-stage distillation process are raw
gasoline, kerosene, and diesel fuel.

(2) Residuum distillation.

The second-stage process involves distilling the

portion of the first-stage that did not volatilize.
Lubricating oils are obtained from this portion, which is
referred to as the residuum. To prevent formation of
undesired products, the residuum is distilled under
vacuum so it will boil at a lower temperature. Distillation
of the residuum produces oils of several boiling point
ranges. The higher the boiling point, the higher the
carbon content of the oil molecules in a given range.
More importantly, viscosity also varies with the boiling

- 113 -
point and the number of carbon atoms in the oil
molecules.

c. Impurity removal.

Once the oil is separated into fractions, it must be

further treated to remove impurities, waxy resins, and
asphalt. Oils that have been highly refined are usually
referred to as premium grades to distinguish them from
grades of lesser quality in the producer's line of
products. However, there are no criteria to establish
what constitutes premium grade.

- 114 -
 1- Solvent refining to remove undesirables
compounds.

2- Solvent dewaxing to remove compounds

that forms crystalline materials at low
temp.

3- Catalyt hydrogenation to eliminate

compounds that would easily oxidized.

4- Clay percolation to remove polar

substance.

5- The various fractions are blended to

obtain a finished product with the
specified viscosity.

Solvent
extraction Solvent Clay
upgrade Dewax Finish

Atmospheric Vacuum
or Base
Distillation oils
Residuum

Hydrotreat Hydro-
upgrade Hydro-
Finish
Dewax

Figure 3 Lube processing schemes extraction (top) and conversion (bottom)

- 115 -
Synthesized hydrocarbons fluids (SHFs).

The SHFs comprise the fastest growing type of

synthetic base stock. They are pure hydrocarbons,
manufactured from row material derived from crude oil.
Three types are used in considerable volume: Olefin
oligomers, dialkylated aromatics, and polybutenes. A
fourth type, cycloaliphatics, is used in small volumes in
specialized applications.

1- Olefin Oligomers (polyalphaolefins)

Olefine oligomers, also called polyalphaolefins

(PAOs), are formed by combining a low molecular
weight material, usually ethylene, into a specific olefin.
This olefin is oligomerized into a lubricating oil type
material, and then hydrogen stabilized. In this sense,
oligomerization is a polymerization process in which a
few, usually three to ten, of the basic building block
molecules are combined to form the finished material.
Therefore, the product may be formed with varying
molecular wights and attendant viscosities to meet a
broad rang of requirements. Polymerization in the usual
- 116 -
sense involves condensation of the same basic building
blocks (monomers). The structure of a typical olefin
oligomer base oil molecule is shown in figure 1.

H3C CH CH2 CH CH2 CH2

CH2 H2C CH2

CH2 CH2 CH2

CH2 CH2 CH2

CH2 CH2 CH2

CH2 CH2 CH2

CH2 CH2 CH2

CH2 CH2 CH2

CH3 CH3 CH3

Figure 1. Olifin oligomer. This compound, an oligomer of 1-decene.

Olefin oligomers can be considered to be a special type

of parafinic mineral oil, comparable in properties to the
best components found in petroleum derived base oil.
They have high viscosity indexes (usually > 135 VI),
excellent low temperature fluidity, and very low pour
point. As a result of the saturated nature of the

- 117 -
hydrocarbons, both their oxidation and thermal stability
are good. Volatility is lower than with comparably
viscous mineral oils; thus, evaporation loss at elevated
temperatures is lower

2- Alkylated Aromatics

The alkylation of an aromatic compound, usually

benzene or naphthalene, is another widely used
method of synthesizing hydricarbones. The alkylation
process involves the joining to the aromatic molecule of
substituent alkyl groups. Generally, the alky; groups
used contain from 10 to 14 carbon atoms are of normal
paraffinic configuration. The properties of the final
product can be altered by changing the structure and
position of the alkyl groups. Dialkylated benzene, a
typical alkylated aromatic in the lubricating oil range, is
shown as the following:-

- 118 -
Alkylated aromatic. This structure represents dialky;ated benzene; R is
an alkyl group that usually contains 10-14 carbon atoms for products in
the lubricating oil range.

Alkylated aromatics have excellent low temperature

fluidity and low pour points, and they exhibit good
solubility for additives. Their viscosity indexes are about
the same as, or slightly higher than, those of high VI
mineral oils.

3- Polybutenes

Polybutenes are produced by controlled

polymerization of butenes and isobutene (isobutylene).
A typical structure is shown in figure 2. The lower
molecular weight materials produced by this process
have lubricating properties, while higher molecular
weight materials, usually referred to as
polyisobutylenes (PIBs), are often used as VI improvers
and thickeners.

- 119 -
 Polybutenes in the lubricating oil rang have viscosity
indexes between 70 and 110 and fair lubricating
properties. An important characteristic in a number of
applications is that above their decomposition
temperature, which is approximately 288 °C, the
products decompose completely to gaseous material.

4- Cycloaliphatics

Cycloaliphatics are a class of synthesized

hydrocarbons now used in small quantities because of
certain special properties they possess. One typical
structure is shown in figure. Cycloaliphatics are
sometimes referred to as traction fluids.

- 120 -
 These lubricants provide performance
characteristics closest to mineral oils and are
compatible with them.

Applications include engine and turbine oils,

hydraulic fluids, gear and bearing oils, and compressor
oils.

(B) Organic esters.

Diabasic acid and polyol esters are the most

common types. The properties of these oils are easily
enhanced through additives. Applications include
crankcase oils and compressor lubricants. Organic
esters are oxygen containing compounds that result
from the reaction of an alcohol with an organic acid.
The two commonly use classes of organic esters are
dibasic acid ester and polyol ester.

1- Dibasic acid ester

The various diesters differ in their acid and alcohol

components. For all diesters, the acid and alcohol are
reacted either thermally or in the presence of a catalyst
in an esterfication reactor. After the ester has been
formed, the water by-product is distilled off and
- 121 -
unreacted dibasic acid is neutralized and removed by
filtration. The base stock is then suitable for final
product blending. As shown in figure, the backbone of
the structure is formed by the acid with the alcohol
radicals to its ends.

Dibasic acid ester: Commenly used acids are adipic (n = 4), azelaic (n =
7), and sebcic (n = 8).

These products were developed originally for use as

jet engine oils, but now have been replaced, to a large
extent, by poyol esters.

(2) Polyolester:-

Poyol esters are made by reacting of polyhydric

alcohol with a monobasic acid to the desired ester. In
contrast to diester, as shown in figure, in the poyol
esters, the poyol forms the backbone of the structure
with acid radical attached to it. Trimethylol propane and
pentaerithritol are two of the poyols that are commonly
- 122 -
used. Usually, the acids are obtained from animal or
vegetable oils.

The primary use of poyol diesters is in type II jet

engine oils. They also used ai air compressor oils and
as components in some synthesized hydrocarbon
blends. more, recently, polyol esters have become
widely used as refrigeration lubricants, to take

- 123 -
advantage of their miscibility with hydrofluorocarbon
(HFC) refrigerants.

C- Polyglycols

Polyglycols cover a wide range of the products and

properties. Presently, they are the largest single clss of
synthetic lubricant bases.

Polyglycols are variously described as poyalkene

glycols, poyethers, poyglycols ethers, and polyalkene
glycol ethers. The latter term is the most complete and
accurate for the bulk of the materials used in lubricants.

Small glycols, such as ethylene and polyethylene

glycol, are also used as hydraulic bracke fluids. Typical
structures for the two types are shown in the figure.

` Polyglycols are polymers made from ethylene oxide

(EO), propylene oxide (PO), or their derivatives.

Glycols. Ethylene glycol is the simplest glycol; when polymerized, the

oxygen bond is formed and it becomes a polyglycol ether
- 124 -
(c) Phosphate esters

Phosphate esters are one of the other commonly

used classes of synthetic base fluids. A typical structure
is shown in the figure.

In the figure. Phosphate ester. The R group can be either an aryl or an

alkyl type

One of the major features of the phosphate esters is

their fire-resistance applications which are superior to
mineral oils. Their lubricating properties are also good.

Other synthetic lubricating fluids:-

(1) Silicones. These oils are chemically inert, nontoxic,

fire-resistant, and water repellant. They also have
low pour points and volatility, good low-
temperature fluidity, and good oxidation and

- 125 -
 thermal stability at high temperatures. Its structure
is shown below.

Characteristics of Lubricating Oils

a. Viscosity.

Technically, the viscosity of oil is a measure of the

oil’s resistance to shear. Viscosity is more commonly
known as resistance to flow. If lubricating oil is
considered as a series of fluid layers superimposed on
each other, the viscosity of the oil is a measure of the

- 126 -
resistance to flow between the individual layers. A high
viscosity implies a high resistance to flow while a low
viscosity indicates a low resistance to flow. Viscosity
varies inversely with temperature. Viscosity is also
affected by pressure; higher pressure causes the
viscosity to increase, and subsequently the load-
carrying capacity of the oil also increases. This property
enables use of thin oils to lubricate heavy machinery.
The load-carrying capacity also increases as operating
speed of the lubricated machinery is increased. Two
methods for measuring viscosity are commonly
employed: shear and time.

(1) Shear. When viscosity is determined by directly

measuring shear stress and shear rate, it is
expressed in centipoise (cP) and is referred to as
the absolute or dynamic viscosity. In the oil
industry, it is more common to use kinematic
viscosity, which is the absolute viscosity divided by
the density of the oil being tested. Kinematic
viscosity is expressed in centistokes (cSt).
Viscosity in centistokes is conventionally given at

- 127 -
 two standard temperatures: 40 EC and 100 °C
(104 EF and 212 °F).

(2) Time. Another method used to determine oil

viscosity measures the time required for an oil
sample to flow through a standard orifice at a
standard temperature. Viscosity is then expressed
in SUS (Saybolt Universal Seconds). SUS
viscosities are also conventionally given at two
standard temperatures: 37 °C and 98 °C (100 °F
and 210 °F). As previously noted, the units of
viscosity can be expressed as centipoises (cP),
centistokes (cST), or Saybolt Universal Seconds
(SUS), depending on the actual test method used
to measure the viscosity.

b. Viscosity index.

The viscosity index, commonly designated VI, is an

arbitrary numbering scale that indicates the changes in
oil viscosity with changes in temperature. Viscosity
index can be classified as follows: low VI - below 35;
medium VI - 35 to 80; high VI - 80 to 110; very high VI -
above 110. A high viscosity index indicates small oil

- 128 -
viscosity changes with temperature. A low viscosity
index indicates high viscosity changes with
temperature. Therefore, a fluid that has a high viscosity
index can be expected to undergo very little change in
viscosity with temperature extremes and is considered
to have a stable viscosity. A fluid with a low viscosity
index can be expected to undergo a significant change
in viscosity as the temperature fluctuates. For a given
temperature range, say -18 to 370 °C (0 - 100 °F), the
viscosity of one oil may change considerably more than
another. An oil with a VI of 95 to 100 would change less
than one with a VI of 80. Knowing the viscosity index of
oil is crucial when selecting a lubricant for an
application, and is especially critical in extremely hot or
cold climates. Failure to use an oil with the proper
viscosity index when temperature extremes are
expected may result in poor lubrication and equipment
failure. Typically, paraffinic oils are rated at 38 °C (100
°F) and naphthenic oils are rated at -18 °C (0 °F).
Proper selection of petroleum stocks and additives can
produce oils with a very good VI.

- 129 -
 b- Pour point.

The pour point is the lowest temperature at which oil

will flow. This property is crucial for oils that must flow
at low temperatures. A commonly used rule of thumb
when selecting oils is to ensure that the pour point is at
least 10 °C (20 °F) lower than the lowest anticipated
ambient temperature. The pour point of the lubricating
oil is the lowest temperature at which it will pour or flow
when it is chilled without disturbance under prescribed
conditions. Most mineral oils contain some dissolved
wax and as an oil is chilled, this wax begins to separate
as crystal that interlock to form a rigid structure that
traps the oil in small pockets in the structure. When this
wax crystal structure becomes sufficiently complete, the
oil will no longer flow under the conditions of the test.

While the pour point of most oils is related to the

crystallization of wax, certain oils, which are essentially
wax free, have viscosity-limited pour points. In these
oils the viscosity becomes progressively higher as the
temperature is lowered until at some temperature no
flow can be observed. The pour points of such oils
cannot be lowered with pour point depressant, since
- 130 -
these agents act by interfering with the growth and
interlocking of the wax crystal structure.

b. Cloud point.

The cloud point is the temperature at which

dissolved solids in the oil, such as paraffin wax, begin
to form and separate from the oil. As the temperature
drops, wax crystallizes and becomes visible. Certain
oils must be maintained at temperatures above the
cloud point to prevent clogging of filters.

e. Flash point and fire point.

The Flash point of an oil is the temperature at which

the oil releases enough vapor at its surface to ignite
when an open flame is applied. Foe example, if
lubricating oil is heated in an open container; ignitable
vapors are released in increasing quantities as the
temperature rises. When the concentration of the
vapors at the surface becomes great enough, exposure
to an open flame will result in a brief flash as the vapors
ignite. The release of vapors at this temperature is not
sufficiently rapid to sustain combustion, so the flame
immediately dies out. However, if heating is continued,
- 131 -
a temperature will be reached at which vapors are
released rapidly enough to support combustion. This
temperature is called the fire point. The flash and fire
points are useful in determining a lubricant’s volatility
and fire resistance. The flash point can be used to
determine the transportation and storage temperature
requirements for lubricants. Lubricant producers can
also use the flash point to detect potential product
contamination. A lubricant exhibiting a flash point
significantly lower than normal will be suspected of
contamination with a volatile product. Products with a
flash point less than 38 °C (100 °F) will usually require
special precautions for safe handling. The fire point for
a lubricant is usually 8 to 10 percent above the flash
point. The flash point and fire point should not be
confused with the auto-ignition temperature of a
lubricant, which is the temperature at which a lubricant
will ignite spontaneously without an external ignition
source.

f. Acid number or neutralization number (NN).

The acid or neutralization number is a measure of

the amount of potassium hydroxide required to
- 132 -
neutralize the acid contained in a lubricant. Acids are
formed as oils oxidize with age and service. The acid
number for an oil sample is indicative of the age of the
oil and can be used to determine when the oil must be
changed.

g. Carbon Residue

The carbon residue of a lubricating oil is the amount

of deposit, in percentage by weight (W %), left after
evaporation and pyrolysis of the oil under prescribed
conditions. In the test, oils from any given type of crude
oil show lower values than those of similar viscosity
containing residual stocks. Oils of naphthenic type
usually show lower residue than those of similar
viscosity made from paraffinic crudes. The more sever
the refining treatment—whether an oil is subjected to
solvents, hydroprocessing, filteration, or acid
treatment—the lower the carbon residue value will be.

LUBE REFINING PROCESSES

The most common processes used to produce lube

base stocks in refineries worldwide involve separation
processes that is, processes that operate by dividing
- 133 -
feedstock, which is a complex mixture of chemical
compounds, into products.

Usually, these results two sets of products: the desired

lube product and by—product. On the other hand, the
fastest—growing method for lube manufacture is by the
alternate conversion process, which involves converting
undesirable structures to desirable lube molecules
under the influence of hydrogen pressure and selected
catalysts.

H2 Desired product
Feedstock Pressure (A mixture)
Temp.
(A mixture) Catalysts By--products
( mixtures)
Figure 2 Lube conversion process.

- 134 -
 The concept of a separation process is basic to
understanding lube base stock manufacture. Figure1 is
a simple diagram of a separation process. By
comparison, figure 2 shows a simple schematic of a
hydroprocessing conversion process. While the desired
lube products from the two processes have many
similarities, the respective by—products of the two
processes are quite different, because of the different
processes. However, while the basic properties (e.g.
viscosity) of the desired products from the two
processes are similar, there are differences in
hydrocarbon structure and heteroatom (S, N, O)
content that can be important in final quilty.

The two processes are compared in figure 3, which

shows the (alternate) paths, with approaches starting
with distillation processes (extraction). Following
vacuum distillation, the extraction approach includes
solvent extraction (propane deasphalting and removal
of aromatics with furfural or other solvent), removal of
waxy components by solvent extraction with methyl
ethyl ketone (MEK) or other solvent, and finally a clay
finishing process, which removes some heteroatoms.
- 135 -
For the conversion approach, the primary upgrade is
through catalytic hydrotreatment, which results in
conversion of hydrocarbons to more desirable
structures (as willas some removal of heteroatoms as
gasas). Conversion uses a separate catalytic hydrogen
process for conversion of waxy paraffin and employs a
final hydrotreatment step as finishing step.

Lubricating oil is refined from crud oil. After

undergoing purifying process called sedimentation, the
crude oil is heated in huge fractionating towers. The
various vapors—which can be used to make fuel,
waxes ...etc. are collected at different points in the

- 136 -
tower. The lube oil that is collected is filtered and then
additives are mixed in.

Raw Materials

Lube oils are just one of the many fractions, or

components, that can be derived from raw petroleum,
which emerges from an oil well as a yellow—to—black,
flammable, liquid mixture of thousands of hydrocarbons
(organic compounds containing only carbon and
hydrogen atoms, these occurs in all fossil fuels).

- 137 -
 PART THREE

GENERAL BANK OF QUESTIONS

PART-I: Multiple-Choice Questions (MCQs):

1. Which word corresponds to crude oil?
a. compound b. fraction c. mixture d. element.
2.Which method of cracking petroleum (crude oil) produces
the most Alkenes? a. Catalytic b. Thermal
3.Thebest yield of gasoline from crude petroleum distillation
towers is from:a) catalytic cracking of lighter fractions b) lower
boiling fractions at the bottom of the column
c) simple distillation d) lower boiling fractions at the top of the
column
4. In general, a lower proportion of branched chain hydrocarbons
in a gasoline formulation: a) increases octane ratingc) burns without
knocking b) decreases octane rating d) is formulated by catalytic
reforming
5. Which liquid fuel, by fractional distillation of petroleum, is
obtained at the highest boiling point? a) asphalt b) gasoline c)
kerosene d) Diesel oil
6. Petrol and diesel are best described as examples
of:a. Fuelsb. lubricants c. crackatesd. plastics
7. Which TRUE about the process of 'cracking' in the
petrochemical oil industry:a. it needs a low temperature b. it
makes big molecules into more useful smaller molecules like
petrolc. it can make plastics d. it doesn't need a catalyst.
8. The antiknock characteristics of a gasoline are rated by the
octane-number scale. This scale is based on: a. heptane, given an
octane number of 0 b. heptane, given an octane number of 100 c.
2,2,4-trimethylpentane, given an octane number of 0d. 2,2,4-
trimethylpentane, given an octane number of 100 e. heptane with
the octane no. of 0 and isooctane with the octane no. of 100.

- 138 -
 9. The substance contains in the gasoline that has a high value
of combustion isa. heptanes b. isoheptane c. isooctaned. octane
e. 2-methylheptane
10. Cracking process needs a high temperature, because
a. it needs energy b. the reaction is exotherm c. the reaction is
endotherm d. the reactant is a polar substance e. the reactant is
a non polar substance
11. The statements below are about a catalytic cracking. The
wrong statement is:a. Al2O3/SiO2 are as catalysts b. can undergo at
lower temperature c. hydrogen gas may also be producedd.
alkane with larger molecules cannot be crackede. alkane with
smaller molecules will be produced.
12. The cracking reaction is very important in the petroleum
industry. The wrong information below is a. as a source of alkene
b. it is used to provide extra kerosenec. provide gasoline of a high
octane rating d. under the right conditions usually produce ethene
and propene e. tends to produce branched-chain rather than
straight-chain alkanes
13. Which of the following will not improve the octane rating of a
gasoline?a. increasing the percentage of branched-chain
hydrocarbons b. increasing the percentage of aromatic
hydrocarbons c. increasing the percentage of straight-chain
hydrocarbonsd. adding octane enhancers
14. Petroleum can be classified as mixture ofa.
hydrocarbonb. aliphatic hydrocarbon c. aromatic hydrocarbon d.
aliphatic and alicyclic hydrocarbon e. aliphatic and aromatic
hydrocarbon
15. Petroleum can be separated into petroleum fraction by
fractional distillation because the fraction a. are miscible b. have
different viscosities c. have different boiling pointd. have similar
chemical properties e. have different freezing point
16. Fraction distillation of a sample of crude oil produce the
fraction. The boiling point of the fraction are given below. Which
fraction has the biggest molecules?Fraction Approximate boling

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points (oC) a. 20 – 40 b. 40 – 120 c. 120 – 160d. 160 – 250 e.
Above 250.
17. Which one of the following hydrocarbons would you expect to
find in petroleum gas? a. C3H8b. C16H34c. C6H14d. C17H36
18.Gasoline hydrocarbons contain ………. carbon atoms per
molecule. a. 1-2 b. 3-4 c. 5-12d. 13-18 e. 17
19. Fractional distillation can be used to separate crude oil into
kerosene, diesel oil, lubricating oil and petrol. What is the correct
order of their boiling points?Lowest boiling point > Highest boiling
point a. Lubricating oil, Kerosene, Diesel, Petrol b. Kerosene,
Diesel, Lubricating oil, Petrol c. Diesel, Kerosene, Lubricating oil,
Petrol d. Lubricating oil, Kerosene, Petrol, Diesel e. Petrol,
Kerosene, Diesel, Lubricating oil
20. Which method of cracking petroleum (crude oil) produces the
most Alkenes? Catalytic, Thermal
21. In fractionating crude oil, bottoms area) The gasesb) The
residuesc) The heavy distillatesd) Gasoline and fuels
22. Hydrocarbon boiling points a) Increase as the number of
carbons atoms per molecule increases b) Decrease as the number
of carbons atoms per molecule increasesc) Is unrelated to the
number of carbons atoms per molecule d) Increase as the number
of carbons atoms per molecule decreases
23. Intermolecular forces are strongest ina) Petroleum's
gaseous fraction b) The liquid petroleum fractionc) The
greasy-solid fraction
24. The method used to separate the components of
petroleumis named a. destilationb. fractional destilationc.
heatingd. fractional heating e. filtration
25. The substance contains in the gasoline that has a
high value of combustion is a. heptanes b. isoheptane c.
isooctaned. octane e. 2-methylheptane
26. The formulae of isooctane is a. (CH3)2(CH2)6b.
(CH3)2CH(CH2)5c. (CH3)3CCH2CH(CH3)2d. (CH3)3C(CH2)3CH3

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 27. Petroleum is separated by distillation into fractions such as
gasoline and kerosene. These fractions are usually processed
further—for example, to obtain a greater quantity of gasoline with
the desired fuel characteristics. This processing is calleda.
refiningb. solubility c. filtration d. evaporation e. coagulation.
28. Which is a thermal decompostion reaction in the
petrochemical industry? a. combustion b. addition polymerization
c. crackingd. fractional distillation
29. The liquefied petroleum gas or LPG is the domestic gas that
we use in our kitchen. LPG is mostly (a. butaneb. methane c.
ethane d. propane) but has small amounts of (a. methane
b.butane c. propane d. propane and ethane).
30. Natural gas is mainly … with smaller amounts of the other
gaseous alkanes. a. methaneb. ethane c. propane d. butane
e. pentane
31. Mass of ___________ required to neutralize one gram of
lubricating oil is called as neutralization number. a. potassium
hydroxideb. calcium hydroxide c. magnesium hydroxide d. None of
the above
32. Which of the following is not a property of lubricants?
a. High specific heat b. High flash point c. Low pour pointd. Low
oxidation stability
33. In moving bed catalytic cracking, the catalyst is in the form of
a) fine powderb) pallets c) liquid form d) gaseous form.
Explanation: In moving bed catalytic cracking, the catalyst is made
into fine powder and charged into the catalyst chamber. So, they
move freely like fluids.
34. Which of the following order of petrol knocking is true?
a) aromatics > branched paraffins > olefins > cyclo paraffins >
aromatics b) straight chain paraffins > olefins > branched paraffins
> cyclo paraffins > straight chain paraffins c) straight chain
paraffins > branched paraffins > olefins > cyclo paraffins >
aromaticsd) straight chain paraffins > branched paraffins > olefins
> aromatics > cyclo paraffins.

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Explanation: The order of petrol knocking is given by straight chain
paraffins > branched paraffins > olefins>cyclo paraffins > aromatics.
As we know that aromatics are the best anti knock agents so, the
petrol knock for them is very low.
35. In the catalytic cracking, what Is the catalyst used? a) NaCl
b) KCl c) ZnSO4d) Al2O3Explanation: Al2O3 and also Al2(SiO3)3 acts
as catalysts in catalytic cracking. Usage of these catalysts, the
quality of petrol is high without any heating.
36. Knocking is also called as a) cracking b) pingingc) doping
d) crushing Explanation: Pinging is the other name of knocking.
Cracking means the process of breaking the higher hydrocarbons
into simple atoms. Doping means adding impurity to a pure metal to
improve its conductivity. Crushing means divided into small pieces.
37. Octane number is a rating of a) petrol knockingb) diesel
knocking c) petrol cracking d) diesel cracking
Explanation: Octane number is the rating for petrol knocking and
cetane number is the rating for diesel knocking.
38. Pre-ignition of the fuel is seen in a) petrol knockingb) petrol
cracking c) diesel cracking d) diesel knocking
39. Straight run naphtha is converted into high octane number
petrol (gasoline) by catalytic 1. cracking 2. reforming
3. isomerisation 4. polymerisation
40. Number of carbon atoms per molecule in lubricating oil are
a. 14 to 20 b.20 to 50c. 50 to 70 d. More than 70
41.Which of the following has the highest boiling point? A)
Kerosene B) Petrol C) DieselD) Water
42.Which of the following properties is NOT a characteristic of a
good fuel? A) High ignition temperatureB) Low cost C) Causes
minimum pollution D) Readily available
Explanation: Fuel is said to be good if it has the following
characteristics: (i) Low ignition temperature. (ii) Low cost.(iii)
Causing minimum pollution on burning. (iv) Readily available.
43.Which of the following statements is true about petroleum?

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A) Lighter than water and soluble in it. B) Heavier than water and
insoluble in it. C) Lighter than water and insoluble in it.
D) Heavier than water and soluble in it. Explanation: Petroleum
has less density than water so it floats on water. It is insoluble in
water because petroleum is non-polar while water is polar.
44. Which of these is the main constituent of petroleum gas?
A) Butane B) Propane C) Methane D) Ethane
Explanation: Petroleum gas is a mixture of ethane, propane and
butane. Butane, being a major part of the composition is about
95%.
45.Where is kerosene mainly used? A) In laying down roads. B)
As fuel in jet engines. C) In making water proof materials. D) In
furnaces of industries.
46.In fractional distillation of petroleum, where do the vapours
with highest boiling point condense? A) In the upper-most portion
B) In the lower-most portion C) In the middle portion D) Cannot
be said Explanation: In fractional distillation of petroleum, the
vapours with the highest boiling point cannot move up in the
fractionating column, (as they have low vapour pressure). So, the
liquids with high boiling points condense in the lowest (tray) portion
of the fractionating tower.
47.In LPG cylinder, how is the gas liquified? A) By increasing
volume B)By applying high pressure C) By increasing
temperature D) By reducing pressure. Explanation: Generally,
gases are liquified by applying high pressure (or) low temperature.
In LPG cylinders especially, the gas is liquified by applying high
pressure and it is stored in cylinders.
84. What does natural gas mainly consist of? A) C2H6B) CH4 C)
C3H8 D) C4H10Explanation : Natural gas is a mixture of methane,
ethane, propane, butane, carbon dioxide, nitrogen and oxygen. But
methane CH4 constitutes a major percentage of about 85.
49. Which of the following is a fossil fuel? A) PetroleumB)
Wood C) Cow dung D) Dry leaves Explanation: Petroleum
is a fossil fuel as it is obtained by the decomposition of the remains
of plants and animals under the sea over millions of years.
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 50. Where does natural gas occur? A) Above petroleum
oilB) Below petroleum oil C) Along with petroleum oil D)
Inside volcanic mountains Explanation: Usually petroleum
and natural gas occur at the same place. Petroleum occurs as
liquid, whereas natural gas is in the gaseous state above
petroleum.
51.What is the common name of petroleum? A) Black goldB)
Yellow gold C) Green gold D) Blue gold Explanation: Petroleum is
a thick, black colored, viscous liquid which is a rich source of
different, useful and expensive products like kerosene, petrol,
diesel etc., as gold, hence it is called as black gold.
52.By what process is petroleum refined?A) Fractional
distillation B) Destructive distillation C) Distillation D) All of the
above. Explanation: Petroleum is refined by the process of
fractional distillation as the constituents of petroleum products are
in the liquid state and differ in their boiling points.
53. During fractional distillation, the crude petroleum is heated to
A) 600 oCB) 400−500 oC C) 200 oC D) 100 oC
Explanation:During fractional distillation, crude petroleum that is
obtained from the earth's crust is heated to a temperature of about
400−500 oC The different constituents present start separating out
at different heights of the fractionating column depending upon their
boiling points.
54. What is the underlying principle based on which fractional
distillation is carried out? A) Different densities of each fraction B)
Different molecular weights of each fraction C) Different boiling
points of each fraction D) Different melting points of each fraction
Explanation: Fractional distillation is a method of separation of
liquid substances based on their different boiling points.
55.Which of the following is used as a fuel? A) GasolineB) Ether
C) Tar D) Grease Explanation:Gasoline is one of the products
obtained during the fractional distillation of petroleum. Gasoline
works as petrol. Hence, it is used as fuel in vehicles.
56. What is one example of Biomass? A. .Electricity b .Treesc
Windd .Water
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57. What is one disadvantage of coal? A. Coal produces air
pollution. B. There isn't a lot of coal left which makes it expensive.
C. The world isn't using a lot of coal which makes it an undesirable
job. D. You can only use it to roast hot dogs and cook hamburgers.
58. All are examples of Nonrenewable energy sources EXCEPT...
A. Coal B. Petroleum C. Hydropower D. Uranium (Nuclear)
59. When compared to gasoline and coal, natural gas is the
cleanest fuel we can burn. A. True B. False
60. Biomass energy is eco-friendly? A. True B. false
PART- II. What is the scientific term for the following:
1. is made of a mixture of different hydrocarbons and exhibit
either branched or straight chains...Ans.: petroleum
2. are very pure hydrocarbons and contain only hydrogen and
carbon; and give petroleum chemistry its combustible nature as well
as different applications. Ans.: paraffins
3.petroleum fractions that are rich in cycloalkanes. Ans.
Naphtha
4. an oily, viscous liquid which has many impurities like sulfur,
containing organic compounds. Ans. Crude petroleum/oil
5. The process whereby the petroleum is separated into its
components. Ans. refining of petroleum
6. Each hydrocarbon component with its own boiling point
separates out neatly when the crude petroleum is heated Ans.
fractional distillation
7. An industrial processplant where crude oil is processed and
refined into more useful petroleum products. Ans. petroleum
refinery
8. Major petroleum products distilled and separated into
fractions. Ans. distillates
9.Hydrocarbons have 15 to 18 carbon atoms and boiling points
between 350 C and 400 oC. Ans. Fuel oil
10. Hydrocarbons have 13 to 15 carbon atoms and boiling points
between 250 oC and 350 oC. Ans. Diesel oil
11.hydrocarbons have 10 to 12 carbon atoms and boiling points
are between 170 oC and 250 oC. Ans. Kerosene oil.
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 12. hydrocarbons have 5 to 10 carbon atoms and boiling points
between 40 o C and 170 o C. Ans. Gasoline or petrol
13.Gasoline is used primarily in light- and medium-duty cars and
trucks.
14.Saturated cyclic hydrocarbons, Ans: naphthenes,
15.Hydrocarbon, containing 20 to 70 carbon atoms per molecule
with boiling point more than 400 oC and used in various mechanical
and machine parts. Ans.Lubricating oil
17.Hydrocarbons have 30 to 50 carbon atoms, is a black sticky,
viscous substance and used for making road surfaces. Ans.
Asphalt
18. to cleave heavy hydrocarbon molecules into lighter ones.
Ans. Cracking
19. Using intense heat, low pressure and a powdered catalyst to
convert heavy hydrocarbon molecules into lighter ones: Catalytic
cracking
20.uses heat, moderate pressure and catalysts to turn naphtha
into high-octane petrol. Reforming
21. Convert hexane to methylcyclopentane, then to benzene:
Reforming
22.A mixture of iso-octane and n-heptane that has the same
knocking as the fuel under examination' The octane number:
23.Running straight-chain alkanes in the presence of hydrogen
and a catalyst such as a mixture of silica (SiO2) and alumina (Al2O3)
isomerize to form branched alkanes and cycloalkanes Ans.
Catalytic reforming
24. is a severe thermal cracking process designed to handle
heavy residues with high asphaltene and metal contents.

25. A process is usually required to saturate olefinic compounds

and to desulfurize products from coking units. Ans. Hydrotreatment
26.Process used to lower or break the viscosity of high-viscosity
residuum by thermal cracking of molecules at relatively low
temperatures. Ans.: Viscosity Breaking
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 27. A petrochemical process in which saturated hydrocarbons
are broken down into smaller, often unsaturated, hydrocarbons.
Ans. Steam cracking
28. A process where a gaseous or liquid hydrocarbon feed like
naphtha, LPG or ethane is diluted with steam and briefly heated in
a furnace without the presence of oxygen. Ans. Steam cracking,
29. It is an acid catalyzed process and intended to produce
highlybranched hydrocarbon mixtures. Ans.: Isomerization
30. Process produces polymer gasoline with a high octane
rating. Ans.: Oligomerization of Olefins
31. The minimum temperature of a liquid, particularly a lubricant,
after which, on decreasing the temperature, the liquid
ceases to flow. Ans. Pour point
32. The temperature at which sufficient vapor concentration
exists above the surface of the lubricant. Ans. Flash point/Fire
point
33. The tendency of lubricating oil to resist flow. Ans. Viscosity
34. The effect of temperature changes on the viscosity of the oil.
Ans. Viscosity Index
35. The temperature at which a grease changes from a semisolid
to a liquid: Ans. dropping point.
36. The use of organic material to generate energy. Ans.
Biomass energy
37. Fuel that is derived from biomass. Ans: Biofuel
Part-III.Correctly answer/complete the following statements:
a. The crude oil mixture is composed of the following groups of
compounds:1……..….….. 2...................... 3. ………
b. "Cracking" breaks ……………into …………... This can be done
with …………..or …………… The thermal cracking process follows
…………..mechanism, that is, bonds break ……………and thus
pairs of …………….are formed. The catalytic cracking process
involves the presence of …………… such ……………which
promote ……………….breakage of bonds yielding pairs of
……………….usually ……………and the very unstable
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…………………………c. Straight chain alkanes have ………..
octane numbers, the value of which decreases with the
………………. in the length of the chain. d. Cyclic alkanes have
…………………..octane numbers than the corresponding …………..
alkanes. e. The unsaturated hydrocarbons such as ………….
have higher octane numbers than the corresponding
……………hydrocarbons. f. The relationship between knocking and
the structure of the hydrocarbons in gasoline is summarized in the
following general rules.
1.……..……...2.……..………...3…………….4 .…….………...
g. Conversion processes in the petroleum industry are generally
used to:
1.…………………………..2…………………….3…………………….
21. The first step in thermal cracking reaction is the ---------------------
- of ------------- to two ---------------------------- fragments.
22. Isomerization process in the petroleum industry refer to -----------
------ and is used to:------------------
23. Alkylation process in the petroleum industry is used to:------------
-------------
24. The process produces polymer gasoline with a high octane
number is called ----------------
25. Hydrotreatment processes in the petroleum industry is -----------
----------- and primarily used to -----------------------------------------
26..Hydrodealkylation process in the petroleum industry is -------
--------and is designed to ----------------------
27. Zeolite catalyst is consisting of ------------------------- and
used in ------------------ and it provide ------------------- and --------------
------------------------and it promote ------------------ formation.
28. Catalytic cracking produces more gasoline of higher ---------------
------------ than thermal cracking. This is due to the effect of the ------
---------------- which promotes ------------------------ and --------------------
--------------- reactions.
29. Coking process is ---------------------------- designed to handle -----
---------- with -------------------------- and ---------------------------.

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30. Conversion processes in the petroleum industry are used to:1.
--------------------2.------------------------ 3.-------------------------
31. In domestic LPG cylinders, small quantities of foul smelling
………………are added so that any ………..…… can be detected.
32. All crude oils are mainly constituted of …………………. mixed
with variable amounts of ………….., ………………and
……………..compounds.
33. Naphtha is…………………, usually boiling below
………………and is classified into
1. …………………………2…………………………3…………………
34. The naphthenes are…………………and are classified into
1.………………..2. ……………3…………………4. ………………
PART- IV: True (T) or false (F) and correctthe falsesentences:
1. All the fractions of crude oil or petroleum are (not) single
compounds but they are mixtures of hydrocarbons.(F)
2. During the fraction distillation the crude petroleum separated
into fractions where the column is hot at the bottom and cool at
the top.(T)
3. In crude petroleum refinery the crude oil separates into fractions
according to weight and boiling point. (T)
4. In crude petroleum refinery the lightest fractions vapourise and
rise to the bottom (top) of the tower. F
5. More energy is needed to break the forces between large
molecules, and so the boiling point is higher. (T)
6. In crude petroleum refinery the Kerosine (aviation fuel) and
diesel oil, stay in the middle of the tower. (T)
7. In crude petroleum refinery the heaviest fractions settle at the
very top (bottom). F
8. Petroleum is range from clear, light color to dark, viscous liquid
which has a strong smell. (T)
9. Crude oils differ appreciably in their properties according to
origin and the ratio of the different components in the
mixture.(T)

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10. Crude oil containing a high percent of impurities, such as sulfur
compounds, are less desirable than low-sulfur crudes.(T)
11. Corrosivity of crude oils is a function of many parameters
among which are the type of sulfur compounds and their
decomposition temperatures. (T)
12. Metallic compounds are not (found) in crude oil.(F)
13. Cracking is to "crack" lighter (heavy) hydrocarbon molecules
into lighter heavy ones.(F)
14. Catalytic cracking: Using intense heat, low pressure and a
powdered catalyst to convert heavy hydrocarbon molecules into
lighter ones (T)
15. Reforming uses heat, moderate pressure and catalysts to turn
naphtha into high-octane petrol. For instance, convert hexane to
methylcyclopentane, then to benzene (T)
16. A low quality fuel does not burn smoothly and causes an
occasional explosive sound, which is known as knocking.(T)
17. The quality of a fuel is indicated in terms of its octane number.(T
18. Different hydrocarbons have different knocking tendencies.(T)
19. A fuel that produces minimum knocking is considered as a good
fuel.(T)
20. The scale of octane number has been set up with n-heptane
and 2,2,4-trimethylpentane (iso-octane) as the reference
compounds.(T)
21. Iso-octane has excellent anti-knocking properties and has been
arbitrarily assigned an octane number of 100.(T)
22. n-Heptane, is very prone to knocking is assigned an octane
number of zero (0).(T)
23. The antiknock property of a fuel increases with the increase in
its octane number. (T)
24. The octane number of any fuel is defined 'as the percentage of
iso-octane in a mixture of iso-octane and n-heptane that has the
same knocking as the fuel under examination'(T)

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25. A fuel having an octane number of 80 behaves in a manner
similar to a mixture having 80% of iso-octane, and 20% of n-
heptane.(T)
26. Straight run gasolines may have octane values ranging from 20
to 73.(T)
27. Aviation fuel is rated as 50 (100) octane.(F)
28. The octane number of a hydrocarbon depends upon its
structure. (T)
29. Branched-chain alkanes, alkenes and aromatic hydrocarbons
have high octane numbers(T)
30. branched-chain alkanes, alkenes, and aromatic hydrocarbons
are prepared by catalytic cracking and catalytic reforming.(T)
31. Straight chain alkanes have low octane numbers, the value of
which decreases with the increase in the length of the chain.(T)
32. Cyclic alkanes have higher octane numbers than the
corresponding straight chain alkanes.(T)
33. The unsaturated hydrocarbons such as aromatics hydrocarbons
have higher octane numbers than the corresponding straight
chain hydrocarbons.(T)
34. Crude Oil is a natural source of lubricants(T)
35. Pour point depressant inhibit formation and agglomeration of
wax particles keeping the lubricant fluid at low temperatures.(T)
36. Smaller chain molecules have higher octane number (whichever
applicable) and they burn efficiently & smoothly.(T)
37. Cracking increases (reduces) the viscosity of fuel.(F)
38. A gasoline that has an octane number of 92 contains 92% iso-
octane and 8% heptane(T)
39. Distillation of crude oil is a chemical (Physical)process.(F)
40. Reforming of crude oil does not change the number of carbon
atoms in the molecule.(T)
41. Cracking is a chemical process.(T)
42. Reforming of crude oil is physical (chemical)Processing(F)
43. Biomass is considered to be nonrenewable source of energy (F)
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44. Coal is considered to be renewable source of energy (T)
45. Energy derived from crude oil is called non–renewable energy
because once used up it cannot be replaced. (T)
Part v: Miscellaneous questions and answers:
1. What is Petroleum and how it is formed? Ans.: Petroleum
is a liquid found deep within the Earth's surface. It's categorized as
naturally occurring and is collected from drilling into the Earth.
Petroleum is often described as brown or black in color. Although
it's commonly found in liquid form, underneath the Earth's surface, it
can also be in the form of a gas. Crude oil was formed from the
fossilized remains of dead plants and animals and therefore is
called a fossil fuel. It is a finite (limited) resource. The continued use
of crude oil at the present rate will result in it running out in the
future. Fossil fuels take many millions years to form and are
currently being depleted (used up) much faster than new ones are
being formed. Energy derived from crude oil is called non–
renewable energy because once used up it cannot be replaced.
2.What is the relationship between knocking and the
structure of the hydrocarbons in gasoline?:Ans. Branched
alkanes and cycloalkanes burn more evenly than straight-chain
alkanes. Short alkanes (C4H10) burn more evenly than long alkanes
(C7H16). Alkenes burn more evenly than alkanes. Aromatic
hydrocarbons burn more evenly than cycloalkanes. The most
commonly used measure of a gasoline's ability to burn without
knocking is its octane number. Octane numbers compare a
gasoline's tendency to knock against the tendency of a blend of two
hydrocarbons heptane and 2,2,4-trimethylpentane, or isooctane to
knock. Heptane (C7H16) is a long, straight-chain alkane, which
burns unevenly and produces a great deal of knocking. Gasolines
that match a blend of 87% isooctane and 13% heptane are given
an octane number of 87.
Another way to increase the octane number is thermal reforming.
At high temperatures (500-600C) and high pressures (25-50 atm),
straight-chain alkanes isomerize to form branched alkanes and
cycloalkanes, thereby increasing the octane number of the
gasoline.
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 Running straight-chain alkanes in the presence of hydrogen and
a catalyst such as a mixture of silica (SiO2) and alumina
(Al2O3)isomerize to form branched alkanes and cycloalkanes
Catalytic reforming, which can produce a gasoline with even
higher octane numbers.
Thermal or catalytic reforming and gasoline additives such as
tetraethyllead increase the octane number of the straight-run
gasoline obtained from the distillation of crude oil, catalytic
reforming increases the yield of gasoline from a barrel of oil.
3. What is naphtha?Ans. Naphtha is a refined light distillate
fraction, usually boiling below 250 oC, but often with a fairly wide
boiling range. Gasoline and kerosine are the most well-known, but
there are a whole range of special-purpose hydrocarbon fractions
that can be described as naphtha. The petroleum refining industry
calls the 0-100 oC fraction from the distillation of crude oil "light
naphtha" and the 100-200 oC fraction "heavy naphtha".The product
stream from the fluid catalytic cracker is often split into three
fractions, <105 oC = "light naphtha", 105-160 oC = "intermediate
naphtha" and 160-200 oC "heavy naphtha".
4. What is naphthene? Ans. The naphthene (not to be
confused with naphthalene) series has the general formula CnH2n
and is a saturated closed-ring series which is called cycloalkanes or
polycycloalkanes. Cycloalkanes are classified into small, common,
medium, and large cycloalkanes, where cyclopropane and
cyclobutane are the small ones, cyclopentane, cyclohexane,
cycloheptane are the common ones, cyclooctane through
cyclotridecane are the medium ones, and the rest are the larger
ones. This series is an important part of all oil refinery products, but
it also forms most of the complex residues from the higher boiling-
point ranges. For this reason, the series is generally heavier. The
residue of the refinery process is an asphalt, and the crude oils
5. What is Petroleum gas?Ans.: The component of petroleum
gas is butane (C4H10). The other components are propane (C3H8)
and ethane (C2H6). All these gases burn very easily and are highly
flammable. These compounds are gases under ordinary
temperatures and pressures. But they can be liquefied easily under
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pressure and then they are called liquefied petroleum gas or LPG.
LPG is the domestic gas that we use in our kitchens. LPG is mostly
butane but has small amounts of propane and ethane also. In
domestic LPG cylinders, small quantities of foul smelling ethyl
mercaptan (C2H5SH) are added so that any gas leak can be
detected. This becomes very convenient to handle and transport.
The LPG vapourises and is used as gas in the kitchens.
6. What is the advantages of using LPG ?Ans. ● LPG has
high calorific value and is a good fuel. 1 gm of LPG burns to give 50
kJ of heat energy. ● LPG burns with a smokeless fire. ● LPG does
not cause pollution as all its components burn and they do not
produce any pollution causing gases. ● LPG is convenient to
transport and store in cylinders.
7. What is disadvantages of using LPG : Ans. ● It is a highly
flammable gas and catches fire very easily. ● If LPG gas leaks, it
can cause an explosive mixture with air. There are numerous
episodes of LPG explosions and severe accidents due to such
explosions. ● There are strict procedures for use and maintenance
of LPG for use to avoid hazards associated with it. ● If LPG is
inhaled by accident, it is extremely harmful to health and may cause
even death.
8. Write in brief on uses of natural gas: Ans. Natural gas is
used as fuel in industries. It is also used as domestic fuel where
piped gas is made available from the wells to the homes. Natural
gas is used as a source for obtaining hydrogen. Hydrogen is
needed by industries as a reducing agent. Hydrogen is also used to
make ammonia and ammonium fertilizers. Methane is heated
strongly so that it decomposes into its component gases : carbon
and hydrogen. Carbon obtained from the decomposition of natural
gas is used in tyre industries.
9. What is the advantages of using natural gas:
1. Natural gas burns easily without any smoke. Hence it is very
useful as a domestic fuel.
2. Natural gas has a very high calorific value (55 kJ/g) which is
good for heating.

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3. It causes no pollution or produces no poisonous gases.
4. Natural gas can be supplied directly through pipes from the oil
wells. This eliminates the need for storage and transport of the
gases in cylinders.
10. What is the advantages of using natural gas:
1. Natural gas is highly flammable and many precautions have to
be taken before using it.
2. Pipelines to deliver the gas from the well to the site of use are
very expensive. The pipelines need to be laid underground and
checked for leakage, pilferage, etc. Thus the maintenance cost
of the pipelines becomes very expensive.
11. What does the conversion process of petroleum means
and Why it is used?:?Ans.The conversion of crude oil into
gasoline, diesel fuel, and lubricants by fractional distillation, and
cracking. Why it is used?:Conversion processes in the petroleum
industry are generally used to:1. Upgrade lower-value materials
such as heavy residues to more valuable products such as naphtha
and LPG. 2. Improve the characteristics of a fuel. For example, a
lower octane naphtha fraction is reformed to a higher octane
reformate product. 3. Reduce harmful impurities in petroleum
fractions and residues to control pollution and to avoid poisoning
certain processing catalysts.
12. What is viscosity Breaking?: process used to lower or
break the viscosity of high-viscosity residuum by thermal cracking of
molecules at relatively low temperatures.
13. What is steam cracking? is industrial method for producing
the lighter alkenes
14. What is the difference between thermal cracking and
catalytic cracking process?: The thermal cracking process follows
a homolytic mechanism, that is, bonds break symmetrically and
thus pairs of free radicals are formed. While the catalytic cracking
process involves the presence of acidcatalysts (usually solid acids
such as silica-alumina and zeolites) which promote a heterolytic
(asymmetric) breakage of bonds yielding pairs of ions of opposite
charges, usually a carbocation and the very unstable hydrideanion.
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Carbon-localized free radicals and cations are both highly unstable
and undergo processes of chain rearrangement, C-C scission in
position beta (i.e., cracking) and intra- and intermolecular hydrogen
transfer or hydride transfer. In both types of processes, the
corresponding reactive intermediates (radicals, ions) are
permanently regenerated, and thus they proceed by a self-
propagating chain mechanism. The chain of reactions is eventually
terminated by radical or ion recombination.Here is an example of
thermal cracking reactions: The first step in cracking is the thermal
decomposition of hydrocarbon molecules to two free radical
fragments. This initiation step can occur by a homolytic carbon-
carbon bond scission at any position along the hydrocarbon chain.
The following represents the initiation reaction:

The radicals may further crack, yielding an olefin and a new free
radical. Cracking usually occurs at a bond beta to the carbon
carrying the unpaired electron.

Further bond scission of the new free radical R˙ can continue to

produce ethylene until the radical is terminated. Free radicals may
also react with a hydrocarbon molecule from the feed by abstracting
a hydrogen atom. In this case the attacking radical is terminated,
and a new free radical is formed. Abstraction of a hydrogen atom
can occur at any position along the chain. However, the rate of
hydrogen abstraction is faster from a tertiary position than from a
secondary, which is faster than from a primary position.

The secondary free radical can crack on either side of the carbon
carrying the unpaired electron according to the beta scission rule,
and a terminal olefin is produced.

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 Free radicals, unlike carbocations, do not normally undergo
isomerization by methyl or hydrogen migration. However, hydrogen
transfer (chain transfer) occurs when a free radical reacts with
other hydrocarbons. There are two major commercial thermal
cracking processes, delayed coking and fluid coking. Flexicoking is
a fluid coking process in which the coke is gasified with air and
steam. The resulting gas mixture partially provides process heat.
15. Explain in Brief how petroleum formed? Ans.: Petroleum
is formed due to decomposition of microorganisms which got buried
under the sea over millions of years ago and the effects of
pressure, heat and bacteria got them converted into oily liquids in
the absence of air or oxygen.Bunker fuel, is also know as heavy oil,
is used to power ships.
16. Show in table the 7 different trends as we up and down
the column. Ans.: The more carbon atoms in a hydrocarbon
molecule, the larger the molecule. How does this affect its boiling
point?
17. Petroleum products are usually grouped into three
categories: a. ……..b. …………c………………
Ans. a. Light distillates (LPG, gasoline, naphtha), b. middle
distillates (kerosene, diesel), c. heavy distillates and residuum
(heavy fuel oil, lubricating oils, wax, asphalt).
18. The crude oil mixture is composed of the following
groups:
i. ii. iii.
i. Hydrocarbon compounds ii. Non-hydrocarbon
ii. Organometallic compounds
19. Besides impurities such as Nitrogen and Oxygen
compounds crude oil contaminated with sulfur compounds,
give a list for these sulfur containing compounds and explain

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in brief the harmuful effect of sulfur on petroleum quality and
the name of the method used to remove it.
20. Write in brief on various types of non-hydrocarbon
compounds occur in crude oils and explain how to remove
their harm. .
21. Why the presence of non-hydrocarbon compounds in
crude oil are harmful? Ans. Because it
i. Cause problems to certain catalytic processes.
ii. Cause pollution problems in addition to the corrosive
nature of their oxidization products.
iii. increase production costs.
22. Explain how organosulfur compounds being removed
from petroleum?
Most sulfur compounds can be removed from petroleum streams
through hydrotreatment processes, where hydrogen sulfide is
produced and the corresponding hydrocarbon released. Hydrogen
sulfide is then absorbed in a suitable absorbent and recovered as
sulfur. During hydrotreatment of petroleum fractions, nitrogen
compounds are hydrodenitrogenated to ammonia and the
corresponding hydrocarbon. For example, pyridine is
denitrogenated to ammonia and pentane:
What is hydrotreatment: is a process widely used in the petroleum
industry for producing high quality fuels and as part of a scheme for
upgrading heavy crude oil by reducing sulfur, nitrogen and/or metal
content.
23. What is Catalytic hydrotreating?
Catalytic hydrotreating is a hydrogenation process used to remove
about 90% of contaminants such as nitrogen, sulfur, oxygen, and
metals from liquid petroleum fractions. These contaminants can
have detrimental effects on the equipment, the catalysts, and the
quality of the finished product. Hydrotreating is done prior to
processes such as catalytic reforming so that the catalyst is not
contaminated by untreated feedstock. Hydrotreating is also used
prior to catalytic cracking to reduce sulfur and improve product
yields, and to upgrade middle-distillate petroleum fractions into
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finished kerosene, diesel fuel, and heating fuel oils. The process
also converts olefins and aromatics to saturated compounds.
Hydrotreating for sulfur removal is called hydrodesulfurization. In
this process the feedstock is deaerated and mixed with hydrogen,
preheated in a fired heater, and then charged under pressure
through a fixed-bed catalytic reactor. In the reactor, the sulfur and
nitrogen compounds in the feedstock are converted into H2S and
NH3.
Hydrodesulfurization (HDS). Removal of organic sulfur
compounds from a petroleum fraction and conversion to
hydrogen sulfide (H2S). Sulfur removal difficulty increases in
the following order: paraffins < naphthenes < aromatics. The
type of sulfur compounds can be classified as mercaptans,
sulfides, disulfides, thiophenes, benzothiophenes,
dibenzothiophenes, and substituted dibenzothiophenes. The
ease of removal of these sulfur compounds is in the same
order, the mercaptans being the easiest to remove and
dibenzothiophenes the most difficult.
• Hydrodenitrogenation (HDN). Removal of organic nitrogen
compounds and conversion to ammonia (NH3). Removal of
nitrogen requires more severe reaction conditions than does
HDS. The molecular complexity (five- and six-membered
aromatic ring structures), the quantity, and the difficulty of
nitrogen-containing molecules to be removed increase with
increasing boiling range of the distillate. Nitrogen compounds
can be basic or nonbasic. Pyridines and saturated
heterocyclic ring compounds (indoline, hexahydrocarabazole)
are generally basic, whereas pyrroles are nonbasic.
• Hydrodeoxygenation (HDO). Removal of organic oxygen
compounds and conversion to water. Similar to HDS and
HDN, lower- molecular-weight oxygen compounds are easily
converted, while higher-molecular-weight oxygen can be
difficult to remove. Phenol is one of the most difficult oxygen
compounds to convert.
24. Petroleum products are usually grouped into three
categories:i. ii. iii.
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Ans. i. Light distillates such as LPG, gasoline, and naphtha. ii.
Middle distillates such as kerosene, and diesel. iii. Heavy distillates
and residuum such as heavy fuel oil, lubricating oils, wax and
asphalt.
This classification is based on the way crude oil is distilled.
 Thethree basic steps of refinery are:a.
…………………….….b………………….…….c……………...….….
Ans.: a. Separation (fractional distillation) b. Conversion (cracking
and rearranging the molecules) c. Treatment
25. Show with diagram how the fractional distillation of
petroleum is done including the names of components
separated. Ans. Course book (Ch. 1)
26.What is lubricant? Ans. A lubricant refers to any substance
that is physically integrated for the purpose of reducing friction
between two or more moving surfaces.
27.What is the purpose of using lubricants? Ans. Lubricants
perform the following key functions. Keep moving parts apart,
Reduce friction, Transfer heat, Carry away contaminants & debris,
Transmit power, Protect against wear, Prevent corrosion, Seal for
gasses, Stop the risk of smoke and fire of objects.
28. Define the neutralization number and total base number.
29. What is cracking? Why is cracking used in the oil
industry? What are the effects of this process?
Ans.:Petroleum refinery process in which large heavy oil molecules
are broken down into smaller ones. If conducted only with the
application of heat, it is called thermal cracking. If a catalyst is also
used, it is called catalytic cracking. If hydrogen is used in addition to
heat and catalysts, it is called hydrocracking. cracking needs a high
temperature / heating, cracking needs a catalyst / use of zeolite,
cracking converts large hydrocarbon molecules into smaller ones,
cracking converts less useful hydrocarbons into more useful
hydrocarbons cracking converts named fractions that are in excess
into named fractions that are in short supply e.g. bitumen or paraffin
into petrol or diesel. In general, crude oil consists of a mix of
various molecules (long and short chain) whereas diesel & gasoline
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consists mainly of short chain molecules.These long chain
molecules if present in transportation fuels can cause charring &
inefficient burning.Therefore, in order to break these long chain
molecules into smaller ones (suitable for transportation fuels),
different types of cracking( fluidised catalytic cracking, thermal
cracking etc.) are used. As a matter of fact, most processes in a
refinery aims to break longer chains into smaller ones. These
smaller chain molecules have higher octane number (whichever
applicable).They burn efficiently & smoothly.Cracking also reduces
the viscosity of fuel.
30.The diagram shows a fractionating column. The fractions
are shown by letters. Names the petroleum fraction of each
indicated letter in the following diagram

31.Describe how fractional distillation is used to separate the

petroleum into fractions.In your answer refer to • changes of state, •
differences in boiling points. Key answer • petroleum vaporised (in
furnace);• column is hot at the bottom and cool at the top;• smaller /

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lighter molecules move higher up the column ora;• fractions with
lower boiling points move further up column ora;• smaller / lighter
molecules have lower boiling points ora;• fractions condense when
the temperature in the column fallsbelow the (average) boiling point
of the fraction;
32. what is catalytic cracking?is the breaking up of complex
hydrocarbons into simpler moleculesin order to increase the quality
and quantity of lighter, more desirableproducts and decrease the
amount of residuals.
33. What is catalytic reforming?is a process used to convert
low-octane naphthas into highoctanecompounds such as toluene,
benzene, xylene, and other aromatics whichare useful in gasoline
blending and petrochemical processing.
34.Correctly answer/complete the following questions/statements
by writing the proper phrase(s) in the corresponding blank:
i. Zeolite catalyst is consisting of ------------------------- and used in -
----------------- and it provide ------------------- and -----------------------
---------------and it promote ------------------ formation.
ii. The Steps of catalytic cracking are : 1. 2.3.
iii Catalytic reforming in the petroleum industry are used to:
…………….. and the catalyst generally used in catalytic reforming
are…………………….. An examples of catalytic reforming reactions
are:
iv. Isomerization process in the petroleum industry refer to ----------
and is used to:------------------- . An examples of isomerization
reactions are
v. Alkylation process in the petroleum industry is used to:------------
and an example of alkylation is …………………….
vi. The process produces polymer gasoline with a high octane
number is called ----------------. An example of polymer gasoline is:
vii. Hydrotreatment processes in the petroleum industry is ---------
and primarily used to ------------------------------------------
viii..Hydrodealkylation process in the petroleum industry is --------
and is designed to ----------------------

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ix.. A major difference between thermal and catalytic cracking is
that :---------------------------------------------------------------------------------
35. What Is Biomass Energy? Biomass energy is any kind of
energy that uses a biological organism (plant or animal) as its
source.Because the definition of biomass is so broad, fuels that can
be considered "biomass" include a wide variety of items and
researchers are discovering new biomass energy sources all the
time. Animal manure, landfill waste, wood pellets, vegetable oil,
algae, crops like corn, sugar, switchgrass and other plant material --
even paper and household garbage -- can be used as a biomass
fuel source.
36. Explain by mechanism how you transform methanol to
gasoline (MTG) to make synthetic gasoline?

Ans.: Methanol-to-Gasoline (MTG): Methanol is a small and

versatile molecule which can be converted to different
hydrocarbons by means of the MTG process. Under optimal
conditions a high octane clean gasoline is produced. Since
methanol is easily produced from natural gas, biomass or coal, the
MTG process offers an important alternative route for fuel supply to
the existing transportation market.Zeolites are the catalysts used in
the MTG-process. The mechanism involved the dehydration of
methanol to dimethyl ether on acidic catalysts. In the next reaction
step C-C bond formation occurs and it is indicated that ethane and
propene are the primary formed olefins. These primary formed
olefins are readily converted to higher hydrocarbons by
oligomerization and isomerization reactions. In the subsequent
reaction step the aromatics and paraffins are formed in cyclization
and hydride transfer reactions.The chemistry of the reactions of the
primary formed olefins, can be explained by well known reactions of
carbenium ions. Because of the size of the molecules to be formed
in this part of the reaction sequence, the shape selectivity of the
zeolite is of great importance. This process makes gasoline from
methanol. Since methanol can be made frompractically any organic
material, the process can make synthetic gasoline fromcoal, natural
gas, petroleum residua, agricultural wastes, garbage,wood, etc.
Reaction pathway: MeOH → dimethyl-ether → light olefins → HC
(alkanes, aromatics).Methanol to Gasoline – Mechanism: The first

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step corresponds to the formation of dimethyl ether DME on acidic
sites as follows:

Oligomerization and skeletal isomerization steps:

The over all transformation reactions are as follows:

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 37. Explain how plastics and rubber are made from petroleum.
Ans: Course book chapt. 3.
38.Explain the catalytic hydrocracking process and apply it on
naphthalene. Ans.: Catalytic hydrocracking is one of the latest
additions to petroleum refining processes and the interest in
hydrocracking has been attributed to the increasing demand for
light and middle distillates., The advantages of hydrocracking
include its ability to handle a wide range of feedstocks that may be
difficult to process by catalytic cracking and its flexibility in
selectivity between light and middle distillates. The principal
objective of hydrocracking is to decrease the molecular weight and
boiling point of heavy oils to produce saturated hydrocarbons
(diesel and jet fuel) from highly aromatic feedstocks.
The hydrocracking process has two dimensions: Hydrogenation of
aromatic rings and cracking of aliphatic compounds, as shown in
Figure below, using naphthalene as an example for an aromatic
ring system. One should note that that the aromatic rings cannot be
cracked before they are saturated with hydrogen. With
hydrocracking it is possible to convert an aromatic compound to a
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paraffinic compounds without any loss of carbon, as shown in
Figure . As a hydrogen-addition process, hydrocracking provides
high yields of valuable distillates without producing low-grade
byproducts (e.g., heavy oils, gas, or coke) as experienced in carbon
rejection processes such as coking.

Give a comparison between the distribution of products from

thermal cracking and catalytic cracking.
Ans.: The following Figure compares the distribution of
products from thermal cracking (free radical chain reactions)
and catalytic cracking (ionic chain reactions). Short chain
paraffins constitute the principal products in both cases with
one important difference – an abundance of iso-alkanes
(branched-chain alkanes) in catalytic cracking products. One
can also note in Figure that catalytic cracking products
contain higher concentration of aromatic compounds. High
octane number of gasoline produced by catalytic cracking can
be attributed to high concentrations of i-alkanes and relatively
more abundant aromatics present in the crackate (catalytic
cracking product). Having no olefins larger than butylene (C4)
from catalytic cracking processes, also distinguishes catalytic
cracking products from thermal cracking products obtained
from gas oil.

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- 167 -
 List of References

Recommended Textbooks

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