Crude Oil Chemistry No Series

Crude Oil
Chemistry
Vastly Simanzhenkov
University Duisburg-Essen
Duisburg, Germany
Raphael Idem
University of Regina
Regina, Saskatchewan, Canada
MARCEL
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Preface
This book is devoted to students as well as scientists and process engineers in-
volved in petroleum science, refining and engineering. Part I of the book gives a
historical overview of the origin of petroleum. The first chapter shows how crude
oil is linked with human civilization. In this chapter it is also shown that the en-
ergy used to run most of today's machinery derives from petroleum. It also pro-
vokes our imagination on how the various moving parts of machinery would oper-
ate without mineral oil or lubricating oil, both of which are also produced from
crude oil. The first chapter also provides insight into the problems that have arisen
as a result of applying different standards by different countries to similar crude oil
products and how these problems are tackled.
The second chapter of Part I deals with modern analytical methods used in crude
oil chemistry. Modern and classical methods of petroleum and petroleum product
characterization are explained. This chapter is an essential chapter for present and
potential crude oil chemists since analytical chemistry constitutes an important
part of crude oil chemistry. Besides, crude oil products have so many special
properties that are important for the industry. The need to determine these proper-
ties gives rise to the use of very many analytical methods in the petroleum indus-
try.
Part II (i.e. chapters 3 and 4) shows the geopolitical and economic nature of pe-
troleum chemistry. In this chapter, the initial stages of development of various
petroleum companies are shown. It gives a historical run-down on how small
companies of the past have blossomed into giant multinational companies of
worldwide repute. For readers, it is especially interesting to learn the history of the
development of the Eastern Bloc companies, especially the Russian companies. In
this chapter, it is shown how the political situation in this country has had a great
influence on the economic development of all Russian industries in general and
the petroleum industry in particular. It is also shown how it has been possible for
the big Russian petroleum concerns to be formed in less than twenty years during
the difficult times of political and economic reforms.
Chapters 5 and 6 of Part III of the book introduce the reader to the science of crude
oil refining. An illustration of the complete process scheme that starts from crude
oil all the way to final products is given. In particular, the process route of crude
oil from the well to the gas station and indeed the car tank is provided. These
chapters also present the techniques and technologies involved in most of the im-
portant processes used in modern petroleum refineries for processing light and
heavy distillate fractions. Chapter 7 in Part III looks at ecological problems that
iii
iv Preface
arise in the crude oil industry. The chapter also shows that, in order to develop an
appropriate technology for crude oil treatment, not only are economically rational
decisions required, but also, ecologically acceptably decisions are needed. This
chapter looks at our environment as a very sensitive system that must be protected
with respect to the many processes that take place in the petroleum refining indus-
try.
Good quality crude oil is often defined in terms of high API gravity and low sulfur
content. However, reserves of this type of oil are disappearing, giving rise to in-
creasing contributions from oil of lower API gravity and higher sulfur content. Is
the chemistry of processing of the two types of oil different? This question is an-
swered in Part IV of this book. The chapter also introduces the presence of asphal-
tenes in crude oil. A list of problems that occur during oil production, transporta-
tion, and processing that could be attributed to asphaltene presence in crude oil is
presented. New concepts and approaches that aid in the processing of crude oils
with significant amounts of asphaltenes are introduced. Part IV also looks at future
processes that may be introduced in the petroleum refinery. These are hybrid fuel
production processes that involve combining the well-known modern cracking
process with the recycling of waste plastics or bio-fuels. The advantages than can
be derived from co-processing of asphaltene-containing crude oils with plastics or
biomass materials are given. Part IV also presents some analytical techniques that
could be used by petroleum engineers and chemists to better understand the nature
of heavy crude oil and residues, and possible ways to positively influence their
processing. In all, Part IV presents critical material that can contribute towards
further development of the petroleum industry. This is especially true for the non-
conventional petroleum industry, and it can be particularly important for North
America, since Canada has the largest reserves of non-conventional petroleum in
the world.
Both authors have worked extensively in the areas of petroleum science and engi-
neering. We hope that this book will go a long way in introducing the reader to the
fascinating world and concepts of the black gold of our planet.
Vasily Simanzhenkov
Raphael Idem
Contents
Preface Hi
Part I Classification and Characterization of Crude Oil 1
1 Nature and Classification of Crude Oil 3
1. History and nature of petroleum 3

1. .1 Origin of petroleum 13
1. .2 Oil formation in the world's oceans 16
1. .3 Modern concept of formation of petroleum 18
1. .4 Consequences of intensive extraction and processing of oil 26
1. .4.1 Dangerous fogs 28
1. .4.2 Black oceans 31
1.2 General properties and classification of petroleum:
comparison of petroleum from different countries 33
1.2.1 Fractions and chemical composition of petroleum 33
1.2.2 Chemical classification of petroleum 35
1.2.3 Classification by density 37
1.2.4 Characterization by viscosity-gravity constant (vgc) 38
1.2.5 Technological classification of petroleum 39
1.3 Products from crude oil 39
1.3.1 Gasoline 40
1.3.2 Jet fuel (kerosene) 48
1.3.3 Diesel 49
.3.4 Residual fuel 55
.3.5 International standards for fuels 58
.4 Lubricating oils and lubricants 59
.4. International standards for lubricating oils 66
.4. . 1 Industrial oils 66
.4. .2 Motor oils 67
.4. .3 Transmission oils 70
.4. .4 Hydraulic oils 72
2 Modern Characterization and Analysis Techniques for Crude Oil 73

2.1 Chromatographic methods 73
2.1.1 Gas chromatography 74
2.1.2 High performance liquid chromatography 97
2.1.3 Thin layer chromatography 107
2.2 Spectroscopic methods 112
2.2.1 Infrared spectroscopy 112
VI Contents
2.2.2 Raman spectroscopy 127

2.2.3 Colorimetry and photometry 131
2.2.4 Fluorescence and phosphorescence spectroscopy 136
2.2.5 Atomic absorption spectroscopy and atomic emission
spectroscopy 139
2.2.6 X-ray fluorescence spectroscopy 144
2.3 Other methods for elucidating the structure of crude oil 146
2.3.1 Separation methods 146
2.3.2 Chemical analysis methods of crude oil products:
determination of unsaturated compounds 149
2.3.3 Structural bulk analysis of heavy crude oil fractions:
n-d-M method 150
2.4 Methods of characterization of colloidal properties of crude oil
and its products 153
2.4.1 Direct methods 153
2.4.2 Indirect methods 156
2.5 Determination of the physical properties of crude oil 157
2.5.1 Density determination 157
2.5.2 Viscosity determination 159
2.5.3 Refractive index determination 161
Bibliography 163
Part II Regional Petroleum Industry 171

3 Petroleum Producing Countries: OPEC and Non-OPEC 173
3.1 Introduction 173
3.1.1 Short background on OPEC 174
3.2 North America 175
3.2.1 United States 175
3.2.2 Canada 178
3.3 Russia 178
3.3.1 The role of the petroleum industry for Russia 179
3.3.2 Reforms in the Russian oil industry 180
3.3.3 Russian petroleum and gas in the world market 182
3.3.4 Structure of the petroleum sector in Russia 183
3.4 Arabian East 185
3.4.1 Oman 187
3.4.2 Iraq 187
3.4.3 Iran 188
3.4.4 Qatar 190
3.4.5 Kuwait 191
3.4.6 United Arab Emirates 194
3.4.7 Saudi Arabia 194
Contents vii
4 International Petroleum Companies 197

4.1 British Petroleum 197
4.2 Castrol 200
4.3 ExxonMobil 201
4.4 Neste/Fortum 205
4.5 Shell 206
4.6 Total /Fina/ Elf 208
4.7 LUKOil 214
4.8 Yukos 215
4.9 TNK 216
Bibliography 217
Part III Main Processes in the Petroleum Refining Industry 219

5 Crude Oil Distillation 221
5.1 Petroleum and gas preparation 221
5.1.1 Formation of petroleum emulsions and their basic properties 222
5.1.2 Separation of water-oil emulsions 224
5.1.3 Mechanical petroleum drying 227
5.1.4 Thermal petroleum drying 227
5.1.5 Chemical methods of petroleum drying 228
5.1.6 Thermal chemical petroleum drying 229
5.1.7 Stabilization of petroleum 230
5.1.8 Technological schemes for petroleum preparation 231
5.1.9 Pressure extraction system 231
5.2 Desalting 234
5.3 Atmospheric rectification 235
5.4 Vacuum rectification 251
5.5 Heat exchangers and separators 256
6 Processing of Light and Heavy Distillates 261

6.1 Thermal cracking 261
6.2 Catalytic cracking 275
6.3 Visbreaking 285
6.4 Coking 285
6.5 Hydroprocessing 287
6.6 Reforming 292
6.7 Isomerization 296
6.8 Alkylation 298
6.9 Blending 301
7 Environmental Issues Facing the Refining Industry 303

7.2 Methods of cleaning crude oil contaminated water and soil 304
viii Contents
7.3 Methods of air and gas cleaning used in the crude oil industry 309
7.4 Conclusion to Part III 318
Bibliography 320
Part IV Heavy Oil Processing - Chemistry of Asphaltenes 325

8 Chemistry of Crude Oil Asphaltenes 327
8.2 Problems of crude oil residue treatment with respect
to asphaltenes 328
8.2.1 Coke formation and reduction of heavy metals 329
8.2.2 Treatment possibilities for crude oil residues 331
8.2.2.1 Physical treatment - deasphalting 331
8.2.2.2 Chemical treatments 333
8.2.2.3 Visbreaking 334
8.2.2.4 Coking 335
8.2.3 Coke forming reactions during residue treatment 337
8.2.3.1 Catalytic treatment 337
8.2.3.2 Thermal treatment 340
8.3 Methods of analysis of crude oil residue 342
8.3.1 Methods and main definitions for the determination
of coke formation tendency 342
8.3.2 Analytical characterization of heavy oil residues and asphaltenes 343
8.3.2.1 Solution analysis 343
8.3.2.2 Coagulation analysis 346
8.3.2.3 Distillation method 349
8.3.2.4 Chromatography 350
B
8.3.2.5 C-NMR analysis 351
8.3.2.6 Ultimate analysis 353
8.3.2.7 Molecular weight determination 354
8.3.3 Temperature influence on molecular weight determination 357
9 Processing of Heavy Crude Oils and Crude Oil Residues 359

9.2 Chemistry and reaction of asphaltenes during co-processing
of crude oil residue and plastics 360
9.2.1 Change of asphaltene structure during thermal processing 360
9.2.2 Evaluation of possibilities of various asphaltene reactions based
on thermodynamics 368
9.2.3 Hydrogen transfer 375
9.3 Co-processing with cracked products 377
9.3.1 Co-processing with cracked products from aromatics containing
plastics (e.g. polystyrene) 380
9.3.2 Co-processing with cracked products from plastics containing
Contents ix
paraffin groups 383

9.3.3 Possibilities that exist for carrying out co-processing of heavy
crude oils and various co-feeds 385
9.3.4 Behavior of heavy metals during co-processing 387
9.3.5 Conclusions of co-processing of crude oil residue and co-feed 387
9.4 Industrial methods of crude oil residue treatment 388
9.4.1 Fluid catalytic cracking 388
9.4.2 Hydrocracking 390
9.4.3 Coking 392
Bibliography 394
Appendix A: Conversion Factors Important for Crude Oil Chemists 397
Appendix B: Glossary 399
Index 407
Parti
CLASSIFICATION AND
CHARACTERIZATION OF CRUDE OIL
OVERVIEW
In this part of the book, fundamental chemical information of interest to

petroleum chemists is given. The first chapter deals with the main definitions as
well as the important properties of crude oil and petroleum products used by
petroleum specialists. A short history is given as to how crude oil became the most
important power source for our civilization for over thousands of years.
A short discussion is also given on the ecological consequences of crude oil
production and treatment as well as problems that generally arise in the petroleum
industry which crude oil chemists have to confront.
A detailed discussion on the properties of crude oil and crude oil products
and some methods for their improvement prepares the reader for the problems the
crude oil chemist faces daily. Some early traditional solutions for these problems,
which never became popular at the industrial scale, will show the reader that there
are many yet-to-be-researched ways to improve the methods for crude oil
treatment. This chapter also highlights the general chemistry of crude oil and crude
oil products.
The last chapter (i.e. chapter 2) of Part I deals with modern analytical
methods used in crude oil chemistry. Modern and classical methods of petroleum
and petroleum products characterization are explained. This chapter is an essential
chapter for present and potential crude oil chemists since analytical chemistry
constitutes an important part of crude oil chemistry. Besides, crude oil products
have so many special properties that are important for the industry. The need to
determine these properties gives rise to the very many analytical methods used in
petroleum chemistry.
1
Nature and Classification of Crude Oil
1.1 HISTORY AND NATURE OF PETROLEUM
Petroleum or crude oil has been known for a long time. Archeologists have
shown that it had already been extracted and used for about 5-6 thousand years
before Christ. The most ancient known oil wells are those at Ephrata and the
Kerch coast in the Chinese province of Sychuan. The mention of petroleum has
been found in many ancient manuscripts and books. For example, the Bible writes
about "pitch wells in the vicinities of the Dead Sea".
In ancient times, petroleum had some applications in medicine as well as
civil works. For example, the ancient Greek scientist Hippocrates (IV-V century
B.C.) has described many recipes of medicines which included petroleum. In one
ancient manuscript is written: "we shall rub the patients with petroleum in such a
way that the illness is taken away. White petroleum takes away the illness (cough
in this case). Black petroleum takes away a reasoning of the cough". The Egyp-
tians used petroleum oils to manufacture preservation mixtures.
Petroleum was also widely applied during construction work. Petroleum
bitumen was added to cement and the resulting product used during the con-
struction of the tower of Babylon. In the Bible, there is a narration that goes:
"Also each other has told to each other: "we shall do bricks and heat it by fire".
And they used the bricks instead of stones, and earthen pitch instead of cement".
Modern chemical analyses show that "earthen pitch" is "asphalt", the viscous
resinous substance remaining after the natural evaporation of the light fractions
from petroleum. Asphalt was applied in the construction of the Great Chinese
Wall as well as the trailing gardens of Semiramida. It was used as a water-
resistant medium for the construction of most of the ancient dams on Ephrata
4 Chapter 1
River. In the ruins of the ancient Indian city Mohengo-Daro was found a huge
pool constructed five thousand years ago. The walls of the pool were covered
with a layer of asphalt.
However, the greatest glory petroleum got was not for its use for construc-
tion. For more than two thousand years, petroleum was applied in military actions
and served as a source of military power. This was found in the discovery of the
antiquity based on the invention of "Greek fire". This new kind of weapon consid-
erably strengthened the military power of the countries that knew how to make
and operate them. It is still not proven scientifically who first invented the napalm.
Some people attribute the invention to the Byzantium alchemists, while others
think that the secret of its preparation was already known in ancient Greece. The
Greeks used to bind a vessel with a mysterious mixture to the end of a stick, and
threw it with the huge fire. Historians indicate that the fire flew with the speed of
light and with sound of thunder. When this vessel impinged on the wall, an explo-
sion occurred that gave rise to a huge cloud of smoke. The flame was distributed
in all directions. Water could not extinguish this fire.
Byzantium won a lot of fights using "Greek fire". The antic napalm was
especially of great service to Byzantium in the VII century during the attack by
the Arabs on Constantinople. The Arabian fleet had besieged the capital of
Byzantium. Besieged inhabitants of Constantinople had lost any hope of rescue
when the great idea came. During one of the attacks, they allowed most of the
Arabian fleet to come very close and unexpectedly unleashed a huge quantity of
"Greek fire" on the sea and burned it. The flame burned all the Arabian ships. It
seemed as if the sea was burning.
The composition of "Greek fire" was kept as a top secret. However Ara-
bian alchemists solved the secret of the "Greek fire" after almost four hundred
years after the fight at Constantinople. The main component of "Greek fire" was
petroleum with the addition of sulfur and saltpeter.
Up till now, petroleum has been used in many branches of construction
work or military service. It is thus hard to imagine what our life today would be
without crude oil. It brings power to all our machines and our houses. It is used
as a lubricant for various parts of machines. Hardly any modern device would
work without relying on various products derived from crude oil.
Even though the history of crude oil could be traced back by more than
two thousand years, real production of crude oil perhaps began in August 27,
1859, when the first industrial-scale crude oil well with a depth of 22 meters was
opened in Oil Creek, Pennsylvania. After this first industrial crude oil well was
opened, there was the commencement of a rapid development of crude oil
production and treatment. Probably, this day could be said to mark the birth of
modern crude oil chemistry. In 1878, the Swedish businessman Alfred B. Nobel
together with his brothers formed the Naphtha Company Brothers Nobel. The
company extracted the crude oil in Baku, Russia and transported it to the first
crude oil refineries via the pipelines built by Naphtha Co., which still exists
now.
It may sound strange but petroleum refers to a mountain mineral. It

usually exists together with sand, clay, stone, salt, etc. We normally think of a
mineral as a firm substance. However, there also exist minerals in the liquid
form and even in the gaseous form. One important property of petroleum is its
ability to burn. Other minerals that have this property are peat, brown and stone
coal, and anthracite. These combustible minerals form the special family of
minerals named "caustobolites" (derived from the Greek words causthos,
combustible; bios, life; cast, stone) meaning combustible organic stone [1].
There is a distinction between coal caustobolites and petroleum caustobolites.
All caustobolites, however, contain carbon, hydrogen and oxygen even
though in different proportions for different caustobolites. Specifically, petroleum
is a complex mixture of hydrocarbons and other carbon compounds. At the ele-
mental level, it consists of elements such as carbon (84-87%) and hydrogen (12-
14%) as well as oxygen, nitrogen and sulfur (1-2%). The sulfur content can some-
times be up to 3-5%. Overall, petroleum consists of hydrocarbons, asphaltenes and
resins, paraffins, sulfur and ash. There are three main groups of hydrocarbons in
petroleum—namely, paraffinic, naphthenic and aromatic hydrocarbons [2].
The paraffinic series of hydrocarbons have the general formula CnH(2n+2) and
can be either straight chains (normal) or branched chains (isomers) of carbon at-
oms. The lighter, straight-chain paraffins are found in gases and paraffin waxes.
Examples of straight-chain paraffinic hydrocarbons are methane, ethane, propane,
and butane (gases containing one to four carbon atoms, respectively), and pentane
and hexane (liquids with five and six carbon atoms, respectively). The branched-
chain (isomer) paraffins are usually found in the heavier fractions of crude oil.
They usually have higher octane numbers than the normal paraffins. Paraffinic
hydrocarbons are saturated compounds with all carbon bonds saturated (i.e., the
hydrocarbon chain carries the full complement of hydrogen atoms).
The amount of paraffins in different crude oils varies from 2 to 50%. The
light paraffins are mainly components of natural gas, which dissolve in the crude
oil in the oil wells. Depending on the composition and conditions in the oil well,
one can specify well classes such as gas wells, gas condensate wells and crude oil
wells. Gas wells contain mainly such light paraffins as methane, ethane, propane
and butane, all of which are gases at normal conditions (0.1 Mpa and 20 °C). Apart
from these hydrocarbon gases, gas wells also contain carbon dioxide (CO2), hy-
drogen sulfide (H2S) and inert gases such as nitrogen (N2), argon (Ar), helium
(He), neon (Ne) and xenon (Xe).
Often, gas condensate wells contain compounds with higher molecular
weights than compounds of gas wells. At natural conditions in the oil well (pres-
sures ranging from 25 to 45 MPa), these high molecular weight compounds
dissolve the gas. Initially during oil production from gas condensate wells, pres-
sure will decrease thereby releasing the low molecular weight compounds and
leaving the high molecular weight compounds behind. This high molecular
weight fraction is called condensate.
6 Chapter 1
Crude oil wells contain crude oil as well as gas. The amount of gas in the
crude oil varies from very little to hundreds of cubic meters per ton of crude oil.
These gases, solved in crude oil, can be released from the crude oil at normal
pressures. After production, crude oil is stabilized by separating the gas from the
oil (see Part III). The crude oil coming to the refinery usually contains less than
1% of dissolved gas.
All paraffins from C, to C7g can be separated from crude oil. However, it
has been shown that the largest fraction of paraffins in the crude oil is composed
of molecules from €7 to CM- Lighter or heavier paraffins are present in crude oil
in smaller amounts or as trace compounds.
All types of paraffins (i.e. «-paraffins and wo-paraffins) are present in
crude oil. The methyl-substituted paraffins were analytically proven to be pre-
sent in crude oil in the 1960s. It has been shown that methyl groups in paraffins
are located in positions 2, 6, 10, 14, 18 and further. Over 20 such isomers have
been found. The most abundant compounds of this kind of isomer are phitane
C2oH42 and pristane Ci9H4o (each was found in different crude oils in amounts up
to 1.5%).
It is known that paraffins from methane to butane are gases, from €5 till
On are liquids, and from C!8 onwards are solid substances. The solid paraffins
are present in all crude oils in different amounts, often up to 5%, but in some
crude oils up to 7% or even 12% have been found. Solid fractions of crude oils
do not only contain paraffins, but indeed these solids are complicated mixtures
of paraffins, naphthenes, aromatics and other compounds. It has been shown that
some heavy fractions from paraffmic oils can contain up to 50% paraffins, 47%
naphthenes and up to 3% aromatic compounds. It is known that the higher the
boiling temperatures of the crude oil fraction, the less the amount of paraffmic
compounds present in the fraction. However, paraffins are present in smaller or
higher amounts in all crude oils, crude oil fractions and products. The kind and
how the paraffins are present in oil (i.e. gas, solved or dispersed) depend on the
properties of the crude oil and the chemical conditions of paraffins.
The carbon atoms in the paraffin molecule are connected by a covalent
sigma (a) bond. The length of these bonds for the free isolated molecule in the
gas phase is 0.154 nm. The covalent angle between these C-C bonds is 112°.
The length and the valent angle can be different from the numbers shown for the
liquids and real gas paraffins. This difference can be explained on the basis of
the formation of hydrogen bonds between paraffin molecules. Through these
bonds, the conditions for intermolecular equilibrium in the paraffin will be
changed. However, it is well known that the power of the crystal field can
strongly influence the geometrical parameters of molecules by the formation of
hydrogen bonds. At the moment, there are very limited studies on the geometri-
cal differences between free isolated molecules and condensed molecules.
Paraffins can be present in crude oil as molecular paraffins as well as
associated molecules. The fraction of associated or molecular paraffins in crude
oil depends on many factors. However, one of the more important factors is
Nature and Classification of Crude Oil 7
temperature; the higher the temperature, the less the fraction of associated paraf-
fins in crude oil.
Usually paraffins are less prone to most known industrial reactions. The
most important industrial reactions of paraffins are oxidation, catalytic isomeri-
zation and sulfurization.
Naphthenic hydrocarbons have the formula CnH2n. All bonds of carbon with
hydrogen are saturated. As such, naphthenic hydrocarbons in petroleum are also
relatively stable compounds.
Naphthenic hydrocarbons are the most abundant class of hydrocarbons in
most crude oils. Their composition in oil can vary from 25 to 75%. Usually, the
amount of naphthenes in crude oil fractions increases as the boiling point of the
fraction also increases. However there is an exception: The amount of naphthenic
hydrocarbons decreases with an increasing boiling temperature for heavy oils.
This can be explained on the basis of the increasing amounts of aromatic com-
pounds in heavy oils.
The distribution of monocyclic naphthenes is well investigated at the mo-
ment in comparison to polycyclic naphthenes. Monocyclic naphthenic compounds
are distributed mainly in the light fractions of crude oil. So, naphthenic hydrocar-
bons in the gasoline fraction are mainly present as substituted cyclopentanes and
cyclohexanes. The amount of these compounds in gasoline fractions varies from
10 to 85%. The polycyclic naphthenes can be found mainly in the heavy fractions
of crude oil (with boiling temperatures over 350°C).
At the moment, chemical analysis has identified only 25 dicyclic, five tricy-
clic and four terra- and pentacyclic naphthenic compounds in crude oil. In cases
where there are over one naphthenic ring in one molecule, a part of the molecule
normally consists of a polycondensed ring.
Bicyclic naphthenes (C7 - C9) are usually used as an indication of a naph-
thenic crude oil. The following bicyclic naphthenic compounds were observed in
different crude oils: bicyclo[3,3,0]octane, bicyclo[3,2,l]octane, bicy-
clo[2,2,2]octane, bicyclo[4,3,0]nonane, bicyclo[2,2,l]heptane and their isomers or
substituted compounds.
The tricyclic naphthenes are mainly present by alkylperyhydrophenantrens.
The following compounds of this class, a), b) and c), have already been analyti-
cally identified.
a) b) c)
Chapter 1
Tetracyclic naphthenic compounds are mainly isomers and substituted

cyclopentanperhydrophenanthrene (C27 - C30). Examples are presented as com-
pounds d), e) and f).
d) e)
The most important compounds of the class of pentacyclic naphthenes are

represented by gopan (g), lupan (h) and phridelan (i).
g) h)
There are no analytical proofs for the exact structure of polycyclic naph-
thenic compounds with number of rings over five. However, based on the results
of mass spectral analysis of heavy oil fractions, it can be said that there are poly-
cyclic naphthens with seven or eight rings in their structure. At the moment, it is
very difficult to be specific in analytical terms of the exact chemical structure of
such molecules.
Since naphthenes are saturated hydrocarbons, the chemical activity of the
naphthenic compounds is similar to the chemical activity of paraffins. During
thermal treatment of the naphthenes, it takes part in reactions involving C-C bond
cleavage, dehydration and, to a lesser extent, aromatization reactions.
Aromatics are unsaturated ring-type (cyclic) compounds that react readily
since they have carbon atoms that are deficient in hydrogen. All aromatics have at
least one benzene ring as part of their molecular structure. Aromatics may also
have two or more of the ring structures fused together. An example of a fused
double-ring aromatic compound is naphthalene. The most complex aromatics are
polynuclear (i.e. they have three or more aromatic rings fused together). These are
found in the heavier fractions of crude oil.
The amount of aromatics in different crude oils varies from 15 to 50%. The
highest amounts of aromatics are typically found in naphthenic oils. The amounts
of different types of aromatic compounds decrease in the following order: benzols
> naphthalenes > phenanthrenes > hriezenes > pyrenes > anthracenes.
The highest amounts of aromatic compounds are concentrated in crude oil
fractions with high boiling temperatures. It has been shown analytically that aro-
matics are usually present as substituted aromatic compounds with the length of
the substituents up to thirty carbon atoms.
Asphaltenes and resins are dark substances (from dark red to brown). They
are soluble in aromatic solvents but insoluble in paraffin solvents [3]. Asphaltenes
have various types of heteroatoms present in crude oil in their structure. Asphalte-
nes are the most complicated known compounds in crude oil.
10 Chapter 1
Special properties of asphaltenes include the tendency to associate, high

molecular weight and paramagnetism. All these properties make asphaltenes very
difficult to analyze or investigate. This is why approximately since the 1970s,
asphaltenes chemistry exists as a separate science independent from crude oil
chemistry. In part four of this book, some problems that arise in asphaltenes stud-
ies will be discussed.
Porphyrins, special nitrogen compounds of organic origin, are also present
in petroleum. They are believed to be formed from chlorophyll of plants and he-
moglobin of animals. Porphyrins can be cracked at temperatures ranging from 200
to 250°C. The basic structural unit of porphyrins is given in Fig. 1.1.
.R'
R
\ \
N N
R"
R'"' R
Fig. 1.1: The structure of porphine basic structural unit of porphyrins.
The amount of nitrogen in different crude oils varies from 0.02 to 1.5%.
There are many types of nitrogen compounds in crude oil. The example shown in
Figure 1.1 is only one of them.
Studies of nitrogen compounds present in crude oil are made possible in two
ways. First, these compounds can be analyzed directly in crude oil. The biggest
advantage of such an analysis is the possibility to investigate these compounds
both in their natural form and natural environment. However, the concentration of
nitrogen compounds in crude oil is relatively small, and this makes the analysis
not only difficult but results in a rather wide divergence of the measurements. The
second method is that the nitrogen compounds can be separated before analysis.
The disadvantage of this method is the possibility that during separation, the native
structure could be destroyed. However, despite the difficulties in investigating
nitrogen compounds, analysis has shown that, at the moment, nitrogen compounds
are present in crude oil mainly as cyclic compounds. Nowadays, nitrogen com-
pounds can be classified as alkaline (lye) nitrogen and neutral nitrogen com-
pounds.
Pyridines (a), hinolines (b) and acredines (c) belong to the strong alkaline
(lye) nitrogen, because of their free, non-compensated electron pair.
a) b) c)
The substituted anilines (d), amides and/or imides belong to the weak alka-
line (lye) nitrogen compounds.
d)
NH
LJ*
The non-substituted compounds such as indols (e) or carbozoles (f) are
typical nitrogen neutral compounds.
f)
NH
The above are some examples of nitrogen compounds in crude oil. It is

however difficult to show all the possible nitrogen compounds present in crude oil.
Recent investigations have shown that compounds with two nitrogen atoms or one
nitrogen atom and one sulfur atom in one molecule can be found in crude oil.
The nitrogen compounds are very important in their role as natural surfac-
tants. The concentration of these compounds in crude oil has a great influence on
the chemical and physical activities of the crude oil, on metal/crude oil interface
and ground/crude oil interface. This property of nitrogen compounds is used dur-
ing the production of crude oil from the oil well. For example, hinoline can pre-
vent the corrosion of metal parts; this is very important for the continuous working
of many oil production plants.
The next class of heteroatom compounds in crude oil is the oxygen com-
pounds. The amount of oxygen in crude oil can vary from 0.1 to 3% or even 4%.
The amount of oxygen in crude oil fractions increases with the boiling temperature
12 Chapter 1
of the fraction. Over 20% of all oxygen compounds are concentrated in asphalte-
nes and resins.
Almost similar to nitrogen compounds, the oxygen compounds can be clas-
sified as neutral oxygen and acidic oxygen compounds. The cyclic and aromatic
compounds, ethers, anhydrides, furans and so on usually belong to the neutral
oxygen compound class.
The acidic oxygen compounds are usually represented by carbon acids. The
presence of these compounds in crude oil has been known for a very long time. It
was noticed during the production of light kerosene. In the production of high
quality light kerosene, it was necessary to clean the kerosene with lye. Compounds
with strong emulsifying properties were produced during this process. At the end
of the nineteenth century, it was shown that these compounds were sodium salts of
carbon acids.
Sulfur may be present in crude oil either as hydrogen sulfide (H2S), or as
compounds such as mercaptans (a), thiophenols (b), cycloalkanethiols (c), thio-
phenes (d), benzothiophenes (e), alkylbenzothiophenes (f), etc., or as elemental
sulfur.
a) b) c) d)
CH2
CH2
i ;s
R
e)
Each crude oil has its own types and proportions of sulfur compounds. As a
general rule, however, the proportion, stability, and complexity of the compounds
are greater in the heavier crude oil fractions. Hydrogen sulfide is a primary con-
tributor to corrosion in refinery processing units. Other corrosive sulfur materials
are elemental sulfur and mercaptans. Pyrophoric iron sulfide results from the cor-
rosive action of sulfur compounds on the iron and steel materials used in refinery
process equipment, piping and tanks. The combustion of petroleum products con-
taining sulfur compounds results in the production of undesirable by-products such
as sulfuric acid and sulfur dioxide. Catalytic hydrotreating processes such as hy-
drodesulfurization remove sulfur compounds from refinery product streams.
Sweetening processes either remove obnoxious sulfur compounds (example, mer-
captans) or convert them to odorless disulfides. The amount of sulfur in petroleum

of different origins ranges from 0.1 to 5% [2].
Sulfur compounds in crude oil sharply decreases the quality of fuels and
oils produced from the crude oil. They cause corrosion of equipment during
treatment, reduce activity of antidetonation additives and antioxidizing stability
of gasoline, raise the propensity to form hard residues in cracking gasoline frac-
tions, and result an environment pollution.
Metals (including heavy metals) have been found in all crude oils. Their
composition varies from 0.01 to 0.04% of crude oil. About thirty different met-
als are found in different crude oils. The most common are vanadium, nickel,
iron, zinc, mercury, boron, sodium, potassium, calcium and magnesium.
Unsaturated compounds like alkenes are not presented in crude oil. How-
ever, these compounds can be produced during the thermal or/and catalytic
treatment of the crude oil. These compounds differ from all crude oil com-
pounds by their high chemical activity. Based on the high chemical activity of
unsaturated compounds, it is clear why this class of compounds does not exist in
crude oils.
Ash forms the balance in petroleum. It is the noncombustible portion that is
left behind after petroleum is burned. Ash is composed of various metallic com-
pounds such as compounds of iron, nickel and vanadium as well as various salts.
Petroleum is also characterized by physical properties such as density, vis-
cosity, temperature of hardening, boiling temperature and solubility as well as
electrical and optical properties [4].
1.1.1 Origin of Petroleum
The first attempt to explain the origin of petroleum dates back to antiquity.
For example, the Greek scientist Strabon, who lived about 2000 years ago wrote:
"At the place named Nymphey, there is a rock spiting fire, and under it are the
sources of warm water and asphalts... ". Strabon united two facts: the eruption of
volcanoes and the formation of asphalts (the way he named petroleum). This con-
nection between the two facts was a mistake. In the places mentioned by his work,
there were no erupting volcanos. The events which Strabon described as "erup-
tions" were actually "emissions", i.e. breaking out of underground waters (so-
called geysers), accompanied by outputs of petroleum and gas on the surface.
M.V. Lomonosov was one of the first scientists to introduce a reasonable
scientific concept of the origin of petroleum. In his mid-eighteenth century work
on "terrestrial layers", this Russian scientist wrote: "It is expelled from under-
ground with heat, prepared from stone coal and brown coal, this black oily mate-
rial... And this is a birth of a different grade of combustible liquid and dry hard
matter. This is the essence of stone oil, liquid pitch, petroleum, and similar materi-
14 Chapter 1
als which are different by cleanliness, but occur from the same origin" [5]. It can
therefore be stated that the idea of the organic origin of petroleum from stone coal
was conceived more than 200 years ago. The initial substance was an organic
material transformed at first into coal and then into petroleum.
Lomonosov was not the only one who addressed the question of the origin
of petroleum in the eighteenth century. However, some of the other hypotheses
formed at this time were less than scientific. For example, a hypothesis credited to
a Warsaw priest was that the Earth was very fertile in the paradise period. The
core of the earth contained a fatty impurity. After the paradise period, this fat was
partially evaporated, and the vapor partially condensed on the ground where it
mixed up with a variety of materials. This was later transformed to petroleum by
the world flood.
There are many other less scientific hypotheses about the origin of petro-
leum even by scientists. At the end of the nineteenth century, the authoritative
German geologist H. Hefer reported of an American petroleum industrialist who
considered petroleum to have resulted from wet whales that existed at the bottom
of polar seas. This petroleum penetrated into Pennsylvania by seeping through
underground channels [5].
In any case, the most widespread ideas among the scientists in the nine-
teenth century centered on the organic origin of petroleum. Disputes were mainly
around the initial material for petroleum formation: animals or plants? German
scientists H. Hefer and K. Engler carried out experiments in 1888 in which they
sought to prove that petroleum formation was from animal origin. The experi-
ments were performed by evaporation of fish fat at 400°C and 1 bar. Oil, combus-
tible gases, water, fats and different acids were formed from the 492 kg of fat
used. The largest fraction of evaporated material was oil (299 kg, or 61%) with a
density of 0.8105 g/cm3. Subsequent evaporation of the oil product yielded satu-
rated hydrocarbons (ranging from pentane to nonane), paraffin, lubricant oils as
well as olefms and aromatic hydrocarbons. Later, a Russian scientist (N.D. Ze-
linskiy) carried out a similar experiment in 1919. However, his initial material was
organic silt of mainly vegetative origin from Lake Balhash. The evaporation prod-
ucts in this case were: crude pitch - 63.2%, coke - 16.0%, and gases (methane,
carbon oxides, hydrogen, hydrogen sulfide) - 20.8% [5]. Subsequent processing of
the pitch yielded gasoline, jet oil and heavy oil.
By the end of the nineteenth century, two different hypotheses of petroleum
origin had emerged: organic and inorganic hypothesis. The main concept of inor-
ganic petroleum origin was illustrated by the experiments of Berthelot. In 1866,
Berthelot considered that acetylene was the basic material. Large quantities of
acetylene were assumed to be produced by the reaction of water with carbides
which, themselves, were formed by the reaction of alkali metals with carbonates.
The conversion of acetylene to petroleum was accomplished at an elevated tem-
perature and pressure according to the following:
CaCO3 -> CaC2 + H2O -» C2H2
petroleum
Indeed, the idea of the inorganic origin of crude oil did not initially have
any success with geologists, who considered that experiments carried out in the
laboratory considerably were different from processes that occur in a nature.
However, the inorganic theory of crude oil formation unexpectedly received
support due to new evidence from astrophysics. Research on the spectra of plan-
ets showed that, there are hydrocarbon compounds in the atmosphere of Jupiter
and other large planets as well as in gas environments of comets. If hydrocar-
bons are widespread in space, it means natural processes of synthesis of organic
substances from inorganic substances are possible.
In the 1950s, the Russian scientist N.A. Kudryavzev collected a lot of
geological material involving petroleum and gas deposits in the world. First of
all, Kudryavzev noticed that many gas and petroleum deposits were found in
zones of deep cracks of the terrestrial core. This knowledge was not new at this
time since other scientists had noticed this fact much earlier. However, Ku-
dryavzev extended the application of such ideas to a great extent. For example,
in the north of Siberia, near the area of the so-called Marhiinskij shaft, there are
frequent outbursts of petroleum onto the surface. At a depth of about two kilo-
meters, the mountain layers are literally impregnated with petroleum. At the
same time, it has been shown that the amount of carbon formed simultaneously
with mountain layers is extremely small (only 0.02 to 0.4%). But further from
the shaft, the amount of organic compounds in the layers increases. Neverthe-
less, the quantity of petroleum sharply decreases. Based on these extra data,
Kudryavzev suggests that crude oil formation in the Marhiinskij shaft can most
likely be explained not on the basis of formation from organic substance, but by
an inorganic theory of oil formation in the deep layers (or shells) of the planet.
Similar oil wells have been found in other regions of the world as well. A long
time ago in Wyoming (USA), the inhabitants heated their houses using pieces of
asphalt, which they collected from the cracks in mountain layers in the Copper
Mountains. But the minerals, of which these mountains consisted, could not
accumulate petroleum and gas. This means that the asphalt (similar to oil) could
only be formed according to the inorganic theory.
The space hypothesis of the origin of oil deserves mention as well. In 1892,
Sokolov stated that the dust cloud from which the Earth and other planets of the
solar system were formed consisted of hydrocarbons. In the process of the forma-
tion of the Earth, hydrocarbon substances were buried in the core of the earth.
Further, during the cooling of the planet, the hydrocarbons were pushed out. As a
result, they penetrated into cracks of friable minerals. This hypothesis is also one
of the representations of petroleum synthesis from minerals.
16 Chapter 1
However, the origin and formation of petroleum are very difficult questions
and it is almost impossible to answer them using only one theory. A more detailed
discussion concerning the origin of crude oil formation can be found in references
[6-9].
1.1.2 Oil Formation in the World's Oceans
All seas and oceans are populated with biomass which are essentially a wide
variety of animals and plants. Of all sea biomass, the ones with the most signifi-
cant role in petroleum formation are microorganisms, typically plankton, 90% of
which is microscopic seaweed (phytoplankton). Plankton is the basic source of
organic material in the sea. Plankton is contained not only in the silts at the bottom
of seas or lakes but also dispersed or dissolved in the water. Approximate quanti-
ties of organic material dissolved per m3 of water are 2 g in the Atlantic and Pa-
cific oceans, 5-6 g in the Baltic and Caspian sea, and 10 g in the Azov sea. It is
interesting that the dissolved organic material is like greasy acids that is structur-
ally similar to plankton fats. The concentration of organic material is highest at the
bottom of the oceans. This is obvious because, for the most part, these organisms
are denser than the liquid medium. As such, they fall down to the bottom by grav-
ity. Shallow conditions are the preferable places for accumulation of organic mate-
rial. Generally, the process of mineral (clay, sandy minerals, etc.) accumulation
promotes fast trapping or collection of organic material as well as its protection
from decomposition. On the other hand, for organic material found deep in the
ocean water, there is sufficient time for it to be substantially dissolved and dis-
persed in the water due to the activity of bacteria. Consequently, only 1% of or-
ganic material is usually collected annually per m2 of ocean bottom in the world's
oceans out of 150 g that is formed.
Now, let us consider what occurs when organic material is collected on the
sea bottom. Organisms that are either brought from different continents or are
formed directly in the sea are collected rapidly in clay or sandy minerals. Although
organic materials contain various substances, the one with the greatest interest for
subsequent petroleum formation is "bitumoid". Birumoid can be extracted from
organic material using various solvents such as chloroform, benzene or ether. The
main source of bitumoides are lipoid (i.e., fat or a similar compound). The propor-
tion of bitumoides in the sea bottom deposits ranges from 2 to 20% of all organic
material. Apart from bitumoides, materials such as hydrocarbons (from 0.1 to 3%)
are also available in organic material. Approximately 300 g (and in some cases up
to 15 kg) of hydrocarbons are contained in 1 m3 of minerals formed. The average
quantity of dispersed hydrocarbons in minerals is 70-80xl012 ton. This exceeds the
established volume of hydrocarbons in oil fields (about 2.2xl012 ton) by about
tenfold. It is therefore evident that the organic material collected as described
earlier in this section is sufficient to form the established world petroleum re-
serves.
Dispersed hydrocarbons in solid minerals and silts in the seas are similar to
petroleum hydrocarbons. They are called dispersed petroleum or micro-petroleum.
Mountain minerals are hydrofill, meaning that they are moistened with wa-
ter instead of petroleum. Thus, in addition to mountain pressure, capillary forces
enhance the displacement of petroleum in the solid minerals.
The process of petroleum displacement in the native minerals (i.e. from
which it is formed) is referred to as primary migration or emigration. By getting
into loose solid minerals (collectors or traps), petroleum begins a new life.
Petroleum migration through collectors proceeds as long as it does not encounter
a trap (i.e. a layer that is capable of keeping the petroleum as a trapped deposit).
Examples of these traps are anticline traps, traps associated salt domes and oil
entrapment in a limestone reef. These are shown in Figures 1.2-1.4. Thus, the
pre-history of petroleum begins in live organisms from which are synthesized
initial biochemical compounds. On the other hand, the history of petroleum
begins with the collecting of biological and organic substances in the solid min-
erals [3].
oil
Fig. 1.2: Anticline traps.
Traps associated with salt intrusions are of many types (example: Fig. 1.2-
1.3); limestone reefs (Fig. 1.4) can also serve as reservoir rocks and give rise to
overlying traps of anticlinal form as a result of different compaction. Examples are
also known in which the reservoir rock extends to the surface of the earth but oil
and gas are sealed in it by clogging of the pores by bitumen or by natural cements
[3]. Many reservoirs can display more than one of the factors that contribute to the
entrapment of hydrocarbons.
18 Chapter 1
water
oil
water
salt dome
Fig. 1.3: Traps associated with a salt dome.
oil
water
Fig. 1.4: Oil entrapment in a limestone reef.
Detailed discussions on oil and gas formation and modern methods of inves-
tigation in this area can be found in references 10-33.
1.1.3 Modern Concept of Formation of Petroleum
The characteristic feature of the modern concept of petroleum formation is

based on a new geological idea. Here, there is the representation that there occurs
a horizontal movement of separate blocks of the lithosphere, the so-called, "litho-
sphere-plates". Deep down our planet is a circulation of material according to the
so-called "convective movement" [5], which began a long time ago at a depth of
about three thousand kilometers into the earth where hot and rather light material
started moving upwards. After 15-16 million years, this movement reached the
lithosphere - the top and thinnest terrestrial environment. This material spread
over and "broke off' on the lithosphere into plates as a result offerees of viscous
friction. The plates moved apart from the region of outward flow of material and
drifted in a horizontal direction. The original structures were formed as huge fail-
ures or "rifts". These were then transformed into the ocean. Today, typical conti-
nental rifts exist in East Africa. They are typically filled with water. An example
of a modern sea rift that illustrates a subsequent stage of transition of an initial rift
structure to the ocean is the Red Sea.
The horizontal movement of the lithosphere plates eventually resulted in the
collision of the plates in which one plate was "pushed" under another plate. This
created the zone of subduction. Typically, during the immersing of lithosphere-
plates, the friction involved generates a considerable amount of heat that results in
increasing the temperature of the zone by hundreds of degrees. This process pro-
motes melting of the moved plate and gives rise to the occurrence of volcanic
processes. The modern subduction zones are widespread on the coast of the Pa-
cific Ocean and on the eastern part of the Indian Ocean. These processes are ac-
companied not only by active volcanic processes, but also by strong earthquakes.
As a result, the lithosphere is always in continuous movement. What is the relation
of the formation of petroleum to these powerful natural phenomena? Formation of
petroleum is a very energy-intensive process. It involves the dissociation of vari-
ous compounds, breaking of chemical bonds between carbon and oxygen, nitrogen
and sulfur, etc. These are processes that require significant amounts of energy to
be expended. For example, C-C bond scission requires 70-100 kcal/mol whereas
C-O bond breaking requires 70-200 kcal/mol. These processes can be initiated and
made to proceed actively within the temperature range 100-400°C. Below this
temperature range, transformation of dispersed organic material to petroleum will
proceed slowly and languidly, and will not completely exploit the potential of the
availability of the organic material resource. Chemists have synthesized a product
that is practically similar to natural petroleum from natural organic material. This
has been made a very rapid process as a result of the high temperature used in the
reactor. Hence, if the situation whereby solid minerals with organic material are
made to pass through the zone of high temperature can be provided in nature, the
formation of petroleum can be facilitated. A required condition for this purpose is
that the layer that contains organic material should be located at a minimum depth
of 2-3 km. This is where the main stage of petroleum formation proceeds. And
what will occur if organic material passes in the zone of rift or subduction? This
area is five to six times hotter than the surrounding areas. Hence, the transforma-
tion of organic material into liquid petroleum will be facilitated. Practically, it can
begin simultaneous with collecting solid minerals to make the trap. That is why
zones of rifts and subduction are usually of special interest to geologists when
performing oil-prospecting work. Since this knowledge gives them a key to a
20 Chapter 1
correct understanding of the genesis of hydrocarbons, they can predict what is

likely to occur in such places.
We will now view the processes in the rifts. The process of rift formation
precedes a strong increase in temperature of the formation zone ("excitation" of
the top layer). This is represented in the structure of modern rifts: thinning of ter-
restrial layers up to 30-35 km; reduction of asthenosphere depth; strong increase of
a thermal flow under the rift; volcano formation; formation of the thermal water
sources; and seismicity. All these characterize rifts as extremely active structures
in the lithosphere. The mineral pools in the rifts are formed during the initial stage
of the destruction of the terrestrial layers. Narrow deflections filled with 4-7 km of
organic containing solid minerals exist for short time intervals of 5-20 million
years. At the initial stages of collecting of the solid minerals in the rifts, the usual
continental river or lake with layers of volcanic formations is formed. Often, the
formation of salt complexes is postponed until later. This postponement is con-
nected with postponing salt formation within the deep thermal water. Normal sea
minerals are collected during the process of rift formation as well as its transfor-
mations from continental layers to sea intercontinental rift (as in the Red Sea). In
the central part of the rifts where there is limited water circulation, clay layers
enriched by organic material (black clay) usually accumulate. A fast immersion
occurs very deep in the earth at the stage of rift formation. This process promotes a
substantially abnormally high thermal flow in the rifts. As a result, petroleum
formation is facilitated. Therefore, it is possible for formation of hydrocarbons to
have already occurred in young superficially located layers. Even the lake miner-
als containing small quantities of organic material are able to form petroleum. For
example, there are numerous petroleum and gas wells in the modern East African
rift system. Separate rifts that are filled with water form a system of lakes where
gas and light petroleum reserves are found.
There are other kinds of geological events that proceed in zones of subdue -
tion, but the result of these processes is the same: the acceleration of the transfor-
mation of dispersed organic material to petroleum. The movement zones are two
very important areas for petroleum formation phenomena: formation of lenses
traps and movement of organic material from the ocean into the trap by means of
the displaced plates.
More about modern theories about oil and gas formation and modern
investigation in this area can be found in other references [34-37].
1.1.3.1 Crude oil prospecting
The basis for oil prospecting lies on the possibility of obtaining a geologi-
cal map of the prospecting area. In certain areas (e.g. Iran), one could easily
detect possible oil wells by air photography of the earth's surface in the pros-
pecting area. Geological prospecting can be made very exactly. However, it can
only enable us to evaluate the structure of the surface complexes of mountain

layers. The structure of the mountain layers prospected on the surface does not
usually represent the structure of the deeper layers. Geologists use geophysical
methods of crude oil prospecting to obtain a deeper insight of what lies below
the Earth's surface. There are four popular geophysical methods of crude oil
prospecting: seismic prospecting, gravimetric prospecting, magnetic prospecting
and electric prospecting.
The seismic method is based on studies of features of the transmission of
elastic fluctuations in the terrestrial core. The elastic fluctuations (or seismic
waves) can be produced artificially, for example by explosion. The speed of
their transmission in each layer varies from 2 to 8 km/s and depends on the den-
sity of environment. The higher the density of the layer, the faster seismic waves
can be transmitted through it. A fraction of the elastic fluctuations is reflected to
a surface (i.e. reflected from the border between two or more layers with differ-
ent densities), another fraction of seismic waves continues movement but re-
fracted deeper through layers up to a new border between terrestrial layers. Re-
flected seismic waves can be detected by using special devices called seismic
detectors. Researchers then perform an evaluation of the diagrams generated
from wave fluctuations of the prospecting surface, including the depth of the
maintain layers that reflected the seismic waves, and in some cases, obtain a
lithological structure of the layer. Based on these data, the structures of deep
layers are clarified, and maps of the underground relief (the so-called structural
maps) are made. Based on these maps, the structure of deep terrestrial layers is
investigated. The method of reflected waves was first used in Russia in 1923.
After then, it became used successfully all over the world. This method is still
used by geologists today.
Another method of seismic prospecting is based on detecting the refracted
seismic waves obtained at the border between two or more layers under a critical
corner. This method is widely applied in the world today. In the practice of seis-
mic crude oil prospecting, other methods, including the method of controlled di-
rected reception and the method of common deep point, are also used. The last
method is especially widely applied for prospecting not only anticline traps, but
also the zones of their formation. The method of common deep point is carried out
by change of a mutual arrangement of the explosion and reception points. In such
way, two or more reflected seismic waves from the same underground point can
be detected.
The use of explosions as a source of seismic waves is actually somewhat ob-
solete for geophysicists. Since the 1960s, first in the US and now worldwide, non-
explosive methods have been used for generating seismic waves. The most popu-
lar of these methods are the method of a falling load, the method based on using
vibrators, and methods based on conversion of explosion energy from mechanical
power. Today, almost all the seismic prospecting work is carried out without using
any explosive sources. Seismic crude oil prospecting in the sea makes use of
pneumatic and/or electrical sources of seismic waves.
22 Chapter 1
The gravimetric method is based on investigating the distribution of the

gravitational force on the Earth's surface. The acceleration of an object (for
example in a mountain area) in a free fall depends on the density of the moun-
tain layers. If the underground is the layer of stone salt having a relatively low
density, the acceleration due to free fall decreases, indicating a negative anom-
aly in the gravitational field. In the case where the layers are composed of a
more dense material (granite for example), a positive anomaly in the gravita-
tional field is indicated.
Usually, the gravimetric method is applied in combination with magnetic
prospecting. Our planet is a huge magnet. That means the Earth has a magnetic
field. The characteristics of the field are influenced by the compositions of the
mountain layers constituting the terrestrial core. For example, magma layers are
more magnetically active than sands. A magnetic anomaly arises above a place
of layer location.
Usually, gravimetric and magnetic methods are carried out before seismic
prospecting. Seismic prospecting is carried out based on what information on the
gravimetrical and magnetic anomalies is obtained. After detecting anticline traps
or any other kind of traps, a detailed seismic investigation of the area is carried
out to establish both the exact contours of the trap and the depth of its location.
After that, drilling is possible.
There is one more geophysical method. This is the electrical prospecting
method developed in France in 1923. This method is based on investigating the
Earth's core by measuring the electromagnetic fields either of an artificial or natu-
ral origin on a ground. The main idea of the method is that the mountain layers
have various electrical properties. For example, petroleum is dielectric, the miner-
als rich in iron are good electric conductors. Geophysicists investigate the Earth's
core by creating an artificial electrical field and studying the electrical resistance
of mountain layers. By tracing high-resistance layers, it is possible to identify deep
relief anticline traps.
The geological and geophysical methods of crude oil prospecting do not
always give the correct answer to the question whether there is an oil or gas
deposit in the Earth. As a matter of fact, the presence of traps or collectors is
necessary, but it is not a sufficient condition for the accumulation of crude oil
deposits. Frequently, it has been observed that after drilling in the prospected
area, neither petroleum nor gas is present. This is why it is recommended to
carry out geochemical and hydrogeological prospecting after geological and
geophysical investigation of the area. Based on results of the geochemical and
hydrogeological prospecting, it is possible to confirm the presence of petroleum
or gas in traps based on the microconcentration of the hydrocarbons on the
Earth's surface in a researched area. Geochemical methods include gas, lume-
nescic, radioactive, photography and hydrochemical methods.
The gas photography method was first used in Russia in 1929. The main
principle of the method is that there is filtration and diffusion of gases through the
pores and cracks in the mountain layers of dispersed hydrocarbon gases around
any crude oil deposit. Such an anomaly is usually a direct attribute of the crude oil
or gas deposits. The disadvantage of the method is that the anomaly can be dis-
placed from a source upwards of the layers.
The lumenescic method is based on an investigation of the bitumen dis-
persion area. The bitumen content in a layer rises above the crude oil or gas
deposits. Samples from the layer are selected from shallow depths, and investi-
gated using ultra-violet light.
The radioactive photography method is based on investigation of distribu-
tion of radioactive elements (first of all uranium) above petroleum and gas depos-
its. The radioactivity above the crude oil deposits is lower than around the deposit.
However, radioactive anomalies in surface layers can be due to changed lithologic
structure of layers. That is why this method is applied rarely.
With the hydrochemical method, the chemical composition of underground
water together with its contents of dissolved gases and organic substances is stud-
ied. A large amount of hydrocarbons in the underground water shows a high pos-
sibility of the presence of petroleum deposit in this area.
More about oil and gas prospecting and modern investigation in this area
can be found in references 38-46.
1.1.3.2 Drilling and crude oil extraction
Practically all the drilling today is carried out according to the rotary prin-
ciple. A drilling tool screwed in at the lower end of the hollow linkage (either
roller chisels or diamond chisels) is shifted in a rotary motion by a turntable
installed in the drilling tower. The chisel drills into the Earth's layers. The bore-
hole usually has a diameter of 10 to 70 cm. The borehole begins with the largest
diameter at the surface and then decreases with depth.
Heavy bars are installed to increase the load pushing on the chisel and to
improve the drilling capacities. The individual parts are lined with steel tubes
and sealed against the mountain layers with cement. The layers of material
drilled out must be removed from the borehole. The scavenge pump is used to
ensure this removal as it maintains a liquid circulation in the drilling borehole.
Water is constantly supplied to the chisel as coolant. It ascends the pipe system
with constant pressure and thereby carries all detached rock particles forward.
During the drilling process, particles that are constantly brought by the flushing
water are examined in order to obtain information on the characteristics of the
drilled layers. The first pipe system (so-called "preventers") is now installed for
protection against uncontrolled oil or gas release. A simplified example of a
drilling tower is shown in Figure 1.5.
24 Chapter 1
Fig. 1.5: Example of drilling tower.
Crude oil extraction begins after successful drilling. The three most popular
extraction methods are:
1. Eruptive extraction. Each crude oil deposit has a natural layer pressure,
which increases by up to one bar for every 10 meters of depth. Dissolved
gas also flows together with the crude oil from the oil well, the combined
flow resulting in pressure depletion in the well. Consequently, the gas
begins to exit from the oil accompanied by volume enlargement. The exit
of crude oil from the oil well in this case can be compared with the exit
of soda water from the bottle when it is opened.
2. Gas elevator extraction. After eruptive extraction has ended naturally,
one then sets the oil well under sufficient pressure that will force the oil
out, and so extend the period of free flowing out of the oil. Gas elevator
extraction has a distinct area of application. Frequently, one prefers to
pump to gas elevators during extraction of oil from larger depths (ap-
proximately between 2500 and 3500 meters).
3. Pumping extraction. Pumping is the most frequently used artificial ex-
traction method. The most important feature of this extraction method is
the use of a pump. The pump consists of three sections: the deep pump,
the pump linkage and finally the drive unit, which is represented by the
pump support (so-called horse head) with the driving motor. The usual
stroke rate for this pump varies from a few strokes up to 20 strokes per
minute. An example of such a pump is shown in Figure 1.6.
Fig. 1.6 Example of pumping extraction.
A special problem in crude oil extraction arises if high viscous petroleum or

bituminous petroleum is being extracted. There is a significant number of oil
wells in some places in the world, especially in Canada, with viscous and paraf-
26 Chapter 1
finic crude oils, which are remote from practical power sources. Most of such oil
wells are concentrated in deposits with porous traps. The most popular method
for extraction of such oils is the thermal method.
In this method, the oil deposit is opened for extraction by the opening of
boreholes, which are located in a uniform triangular grid formed by a thirteen-
borehole system with six boreholes in each of the two concentric circles. These
thirteen boreholes are located as follows: surrounding one central borehole is a
circle (i.e. first concentric circle) of boreholes consisting of six boreholes, and a
further six-borehole circle forming the second concentric circle. Thirteen bore-
holes are thus located so that each of the boreholes is located from the nearest ones
by an identical distance. The heat-medium (for viscosity decrease of the petro-
leum) is carried out cyclically, with each cycle consisting of three stages.
In the first stage, the introduction of the heat-medium is conducted simulta-
neously through the central input borehole and every second extraction borehole
of an external ring. Crude oil is extracted from all the other boreholes.
In the second stage, the introduction of the heat-medium is carried out
through the central borehole as well, but the role of boreholes in the external
ring changes: the heat-medium input boreholes now become extraction bore-
holes and the extraction boreholes now become heat-medium input boreholes.
The amount of heat-medium introduced in the second stage is the same as that in
the first stage.
In the last stage, only the central borehole is used as the heat-medium bore-
hole, and all the other boreholes play the role of extraction boreholes.
More drilling and extraction of crude oil can be found in reference 47.
1.1.4 Consequences of Intensive Extraction and Processing of Oil |6-8]
Initially, the adverse effects of intensive petroleum extraction were not of

any prime consideration. The key was to extract as much petroleum as possible.
However, about fourteen years into the twentieth century, some indications of
these adverse effects had already appeared.
It happened in the oil well in Wilmington (California, USA). This oil well is
located between the southwest areas of Los Angeles and a gulf where Long Beach
reaches the coastal quarters of the same resort city. The area of this petroleum pool
is 54 km2. The oil well was drilled in 1936. In 1938, it became the center of oil
extraction in California. By 1968, almost 160 million tons of petroleum and 24
billion m3 of gas were extracted from this oil well.
The location of the oil well at the center of industrial and densely populated
areas of southern California, and also its proximity to the large oil refineries in Los
Angeles, was considered very crucial to the economic development of the whole
of California. As a result, a very high level of extraction from this well (as com-
pared with other petroleum wells in North America) was constantly supported
from the beginning of the operation of the oil well till 1966.
In 1939, the inhabitants of the cities of Los Angeles and Long Beach ob-
served an appreciable concussion of the ground surface. The lowering of the
ground above the oil pool thereby began. The intensity of this process amplified in
the next fourteen years following when it started. The overall process resulted in
what could be considered as an elliptic rift. After sixteen years, the amplitude of
the lowering had already reached 8.7 m. The horizontal displacement with this
amplitude was up to 23 cm, directed towards the center of the area. Movement of
the ground was accompanied by earthquakes. Five strong earthquakes were regis-
tered in the period from 1949 till 1961. In a literal sense, the earth fell from under
the feet. Ports, pipelines, urban structures, highways, bridges and petroleum wells
collapsed. About 150 million dollars was spent for reparation. In 1951, the rate of
sinking of the ground surface achieved a maximum value of 81 cm per year. There
was a threat of flooding. Frightened by these events, the urban authorities of Long
Beach stopped the operation of the oil wells in order for them to develop a good
method to solve the problem.
In 1954, it was shown that the most effective method to mitigate this prob-
lem was water flooding (i.e., the input of water in the layer). Water input had other
advantages as well. For example, there was an increase in oil extraction. The first
stage of work for the flooding of the oil layer started in 1958, from which time a
southern part of the productive layer was input 60 thousand m3 of water per day.
In the ten years that followed, the rate of flooding of this layer increased to 122
thousand m3 per day. The lowering of the ground surface practically stopped. At
the end of the twentieth century, the rate of lowering of the center of the zone did
not exceed 5 cm per year. In some areas, there was even an elevation of the sur-
face of about 15 cm. The oil wells are again in operation. Now, for each ton of
petroleum extracted, about 1600 liters of water is needed. The maintenance of the
layer pressure gives up to 70% of daily petroleum extraction in the old areas of
Wilmington. Generally, 13,700 ton per day of petroleum is extracted from the oil
wells.
Reports appeared in 1999 about the lowering of the Northern Sea, close to
oil wells in Ecofisc, after the extraction of about 172 million tons of petroleum and
112 billion m3 of gas. It was accompanied by deformations of well trunks and sea
platforms. The consequences are difficult to predict, but their catastrophic charac-
ter is obvious.
Lowering of the ground accompanied by earthquakes also occurred in old
oil-extracting areas of Russia. It was especially strongly felt in Starogroznenskij
oil wells. Weak earthquakes that resulted from intensive petroleum extraction
were felt in this city in 1971. The earthquake was of intensity of 7 M at the epi-
center and was located 16 km from the city of Groznyj. The aftermath was that
owners of homes and office buildings had to be compensated. Workers who were
displaced from working in the oil wells also had to be settled. Lowering of the
ground occurred in the old oil wells in Azerbaijan. This was considered to be due
to horizontal motions. These horizontal motions were responsible for breaking of
pipes in the operational petroleum wells.
28 Chapter 1
An earthquake was registered in April, 1989 in Tataria with an intensity up

to 6 M. In the opinion of the local experts, there was a direct connection between
amplification of petroleum extraction from oil wells and activation of weak earth-
quakes. Cases of breakage of oil well trunks and columns are on record in the
Tataria example. Earthquakes in this area are especially dangerous since Tataria
nuclear power station is located in this area. In all these cases, one effective meas-
ure to mitigate the problem is water flooding. Forcing water into the productive
layer compensates for the extracted petroleum.
1.1.4.1 Dangerous fogs
Another danger in petroleum lies in the use of petroleum and gas as a fuel.
During the combustion of these materials, enormous amounts of carbon oxides
(such as carbon dioxide (CO2)), various sulfur compounds (such as sulfur dioxide
(SO2)), nitrogen oxides (such as nitric oxide (NO) and nitrogen dioxide (NO2)),
etc. are released into the atmosphere. In the last half of the twentieth century, the
contents of CO2 in the atmosphere has increased by almost 288 billion tons, and
more than 300 billion tons of oxygen has been used up for combustion processes
involving various kinds of fuel, including stone coal. Thus, starting from the first
fires of primitive man to the present, the atmosphere has lost about 0.02% of oxy-
gen whereas the content of carbon oxides has increased by 12%. Annually, man-
kind burns 7 billion tons of fuel, for which more than 10 billion tons of oxygen is
used up, and up to 14 billion tons of CO2 is released into the atmosphere. In the
future, these values will grow because of the general increase in the production
and combustion of combustible minerals. It is predicted that in 2020, about 12,000
billion tons of oxygen (0.77%) will disappear from the atmosphere as a result of
being used up for combustion processes. This means that in the next 100 years, the
composition of the atmosphere will be essentially changed, probably, in an ad-
verse direction.
It is feared that reduction in the quantity of oxygen and the growth in the
content of CO2 will cause adverse changes in the climate. The molecules of C02
allow short wave solar radiation to penetrate the atmosphere of the Earth and re-
tain infrared radiation which penetrates into the terrestrial surface. This gives rise
to the so-called greenhouse effect, resulting in an increase in the average tempera-
ture of the planet. It is indicated that the change in climate from 1880 till 1940 is
substantially related to this effect. It seems that the climate will progressively
change due to the greenhouse effect. However, other human influences on the
atmosphere may help to neutralize the greenhouse effect.
Mankind contributes huge quantities of dust and other microparticles into
the atmosphere. These particles shield solar beams and reduce the heating action
of CO2. According to the American expert K. Frazer, the turbidity of the atmos-
phere above Washington in the period from 1905 to 1964 has increased by 57%.
The transparency of the atmosphere above the Pacific Ocean was decreased by
30% from 1957 till 1967.
Atmospheric pollution by itself introduces another problem: it reduces the
quantity of solar radiation that reaches the Earth's surface. According to data re-
leased from studies of the oceans and the atmosphere above the US by a US health
agency, solar radiation in the period from 1950 to 1972 decreased by 8% during
the fall season, and increased by only 3% in the spring. On the average, solar ra-
diation has fallen by 1.3% since 1964. This is equivalent to the loss of approxi-
mately 10 minutes of daylight per day. This apparent triviality can have serious
consequences on the Earth's climate.
In 1975, the atmospheric pollution above the United States resulted in an
absolutely unexpected phenomenon. In the area of Boston (Massachusetts), it was
established that there was a large increase in the quantity of ozone in the atmos-
phere - 0.127 ppm, whereas the established USA EPA safety limit is 0.08 ppm. It
is known that ozone is formed in the atmosphere during the interaction of hydro-
carbons with oxygen. A high concentration of ozone is more poisonous than char-
coal gas. On August 10, 1975, the Department of Public Health Services of the
state issued an "ozone-alarm", which lasted till August 14, 1975. This was already
the second alarm for one year.
Other notable contributors to atmospheric pollution include jet planes, ma-
chines and factories. For example, modern jets need to use 35 tons of oxygen to
enable them to cross the Atlantic Ocean. Also, the process of flying leaves "traces"
behind thereby increasing the cloudiness of the atmosphere. Cars, whose world-
wide total is already more than 500 million, pollute the atmosphere very signifi-
cantly. They use fossil fuel and emit CO2, SOX, NOX, etc. into the atmosphere. In
the US, automobiles contribute up to half of the air pollution. This type of statistic
led a US senator, E. Muskie, to declare in 1976 that 15 thousand men and women
die each year in the US because of diseases caused by air pollution. There are
strong efforts to seek to design automobile engines that can work with other types
of fuel. For example, electric cars are no longer dreams of the past. There are
demonstrations of various types of electric cars in many countries of the world.
However, their commercial application worldwide has been hampered by the low
capacity of the accumulators.
Petroleum fueled electrical power plants are also a major contributor to air
pollution. Such power plants emit about 500 tons per day of sulfur into the envi-
ronment in the form of sulfuric anhydride. This reacts with water resulting in the
immediate formation of sulfuric acid. A French journalist, M. Ruze, has presented
data to show that a French thermal power plant belonging to Electricite de France
emits about 33 tons of sulfuric anhydride into the atmosphere on a daily basis.
This can result in a daily production of about 50 tons of sulfuric acid. The after-
math of acid production is acid rain, the adverse effect of which covers the power
plant and surrounding territory up to a radius of 5 km. Such rains have high
chemical activity. They corrode even cement and marble.
30 Chapter 1
Old monuments also suffer due specifically to atmospheric pollution. For

example, the Athenian Acropolis, which had already seen 2,500 destructive earth-
quakes and fires, is today being threatened by another danger - atmospheric pollu-
tion. Atmospheric pollution has gradually destroyed the surface of the marble.
This destruction is due to a combination of various processes. Smoke released into
the air from industrial enterprises in Athens and wetted by droplets of water find
their way on the marble. By the morning, evaporation of the water takes place,
leaving behind on the marble an uncountable set of rifts that make the marble
hardly appreciable. According to a Greek archeologist, Professor Narinatos, the
monuments of ancient Ellada have suffered more from atmospheric pollution in
the last 20 years than in the last 25 centuries of wars and invasions. To keep these
invaluable creations of the ancient architects for future generations, the experts
decided to cover a part of the monuments with a special blanket made from plas-
tic.
Atmospheric pollution resulting from the release of various harmful gases
and solid particulates has the result that the air in large cities has become unsuit-
able and even dangerous for human life. For example, in some cities of Japan and
Germany, policemen on the streets breathe oxygen from special cylinders. This
opportunity also exists for pedestrians for a fee. In the streets of Tokyo and some
other cities in Japan, oxygen cylinders are provided for children so that they can
get fresh air on their way to school. Japanese businessmen have opened special
bars where humans can get non-alcoholic drinks and fresh air. It should be noted
that in the last few years, conditions have improved considerably.
Another danger to human life is caused by smoke that is frequently emitted
in large cities. The largest tragedy took place in London in 1952. On the morning
of December 5, people in London could not see the sun. Extraordinarily dense
clouds formed from the mixture of smoke and fog that hung above the city for 4
days. According to the official data, this took the life of four thousand people, and
worsened the health conditions of thousands of others. Such smog has worsened
the health conditions of people in other cities of Western Europe, America and
Japan. In the Brazilian city of Sao Paulo, the level of air pollution exceeds three
times the maximum allowable limits, and in Rio de Janeiro, this exceeds two times
the limit. The usual diseases in these cities include irritation of the eyes, allergic
diseases, and chronic bronchitis. It is also because of smog formation that the
Japanese city of Nagoya has received the name "The Japanese smog capital".
Tokyo got third place among Japanese cities with the number of diseases
caused by environmental pollution. More than four thousand patients were regis-
tered in this city in 1975. Also, in October of the same year, there was serious
threat of poisoning in this huge city with a population of almost 12 million people.
The concentrations of various harmful gases in the city had exceeded the allow-
able levels. Tokyo authorities had to order all factories to reduce the consumption
of fuel by 40%. The inhabitants (especially children) were advised to stay indoors.
Even the plants are also affected by smog. For example, the green zone of
Tokyo has been reduced by 12% in the last 10 years.
As a protective measure, the University of Kentucky (USA) has designed a

special mini-gas mask against concentrations of various gases exceeding the al-
lowable limits. If air contamination or pollution reaches a dangerous level, a tiny
bulb flashes on the device.
1.1.4.2 Black oceans
From 2 to 10 million tons of petroleum is released annually into the world's

ocean. One liter of petroleum deprives about 40 thousand liters of sea water of the
oxygen that is used to sustain living inhabitants such as fish. Also, one ton of pe-
troleum can pollute about 12 km2 surface of the ocean.
There are many sources of petroleum pollution in the seas and oceans. These
include failures of tankers and drilling platforms as well as dumping of ballast and
clearing waters.
Perhaps, the first catastrophe that stirred worldwide interest in this issue was
the one that took place in 1967. The supertanker "Tory Canyon" sank at the coast
of Western Europe, and 120 thousand tons of petroleum poured into the sea. A
huge petroleum slick painted the coastal waters of France and England. Approxi-
mately fifty thousand birds died (i.e. almost 90% of the see bird population in
these areas).
In 1974 there was the failure of the American tanker "Transheron", which
had on board 25,000 tons of petroleum. About 3,500 tons of petroleum flowed out
from the holes in the tanker in only the first week. A huge petroleum slick covered
the area often square kilometers and moved slowly towards the coastal city of the
South Indian State of Kerala.
450 tons of petroleum poured from the Gulf Oil tanker "Afran Zodiac" into
the Gulf of Bantry (Ireland) in January of 1976. The whole northern part of the
gulf was under its cover.
In February of 1976, there was a fire onboard the tanker "San-Peter" carry-
ing 33 thousand tons of petroleum as it was navigating its way from Peru to Co-
lombia. The vessel sank and the petroleum content poured into the sea. The sea-
men from Colombia tried unsuccessfully for ten days to clean the waters in the
area of the disaster.
The supertanker "Olympic Bravery", property of the company owned by the
Greek magnate A. Onassis, sank at the coast of Great Britain in 1976. A mixture
of petroleum and sand flooded the coast. The British government was compelled
to involve naval forces in clearing the coast. However, it was not before irrepara-
ble damage was done to vegetation and animals.
About 20 million liters of petroleum was released into the waters in the area
of the Hawaiian Islands in 1977 as a result of the disaster with the tanker "Irins
Challenger". In the same year, 90 thousand tons of petroleum was released into the
32 Chapter 1
waters of the northern part of the Pacific Ocean as a result of the fire on board the
tanker "Hawaiian Patriot".
The year 1978 was marked by the largest tanker disaster on the coast of
Great Britain. The American supertanker "Amoko Cadiz" sank on the reefs, and
about 230 thousand tons of petroleum poured into the sea.
The collision of tankers "Atlantic Empress" and "Idgen Captain" in the
Caribbean Gulf was the largest disaster in 1979. About 300 thousand tons of petro-
leum poured into the sea.
In the November storm of 1981, the Greek tanker "Globe Asini" had a
disaster on the wave protector off the Port of Klaipeda. About 10 thousand tons of
petroleum poured into the sea.
In August of 1983, the tanker "Castillo de Believer" had a disaster near the
European Atlantic coast. The vessel sank, and about 250 thousand tons of petro-
leum was released into the ocean.
The tanker "Baia Paraiso" with one thousand tons of diesel oil on board
sank at the coast of the Antarctic continent in January of 1989. Another tragedy
happened in the Arctic waters of Alaska two months later. The tanker "Exxon
Valdez" sank at the reef because of the fault of the captain. More than 40 thousand
tons of petroleum flowed out from the hole into the waters. A petroleum slick
covering an area up to 800 km2 was formed. The area in the Strait of Prince Wil-
liam was declared "a zone of disaster". The US Navy was involved with the
cleanup. Nevertheless, there was the "potential for ecological disaster" with con-
sequences that are difficult to foresee, according to the Washington Post.
At the end of March of 1989, the Dutch River tanker ran aground in the area
of Bad-Honnefa. Approximately one thousand tons of petroleum poured into the
river. Petroleum film covered the river up to an area of 7 km .
In April of 1989, the Indian tanker "Kanchendgunga" ran aground at the reef
in the Red Sea in the territorial waters of Saudi Arabia 5 km from the port of Jeda.
More than 10 thousand tons of petroleum flowed out into the sea.
The sad list of tanker failures could go on, but their share in petroleum
pollution of seas and oceans is not big. Three times more petroleum is released
due to dumping of the water used in washing tanker tanks into the sea or oceans.
Also, four times more pollution comes from the waste water of petrochemical
factories; and almost the same amount of petroleum is released by the disasters
that occur at sea platforms.
Now, the question arises: How can the ocean be rescued?
Fortunately, there are good methods. Some of these methods involve the
application of dispersing additives - special substances - that adsorb petroleum;
another is the treatment of petroleum slicks with iron powder and the subsequent
collection of iron particles with a magnet. A promising method, however, lies in
biological protection: the use microbes. These micro-organisms (already designed
in the US and elsewhere for this purpose) are capable of splitting molecules of
hydrocarbons.
Russian scientists have established that any bio-organisms that inhabit the
sea are not affected by petroleum pollution. An example is cardium. This plays an
important role in clearing sea water of petroleum by extracting for itself both food
and oxygen from the pollutant. Nature has already designed for the clearing of
seas and oceans following natural penetration of petroleum in the ocean. The
penetration of oil from underground is seen, for example, on the coasts of Califor-
nia, Australia, Canada, Mexico and Venezuela as well as in the Persian Gulf. In
one part of the bottom of the Californian Gulf, in the Strait of Santa Barbara, there
is a natural outflow of petroleum from underground. It is supposed that this oil
penetration had been taking place for the past ten thousand years. However, it was
noticed for the first time in 1793 by the English seafarer D. Vancouver. According
to US scientists, the annual penetration of petroleum into the world oceans from
natural infiltration is approximately 200 thousand tons. This is about 6% from the
total volume of petroleum that penetrates into the seas and oceans on the planet
from anthropogeneous sources. Suffice it to say that during the disaster of the
tanker "Tory Canyon", as much petroleum that will penetrate into water from the
Californian oil wells for 28 years poured into the ocean. This was too large an
amount of petroleum pollution to be mitigated by natural cleaning alone.
1.2 GENERAL PROPERTIES AND CLASSIFICATION OF

PETROLEUM: COMPARISON OF PETROLEUM FROM
DIFFERENT COUNTRIES
1.2.1 Fractions and Chemical Composition of Petroleum
Petroleum is a complex mixture of various organic compounds. It consists

of different hydrocarbons and heteroatomic compounds. It is technically impossi-
bly to separate petroleum into individual compounds. In any case, it is unnecessary
to separate the petroleum to the component level in order to obtain a technological
or industrial classification.
A very important petroleum property is its fractional composition. This
property is determined in the laboratory by slowly heating the oil and separating it
into fractions having specified boiling ranges. Every fraction is characterized by
the temperature at which boiling begins as well as the temperature boiling ends.
In the industrial method, fractionation is achieved by the method of
rectification. Using this method, the fractions with boiling point up to 350°C are
separated at atmospheric pressure. These are called the light fractions. Usually,
during atmospheric rectification, the following individual fractions are obtained:
• Boiling begins -140°C - gasoline fraction

• 140-180°C - heavy naphtha
34 Chapter 1
• 180-240°C - kerosene fraction

• 240-350°C - diesel fraction
The residue after atmospheric distillation is called "atmospheric residue".

This fraction, with a boiling point over 350°C, is usually distillated further at a low
pressure or in a vacuum. This residue can be classified in two different ways de-
pending on the intended application:
For further processing to fuel fractions:
• 3 50-500°C - vacuum gas oil

• over 500°C - vacuum residue
For further processing to lubricating oils:
• 300-400°C - light oil fraction

• 400-450°C - medium oil fraction
• 450-490°C - heavy oil fraction
• over 490°C - vacuum residue
All the fractions obtained from atmospheric residue are called "heavy frac-
tions". On the other hand, the products obtained after secondary processing of the
heavy fractions are considered to be light fractions if boiling of the fraction ends at
< 350°C, and to be heavy fractions if boiling begins at > 350°C.
The amount of light fractions can be very different for oils from different oil
wells. For example, it can be under 20% for some heavy oils from Alberta (Can-
ada) and over 60% for some light oils form western Siberia (Russia). Typical
analysis of a Canadian petroleum from oil wells in McMurray resulted in the fol-
lowing fractions:
• Gasoline and naphtha - 2.8%

• Kerosene - 0%
• Diesel-19.0%
• Light oil - 4.3%
• Medium oil-8.5%
• Heavy oilfraction- 13.2%
• Vacuum residue - 49.5%
The chemical composition of petroleum can be very different too. The main
constituents of petroleum are:
• carbon (83 - 87%)

• hydrogen (11.5-14%)
• hetero-atoms (1-5.5%)
Table 1.1 shows the chemical composition of oils from the US, Canada, and
Russia.
Even though the chemical composition of petroleum varies, almost all the
hydrocarbons found in petroleum do not include alkenes. On the other hand, many
oils with high amounts of paraffinic or naphthenic compounds or arenes are
known.
It is necessary to make a chemical classification of petroleum since chemical
properties are very crucial in selecting the right method for processing the oil.
There are many classifications with regard to fractions and chemical compositions
of petroleum. In this chapter we will present the basis for these classification
methods.
Table 1.1: Ultimate analysis for crude oils.

Origin Composition (wt.%)
Carbon Hydrogen Nitrogen Oxygen Sulfur
USA 86.6 11.8
83.5 13.3
85.5 14.2
83.6 12.9 3.6
Canada 86.9 12.9
83.4 10.4 0.5 1.2 4.5
82.8 11.8 0.3 1.7 3.4
Russia 85.3 11.6
86.1 12.8 0.9 0.2
86.3 12.9 0.6 0.2
1.2.2 Chemical Classification of Petroleum
The chemical classification of petroleum that distinguishes between oils of a

paraffin base from those of an asphaltene base was introduced into petroleum
chemistry to distinguish the oils that separate paraffin on cooling from those that
separate asphaltenes. The presence of paraffins is usually reflected in the paraf-
finic nature of the constituent fractions whereas a high asphaltic content corre-
sponds with the naphthenic properties of the fractions. This could lead to the mis-
conception that paraffin-base petroleum consists mainly of paraffins and that as-
phalt-base petroleum consists mainly of cyclic (or naphthenic) hydrocarbons. In
order to avoid confusion, a mixed base has been introduced for those oils that
leave a mixture of asphaltic petroleum and paraffins as residue from nondestruc-
36 Chapter 1
tive distillation. A fourth class has also been suggested, the hybrid base; it includes
asphaltic oils that contain a small amount of paraffins. A simplified scheme has
been proposed by Speight [3] with paraffinic, naphthenic, aromatic, and asphaltic
petroleums as extremes (Fig. 1.7). It is indeed possible to characterize petroleum
semi-quantitatively in this manner.
An attempt to give the classification system a quantitative basis suggested
that petroleum should be called asphaltic if the distillation residue contained less
than 2% of parafms and paraffinic if it contained more than 5%. A division ac-
cording to the chemical composition of the 250 to 300°C fraction has also been
suggested (Table 1.2), but the difficulty in using such a classification is that in the
fractions boiling above 200°C, the molecules can no longer be placed in one group
because most of them are typically of a mixed nature.
Fig.1.7: Composition diagram for petroleum.
Purely naphthenic or aromatic molecules occur very seldom; cyclic com-

pounds generally contain paraffinic side chains, and often even aromatic and
naphthenic rings occur side by side. More direct chemical information is often
desirable and can be supplied by means of the correlation index (CI).
This index was developed by the U.S. Bureau of Mines. It is based on the
plot of specific gravity at 48.64°C versus the reciprocal of the boiling point in
degrees Kelvin (K = T°C + 273) for pure hydrocarbons for which the line de-
scribed by the constants of the individual members of the normal paraffin series is
given a value of CI = 0, and a parallel line passing through the point for the values
of benzene is given as CI = 100. The following empirical equation (1.2) has been
derived for estimating CI:
CI=473.7d - 456.8 + 48.640/T (1.2)
where T, in the case of a petroleum fraction, is the average boiling point, deter-
mined by the standard Bureau of Mines distillation method
d is the specific gravity.
Table 1.2: Petroleum classification according to chemical composition.

Class of petroleum Composition of 250-300°C fraction, wt.%
Par. Naphth. Arom. Wax Asph.
Paraffinic 46-61 22-32 12-25 1.5-10 0-6

-6
Paraffinic-naphthenic 42-45 38-39 16-20 1-6 -6
Naphthenic 15-26 61-76 8-13 trace 0-6
-fi 1
Paraffinic-naphthenic-
aromatic 27-35 36-47 26-33 0.5-1 0-10
Aromatic 0-8 57-78 20-25 0-0.5 0-20
Thus, values for the index between 0 and 15 indicate a predominance of

paraffinic hydrocarbons in the fraction; values from 15 to 50 indicate a predomi-
nance of either naphthenes or mixtures of paraffins, naphthenes, and aromatics;
values above 50 indicate a predominant aromatic character. Although the cor-
relation index yields useful information, it is in fact limited to distillable materials
and, when many petroleum samples are to be compared, the analysis of results
may be cumbersome.
It is also possible to describe a crude oil by an expression of its chemical
composition on the basis of the correlation index figures for its middle portions.
1.2.3 Classification by Density
Density has been the principal and often the only specification of petroleum
products and was taken as an index of the proportion of gasoline and kerosene
present. As long as only one kind of petroleum is in use the relations are approxi-
mately true. However, since a wide variety of crude oils having various other
properties occur in nature and have come into use, the significance of density
38 Chapter 1
measurements has disappeared. Nevertheless, petroleum samples having other

properties that are similar can still be rated by gravity as can gasoline and naphtha
within certain limits of other properties. The use of the density values has been
advocated for quantitative application using a scheme of the American Petroleum
Institute (API) based on the gravity of the 250 to 275°C (at the pressure 1 bar) and
the 275 to 300°C (50 mbar) distillation fractions. Indeed, analysis of petroleum
from different sources worldwide showed that 85% fell into one of the three
classes: paraffin, intermediate, or naphthene base. It has also been proposed to
classify heavy oils according to characterization gravity, defined as the arithmetic
average of the instantaneous gravities of the distillates boiling at 177°C, 232°C
and 288°C vapor line temperature at 33 mbar pressure in a true boiling point distil-
lation.
In addition, a method of petroleum classification has been developed that is
based on other properties as well as the density of selected fractions. The method
consists of a preliminary examination of the aromatic content of the fraction boil-
ing up to 145°C as well as that of the asphaltene content, followed by more de-
tailed examination of the chemical composition of the naphtha (b.p. <200°C). For
this examination, a graph (a composite of curves expressing the relation between
percentage distillate from the naphtha, the aniline point, refractive index, specific
gravity, and the boiling point) is used. The aniline point after acid extraction is
included in order to estimate the paraffm-naphthene ratio.
1.2.4 Characterization by Viscosity-Gravity Constant (vgc)
This parameter, along with the Universal Oil Products (UOP) characteriza-
tion factor, has been used, to some extent, as a means of classifying crude oils.
Both parameters are usually employed to give an indication of the paraffinicity of
the petroleum. Both have been used, if a subtle differentiation can be made, as a
means of petroleum characterization rather than for petroleum classification.
Nevertheless, the viscosity-gravity constant is one of the indexes proposed
to characterize oil types. For heavy oils, the low-temperature viscosity is difficult
to measure. The viscosity-gravity constant for such type of petroleum is calculated
by the formula
VGS=d - 0. 24 - 0.022 log (v - 35.5)70.755 (1.2)
where d is the specific gravity at 48.64°C

v is the Saybolt viscosity at 99°C
The viscosity-gravity constant is of particular value in indicating petroleum
of a predominantly paraffinic or cyclic composition. The lower the index number,
the more paraffinic the stock; for example, naphthenic lubricating oil distillates
have a vgc of 0.876 while the raffinate obtained by solvent extraction of lubricat-
ing oil distillate has a vgc of 0.840.
The UOP characterization factor is perhaps one of the more widely used of
the derived characterization or classification factors and is defined by the formula
K=TB"3/d (1.3)
where TB is the average boiling point in degrees Rankine (degrees Fahrenheit +

460) and d is the specific gravity at 48.64°C.
This factor has been shown to be additive on a weight basis. It was origi-
nally devised to show the thermal cracking characteristics of heavy oils; thus,
highly paraffinic oils have K of from 12.5 to 13.0 while naphthenic oils have K of
from 10.5 to 12.5.
1.2.5 Technological Classification of Petroleum
According to technological petroleum classification, the oil can be classified

as:
• low sulfur oil containing not more than 0.5% of the sulfur, whereby the gaso-
line fraction contains less than 0.1% sulfur and diesel fraction less than 0.2%.
• sulfur petroleum containing over 0.5% but under 2% of the sulfur, whereby
the gasoline fraction contains less than 0.1 % sulfur and the diesel fraction
less than 1.0%.
• high sulfur petroleum containing over 2% of sulfur.
• low paraffinic petroleum containing under 1.5% of paraffins. This type of oil
can be used for production of jet and winter diesel fuels without
deparaffinization.
• medium paraffinic petroleum containing over 1.5% and under 6% of paraf-
fins. This type of oil can be used for production of jet and summer diesel fuels
without deparaffinization.
• high paraffinic petroleum containing over 6% of paraffins. This type of oil
can be used for production of diesel and jet fuels only after deparaffinization.
1.3 PRODUCTS FROM CRUDE OIL [2-4]
The list of products from petroleum is endless. Oil products fuel planes,
trains, cars, trucks, buses, and so on. Oil is also used to heat homes. Chemicals
made from oil are used to make products that range from makeup, toys, fabrics,
sneakers and football helmets to aspirin, toothpaste, deodorant, clothes, hair dryers
and lipstick to name just a few. Plastics made from oil are widely used in every-
40 Chapter 1
thing from compact discs and video cassette recorders, to computers, television
sets, and telephones. In this chapter we will focus on petroleum fuels since it is
presently the most important power source.
Crude oil contains a wide range of hydrocarbons and other compounds
containing sulfur, nitrogen, etc. In the refinery, petroleum is distilled into various
fractions. Depending on the desired final products, these fractions are further proc-
essed and then blended to yield a wide variety of products.
Typical final products are:
• gases for chemical synthesis and fuel, liquified gases
• aviation and automotive gasoline
• aviation (jet) and lighting kerosene
• diesel fuel
• distillate and residual fuel oils
• lubricating oil base grades
• paraffin oils and waxes
Many of the common processes in the refinery are intended to increase the
yield of blending feedstocks for gasoline. As such, most modern fuels are repre-
sented by fuel fractions compounded from the products of many different proc-
esses.
Typical modern refinery processes for gasoline components include:
• Catalytic cracking
• Hydrocracking
• Isomerization
• Reforming
• Alkylation
1.3.1 Gasoline
In the late 19th century, the most suitable fuels for automobile use were coal
tar distillates and the lighter fractions from the distillation of crude oil. During the
early 20th Century, the oil companies were producing gasoline as a simple distil-
late from petroleum. On the other hand, automotive engines became vastly im-
proved and these required a more suitable fuel. Typical gasoline products in the
1920s had octane numbers (ratings) in the range 40-60. Tetraethyl lead was often
used to enhance the octane number.
Because sulfur in gasoline inhibited the octane-enhancing effect of the alkyl
lead, there was a restriction on the sulfur content of thermally cracked refinery
streams for gasoline. By the 1930s, it was determined that larger hydrocarbon
molecules had major adverse effects on the octane number of the gasoline, and
specifications consistent with the desired properties were developed.
The increase in the compression ratios of cars started in the 1950s. The
consequence was that such car engines required fuels with higher octane numbers.
Thus, octane number, lead levels, and vapour pressure increased whereas sulfur
and olefin contents decreased. Some new refining processes (such as hydrocrack-
ing), designed to provide hydrocarbon components with good lead response and
octane number, were introduced. Minor improvements were made to gasoline
formulations to improve yields and octane number until the 1970s, when unleaded
fuels were introduced to protect the catalysts that were also being introduced for
environmental reasons. From 1970 until 1990, there was a slow but progressive
change in the gasoline produced. Lead was being phased out. Lead levels de-
creased, octane number initially decreased as well, but vapor pressures continued
to increase while sulfur and olefins remained constant. The aromatic content in-
creased. In 1990, the US Clean Air Act started to force the implementation of
major compositional changes in gasoline. This resulted in the plummeting of the
vapor pressure and the increase in the oxygenate levels. These changes will con-
tinue into the 21st century as a way to minimize the polluting effect of the use of
gasoline as fuel in automobile engines.
The move to unleaded fuels continues worldwide. However, several coun-
tries have increased the aromatics content (by up to 50%) to replace alkyl lead.
These highly aromatic gasolines can lead to damage of elastomers and increased
levels of toxic aromatic emissions if is used without catalysts.
Gasoline as a fuel is composed of a mixture of various hydrocarbons, which
can be burnt to form water (H2O) and CO2. If combustion is not complete, carbon
monoxide (CO) is also formed.
The following main groups of hydrocarbons are contained in gasoline:
• saturated hydrocarbons or alkanes
• unsaturated hydrocarbons or olefins
• naphthene or cyclic hydrocarbons
• aromatics
• oxygenates
• other hetero-atom compounds
Gasoline contains over five hundred types of hydrocarbons that have be-
tween 3 to 12 carbon atoms in their structure. Gasoline has a boiling range from 30
to 180°C at atmospheric pressure. The boiling range is narrowing as the initial
boiling point is increasing, and the final boiling point is decreasing. Both these
changes are for environmental reasons.
Saturated hydrocarbons have the following major properties:
• Are thermally and chemically stable, it is the major component of leaded
gasolines.
• Tend to bum in air with a clean flame.
42 Chapter 1
The octane number depends on branching and number of carbon atoms. Gen-
erally octane number is low for n-alkanes and high for the iso-alkanes (iso-
octane is assigned the octane number of 100).
The cyclic hydrocarbons all have the positive properties of the alkanes with
regard to thermal and chemical stability as well as good environmental properties.
In addition, they have a higher octane number in comparison to alkanes.
Alkenes or unsaturated hydrocarbons have the following major properties:
• Are chemically unstable.
• Tend to be reactive and toxic, but have high octane numbers.
Arenes or aromatics are characterized as follows:

• Gradually being reduced to less than 20% in the US.
• Tend to be more toxic than other hydrocarbons, but have the highest octane
ratings.
• Some countries are increasing the aromatic content (up to 50% in some super
unleaded fuels) to replace the alkyl lead octane enhancing additive.
Polynuclear aromatics are high boiling compounds, and are only present in
small amounts in gasoline. The simplest and least toxic polynuclear arene, naph-
thalene, is present in only trace amounts in traditional gasoline, and in even lower
levels in reformulated gasoline. The larger multi-ringed polynuclear arenes are
highly toxic, and are not present in gasoline.
Oxygenates contain oxygen that does not contribute to the energy content,
but because of their structure, provides a reasonable antiknock value. Thus, they
are good substitutes for aromatics. They also reduce the tendencies of the forma-
tion of toxic gases. Most oxygenates used in gasoline are either alcohols or ethers
that contain 2 to 6 carbon atoms per molecule. Alcohols have been used in gaso-
line since the 1930s whereas ether (such as methyl tertiary butyl ether (MTBE))
was first used in commercial gasoline in Italy in 1973 and in the US in 1979.
Oxygenates can be produced from fossil fuels or from biomass. MTBE is
produced by reaction of methanol with iso-butylene in the liquid phase over an
acidic ion-exchanger resin catalyst at 100°C. MTBE production has increased at
the rate of 10 to 20% per year.
Oxygenates are added to gasoline to reduce emissions. However, they can
only be effective if the hydrocarbon fractions are modified to utilize the oxygen-
ate's octane number and volatility properties. If the hydrocarbon fraction is not
correctly modified, oxygenates can even increase smog-forming and toxic emis-
sions both of which are undesirable. It should also be noted that oxygenates do not
necessarily reduce all toxins.
Initially, oxygenates were added to hydrocarbon fractions that were just
slightly modified unleaded gasoline fractions. These were known as "oxygenated"
gasolines. Since 1995, the hydrocarbon fraction has been significantly modified
resulting in "reformulated gasoline".
Oxygenates added to gasoline function in two ways. First, they have a high
blending octane number, and so can replace high octane aromatics in the fuel.
These aromatics are responsible for disproportionate amounts of CO and hydro-
carbons emissions during combustion. Oxygenates cause engines without sophisti-
cated engine management systems to move to the lean side of stoichiometry, thus
reducing emissions of CO (2% oxygen can reduce CO by 16%) and hydrocarbons
(2% oxygen can reduce hydrocarbons emissions by 10%). Other researchers have
observed that similar reductions occur when oxygenates are added to reformulated
gasoline and used on older and newer vehicles. They have also shown that, unfor-
tunately, NOx levels may increase, as may some regulated toxins.
On the other hand, on vehicles with engine management systems, the fuel
volume will be increased to bring the stoichiometric combustion to the preferred
optimum setting. It is to be noted that oxygen in the fuel cannot contribute energy.
Consequently, the fuel has less energy content. Thus, for the same efficiency and
power output, more fuel has to be burned. Therefore, the slight improvements in
combustion efficiency that oxygenates provide on some engines usually do not
completely compensate for the energy loss due to the presence of oxygen.
There are some other properties of oxygenates that have to be considered if
they are to be used as fuels. These relate particularly to (i) their ability to form
very volatile azeotropes that cause the fuel's vapor pressure to increase, (ii) the
chemical nature of the emissions, and (iii) their tendency to separate into a sepa-
rate water-oxygenate phase when water is present. These problems are solved
more successfully in the reformulated gasoline than in the original oxygenated
gasoline.
Table 1.3 shows some hydrocarbons in gasoline and their corresponding oc-
tane numbers.
The main characteristics of gasoline are:
• Vapor pressure and distillation classes. There are six different classes accord-
ing to location and/or season. As gasoline is distilled, the temperatures at
which various fractions are evaporated are recorded. Specifications define the
temperatures at which various percentages of the fuel are evaporated. Distilla-
tion limits include maximum temperatures at which 10% is evaporated (50-
70°C), 50% is evaporated (110-121°C), 90% is evaporated (185-190°C), and
the final boiling point (225°C). A minimum temperature for 50% evaporated
(77°C), and a maximum amount of residue (2%) after distillation. Vapor
pressure limits for each class (54, 62, 69, 79, 93, 103 kPa, respectively) are
also specified.
• Vapor lock protection classes. There are five classes for vapor lock protec-
tion. This classification depends on location and/or season. The limit for each
class is a maximum vapor-liquid ratio of 20 at one of the specified testing
temperatures of 41,47, 51, 56, or 60°C.
44 Chapter 1
• Antiknock index. Limits are not specified, but changes in engine requirements
according season and location are discussed.
• Lead content
• Copper strip corrosion. This determines the ability to tarnish clean copper,
indicating the presence of any corrosive sulfur compounds.
• Maximum sulfur content. Sulfur adversely affects catalysts and fuel hydro-
carbon lead response. Sulfur may also be emitted as polluting sulfur oxides.
• Maximum solvent washed gum limits the amount of gums present in fuel at
the time of testing to 5 mg/100 mLs. The results do not correlate well with ac-
tual engine deposits caused by fuel vaporization.
• Minimum oxidation stability. This ensures that the fuel remains chemically
stable, and does not form additional gums during periods in the distribution
systems (can be up to 3-6 months). The test is conducted by heating the sam-
ple with oxygen inside a pressure vessel. The time required for a significant
oxygen uptake is measured to indicate minimum oxygen stability.
• Water tolerance. This is the highest temperature that causes phase separation
of oxygenated fuels. The limits vary according to location and month.
An understanding of the reasons for detonation makes it obvious that there
are two ways to improve the octane number of gasoline. It is possible to change
the composition of gasoline. However, this is a difficult and expensive method.
It is also possible to add additives that destroy peroxides. However, any "knock"
caused by the fuel will rapidly mechanically destroy the engine. The problem is
to identify economic additives which could be added to gasoline to prevent
knock effects. Originally, iodine was the best antiknock additive available, but
was not a practical gasoline additive, and was used as the benchmark. Later,
terra ethyl lead was added to the gasoline to improve the octane number.
Terra ethyl lead (C2H5)4Pb is an organometallic compound, which is well
soluble in hydrocarbons in the gasoline. At the temperatures of 200-250°C, this
substance is cracked to lead and four ethyl radicals CiHs'. All the compounds
formed prevent the formation of explosive compounds in gasoline, or promote
their fast destruction. However, the application of pure tetra ethyl lead was im-
possible. The formed lead deposits as a residue on the walls of the cylinder, and
further makes the working of the engine impossible. This is why, in practice,
tetra ethyl lead is mixed with various alkyl-halogens. At high temperature, alkyl-
halogens are cracked and react with lead to form volatile salts, which leave the
engine together with the exhaust gases.
Table 1.3: The average gasoline composition.

1 5% n-paraffins RON MON
n-pentane 62 66
n-hexane 19 22
n-heptane 0 0
n-octane -18 -16
n-decane -41 -38
n-dodecane -88 -90
n-tetradecane -90 -99
30% iso-paraffins
2-methylpropane 122 120
2-methylbutane 100 104
2-methylpentane 82 78
3-methylpentane 86 80
2-methylhexane 40 42
3-methylhexane 56 57
2,2-dimethylpentane 89 93
2,2,3-trimethylbutane 112 112
2 ,2 ,4-trimethylpentane 100 100
12% cycloparaffins
Cyclopentane 141 141
Methylcyclopentane 107 99
Cyclohexane 110 97
Methylcyclohexane 104 84
35% aromatics
Benzene 98 91
Toluene 124 112
ethyl benzene 124 107
meta-xylene 162 124
para-xylene 155 126
ortho-xylene 126 102
3-ethyltoluene 162 138
1 ,3,5-trimethylbenzene 170 136
1 ,2,4-trimethylbenzene 148 124
8% olefms
2-pentene 154 138
2-methylbutene-2 176 140
2-methylpentene-2 159 148
cyclopentene 171 126
1 -methylcyclopentene 184 146
1,3 cyclopentadiene 218 149
dicyclopentadiene 229 167
Oxygenates
methanol 133 105
ethanol 129 102
iso-propyl alcohol 118 98
46 Chapter 1
Adding tetra ethyl lead appeared to be quite an effective method to im-

prove antidetonating properties of gasoline. The additive added in a very small
amount in gasoline allows the increase of the octane number by about 5 - 1 0
units. Unfortunately however, lead and tetra ethyl lead are very poisonous sub-
stances. If contacted with the skin, they can filter into the blood. The lead com-
pounds formed in engines falls on the ground and near vegetation. This can
produce tragic consequences for the ecology.
The alkyl leads rapidly became the most cost-effective method of enhancing
octane. Up until the late 1960s, alkyl leads were added to gasoline in increasing
concentrations to improve octane number. However, in later years, the use of tetra
ethyl lead was not encouraged. Presently in most countries of the world, the use of
tetra ethyl lead as an additive to gasoline is prohibited by law.
However, the need for gasoline with high octane number is ever increasing.
The next possible way to improve the octane number of gasoline is to mix it with
other compounds having high octane numbers. In the table above is shown that
oxygenates have very high octane number (over 100). It is known that in the US,
the so-called gasohol, a mixture of gasoline and alcohol, was used. In Europe
syntin was produced from CO2 and hydrogen. The product of this process includes
a mixture of different types of alcohol.
However, the most effective and ecologically sound additive to gasoline
nowadays is methyl tetra butyl ether ((CH3)3COCH3). This additive is well known
as MTBE. The octane number of MTBE is 135. The use of methyl tetra butyl
ether as the additive fortunately solved a problem that resulted from using alcohols
as the additive. In contrast to alcohols, MTBE is not soluble in water. It is known
that water in different amounts can be found in industrial reservoirs. Even gasoline
contains small traces of water. All alcohols are well soluble in water such that
alcohol can stay in water at the bottom of the reservoir during storage. MTBE is
insoluble in water and so this problem does not arise. Another problem with alco-
hol is that light alcohols (for example methanol) have a much lower heat of
combustion than gasoline. It means that the need of fuel in tanks of the cars
should be increased. MTBE has approximately the same fuel characteristics as
gasoline. Moreover the presence of oxygen in its structure essentially improves
the combustion process of gasoline in cylinders and reduces the contents of
products of incomplete combustion in the exhaust gas.
There is only one disadvantage of using MTBE. There is a shortage in the
production of MTBE in comparison to the need for high quality fuel for modern
cars. One more method to improve the antidetonating properties of gasoline was
introduced in the 1970s. In this method, the properties of gasoline were not
changed. Instead the working mechanism of the engine was changed. It was
introduced to make the engine capable of working with two different gasolines.
Because the highest danger of detonation in engine occurs only during the
forced working regime, it is rational to use two different gasolines in one engine:
the high quality gasoline for the forced regime of the engine and the gasoline
with low octane number for the stable working regime. It was shown that nor-
mally the engine works about 20% of the general working time in forced regime.
This means that by using two tanks in a car, one can save up to 80% of the high
quality gasoline by partly using low quality fuel. However, this method did not
become popular and therefore did not result in industrial production of cars with
dual tanks.
It is useful at this stage, close to the end of the chapter on gasoline, to men-
tion additional properties of gasoline of importance:
• Volatility. This affects evaporative emissions and derivability. It is a property
that is changed with location and season. For example, fuel for mid-summer
Arizona would be difficult to use in mid-winter Alaska. For this reason, the
US is divided into zones, according to altitude and seasonal temperatures. The
fuel volatility is adjusted accordingly. Incorrect fuel may result in difficult
starting in cold weather, carburetor icing, vapor lock in hot weather, and
crankcase oil dilution. Volatility is controlled by distillation and vapor pres-
sure specifications. The higher boiling fractions of the gasoline have signifi-
cant effects on the emission levels of undesirable compounds (hydrocarbons
and oxygen containing compounds), and a reduction of 40°C in the end boil-
ing point will reduce the levels of benzene, butadiene, formaldehyde and ac-
etaldehyde by 25%, and will also reduce hydrocarbons emissions.
• Combustion Characteristics. Gasoline contains a wide variety of hydrocar-
bons. Thus, the only significant variable that characterizes different gasoline
grades is the octane number. Most other properties are similar. There are only
slight differences in combustion temperatures (most are around 2000°C in
isobaric adiabatic combustion). It should also be noted that the actual tem-
perature in the combustion chamber is also determined by other factors, such
as load and engine design. The addition of oxygenates changes the pre-flame
reaction pathways and also reduces the energy content of the fuel. The level
of oxygen in the fuel is regulated according to regional air quality standards.
• Stability. Motor gasoline may be stored up to six months. As such, they must
not form gums during storage. Gums formed may precipitate. Gums are
formed due to oxidation and polymerization reactions involving unsaturated
hydrocarbons. Antioxidants and metal deactivators are added to prevent gum
formation due to these reactions.
• Corrosiveness. Sulfur in the fuel facilitates corrosion. The combustion of
sulfur containing fuels results in the formation of corrosive gases that attack
the engine, the exhaust as well as the environment. Sulfur also adversely af-
fects the alkyl lead octane response. Furthermore, it adversely affects the ex-
haust catalysts. However, the monolithic catalysts usually recover when the
sulfur content of the fuel is reduced. In this case, sulfur is considered to be an
inhibitor rather than a catalyst poison. The copper strip corrosion test and the
sulfur content specification are used to ensure fuel quality. The copper strip
test measures the active sulfur whereas the sulfur content reports the total sul-
fur present.
48 Chapter 1
It has to be noted, that aviation gasoline is required to be an all hydrocarbon

product. Its components must be chemicals that contain only carbon and hydrogen
atoms. The use of oxygenated or other oxygen containing compounds, such as
alcohols or ethers, is not allowed. Only a few select additives are permitted and
their use is strictly controlled and limited. The primary ingredient in aviation gaso-
line is isooctane.
More about gasoline can be found in references 51-53.
1.3.2 Jet Fuel (Kerosene)
Kerosene is a hydrocarbon fraction that typically boils between 170-270°C

(for narrow kerosene fraction or Jet Al), 100-250°C (for wide kerosene fraction or
JP-4), or 170-315°C (for heavy kerosene, Russian standards). It contains about
20% aromatics. However, the aromatic content is usually reduced for high quality
lighting kerosene, as the aromatics reduce the smoke point. The other constituents
include 20 to 60% aliphatic compounds, 20 to 60% naphthenes and up to 1%
unsaturated compounds. The major use for kerosene today is as aviation turbine jet
fuels. Special properties are required for this application, including high flash
point for safe refueling (38°C for Jet Al), low freezing point for high altitude
flying (-47°C for Jet Al), and good water separation characteristics.
The quantity and quality of kerosene vary with the type of crude oil; some
crude oils yield excellent kerosene, but others produce kerosene that requires sub-
stantial refining and hydrotreatment. Kerosene is a very stable product, and addi-
tives are not required to improve the quality. Apart from the removal of excessive
quantities of aromatics, kerosene fractions may need only hydrotreatment if hy-
drogen sulfide is present. The kerosene fraction from shale oil is like the gasoline
fraction, which generally contains high amounts of nitrogen and oxygen. How-
ever, hydrotreatment will remove most of the nitrogen, but catalyst degeneration
can be quite severe.
Jet fuels must burn cleanly and remain fluid and free from wax particles at
the low temperatures experienced in high-altitude flight. The conventional freeze-
point specification for commercial jet fuel is -50°C. The fuel must also be free of
any suspended water particles that might cause blockage of the fuel system with
ice particles. Special-purpose military jet fuels have even more stringent specifica-
tions.
The quality of this fuel varies widely. This is why there is no universal jet
fuel. Instead, there very many different types of jet fuels. The main types for North
America and Russia are:
• Jet-A: This is a narrow cut kerosene product. This is the standard commercial
and general jet fuel available in the United States. It usually contains no addi-
tives but anti-icing chemicals may be added.
• Jet-Al: This is identical to Jet-A with the exception of its freezing point. It is
used outside of the US and is the fuel of choice for long haul flights where the
fuel temperature may fall to near the freezing point. It often contains a static
dissipator additive.
• Jet-B: This is a wide cut kerosene with lighter gasoline type naphtha compo-
nents. It is used widely in Canada. It contains a static dissipator and has a very
low flash point;
• JP-4: This is a military designation for a fuel like Jet-B but contains a full
additive package including corrosion inhibitor, anti-icing and static dissipator.
• JP-5: This is another military fuel. It has a higher flash point than JP-4 and
was designed for use by the US Navy on board aircraft carriers. It contains
anti-ice and corrosion inhibitors.
• JP-8: This is like Jet-Al with a full additive package.
• T-5: This is a Russian heavy jet fuel without any additives and had been used
for civil aviation. It has not been used any more since 1971.
• RT: This is a Russian hydroteated jet fuel with antioxidation additive ionol;
• T6: This is a Russian thermo-stabilized jet fuel made from the east sulfuric
petroleums with antioxidation additive ionol.
• T7: This is the same as the RT jet fuel without any additives.
• T8W: This is a Russian hydrotreated jet fuel without any additives.
1.3.3 Diesel
Diesel fuel is derived from petroleum. Diesel, gasoline and jet fuel are dif-
ferent cuts from the refining of petroleum. The difference is that diesel contains
heavier hydrocarbons with a higher boiling point than gasoline and jet fuel. The
term diesel fuel is therefore generic; it refers to any fuel mixture developed to run
a diesel-powered vehicle, i.e. engines with compression ignition engines.
Diesel is a hydrocarbon fraction that typically boils between 250-380°C.
Diesel engines use the cetane (n-hexadecane) rating to assess ignition delay. Nor-
mal alkanes have a high cetane rating, (n-Ci6=100) representing short ignition
delays. On the other hand, aromatics (alpha-methylnaphthalene = 0) and iso-
alkanes have low ratings representing long ignition delays. Because of the size of
the hydrocarbons, the low temperature flow properties control the composition of
diesel. Consequently, additives are usually added to prevent filter blocking in
cooler temperatures. There are usually summer and winter diesel grades. Envi-
ronmental legislation is reducing the amount of aromatics and sulfur permitted in
diesel. Their emission as well as those of small particulates are considered as pos-
sible carcinogens and are also known to cause other adverse health effects.
Cetane number is one of the most widely known quality characteristics of
diesel fuel. It is important to not confuse cetane number with cetane index.
The fuel in a diesel engine is ignited by the high-temperature and high-
pressure air created in the cylinder as the piston nears the end of the compression
stroke. In contrast, fuel in gasoline engines is ignited by a spark plug.
50 Chapter 1
Cetane number is therefore a measure of the power with which diesel fuel is
ignited during the compression stroke. The number is determined using a specified
laboratory test engine. Cetane index is calculated using an equation involving the
density and the distillation curve of the fuel. Consequently cetane index cannot be
increased and improved by cetane-improving additives because the equation does
not account for the type and amount of cetane-improving additive in the fuel.
However, cetane index can be modified through changes in the density or distilla-
tion curve of the fuel.
The time between the beginning of fuel injection and the start of combustion
is called "ignition delay". As stated earlier, higher cetane number fuels result in
shorter ignition delays, providing improved combustion, lower combustion noise,
easier cold starting, faster warm-up, less smoke, and in many engines, reduction of
emissions.
In most diesel engines, the ignition delay is shorter than the duration of
injection. Under these circumstances, the total combustion period can be divided
into the following four stages:
• Ignition delay
• Rapid pressure rise
• Constant pressure or controlled pressure rise
• Burning on the expansion stroke
Rapid pressure rise results from the large number of ignition points and the
accumulation of fuel during the ignition delay period. Following this stage, the
rate of combustion can be controlled to a much greater degree by controlling the
injection rate since the fuel is being injected into the flame. Because the rapid
pressure rise represents uncontrolled and inefficient combustion, it is necessary to
limit the ignition delay to a minimum. This limitation can be accomplished me-
chanically by the selection of a spray pattern configuration properly tailored to the
combustion chamber.
The nature of the fuel is also an important factor in reducing ignition delay.
Physical characteristics such as viscosity, density, and medium boiling point are
influencing parameters. Hydrocarbon composition is also important as it affects
both the physical and combustion characteristics of the fuel. Ignition delay charac-
teristics of diesel fuel are of primary importance since they directly influence the
interval of uncontrolled combustion during the injection and, as such, the overall
engine performance.
The next important parameter of diesel fuel is stability or storage stability.
As fuel ages, it can become unstable and form insoluble particulates that accumu-
late and eventually end up on the fuel filter. For the most part, instability involves
the chemical conversion of precursors to compounds of higher molecular weight
with limited fuel solubility. The precursors are certain nitrogen and/or sulfur con-
taining compounds, organic acids, and reactive olefins. The conversion process
often involves oxidation of the precursors. Certain dissolved metals, especially
copper, contribute by functioning as oxidation catalysts. Fuel solvency also plays a

role because the development of insoluble compounds is always a function of both
the presence of higher molecular weight compounds and the capacity of the fuel to
dissolve them. Diesel fuel is increasingly used as a coolant for high-pressure fuel
injection systems in which the fuel can be thermally stressed. Sometimes, this can
cause the fuel to degrade and form insoluble materials that can restrict fuel flow
through filters and injection systems. Three tests are routinely used to evaluate fuel
stability in the USA. These are ASTM D 2274, the Octel F21-90, and the Octel
F21-180. ASTM D 2274 is an accelerated oxidation stability test. Oxygen is bub-
bled through a fuel sample for 16 hours, after which the fuel is filtered to collect
any insoluble materials. Fuels that have insoluble materials of less than 15 mg/liter
are considered to be stable.
Both Octel tests are thermal stability tests. The difference between the two is
the length of time the fuel is thermally stressed. A sample is subjected to a 150°C
bath for either 90 or 180 minutes, filtered to collect insoluble materials, and meas-
ured by light reflectance. ASTM has developed the 180-minute test as a standard
because it works better than the 90-minute test.
The storage stability is very important for bio-stability as well, especially for
states with a warm climate. Microorganisms in diesel fuel have increasingly be-
come a concern for fuel users. Prevention is important in fuel storage facilities.
These bugs grow wherever water comes into contact with fuel, feeding at the
interface, but living in the water.
The best way to prevent the problem is to keep water out of the fuel system.
This is, however, practically impossible. The storage tanks cannot always keep the
fuel from the humidity from the air.
In order to make diesel work most efficiently in engines year round, the low
temperature properties of seasonal diesels are adjusted throughout the year accord-
ing to historical temperature data of the region where the fuel is used. Generally all
the diesel fuels can be divided into two groups:
• diesel fuel for summer season
• diesel fuel for winter season
For this classification of diesel fuel, the low temperature properties of the
fuel are especially important. At low temperatures, wax crystals can be formed in
the diesel fuel. These wax crystals can collect on and plug fuel filters in a vehicle's
fuel system causing the engine to stumble or stall. The temperature at which this
occurs is called the low temperature operability limit of the fuel and vehicle. Both
the fuel system design and the fuel properties are important factors in determining
this minimum temperature for acceptable operation.
The next quality parameter of diesel fuel is the ability to keep the fuel injec-
tor clean. The fuel injector is the heart of a diesel engine. These precision compo-
nents meter fuel to a high degree of accuracy. Correct engine behavior depends on
the injector functioning properly.
52 Chapter 1
Proper injector functioning is essential for optimum performance. As such, it

is beneficial to keep the nozzles operating at their optimum. Build up of carbon on
the injector can disrupt the spray pattern of the fuel being injected into the cylin-
der. This can lead to incomplete combustion, which, in turn, can cause increased
emission and high fuel utilization.
Many various additives are used to improve the quality of diesel fuel. These
additives are used for a variety of purposes that can be classified into four major
categories:
• Engine performance
• Fuel handling
• Fuel stability
• Contaminant control
The engine performance additives improve engine performance. Different

members of this class are used to improve engine performance in different time
frames. Any benefit that is provided by a cetane number improver is immediate,
whereas that provided by detergent additives or lubricity additives is typically seen
over the long term.
Cetane number improvers or diesel ignition improvers reduce combustion
noise and smoke. The magnitude of the benefit varies among engine designs and
operating modes, ranging from no effect to readily perceptible improvement.
2-Ethylhexyl nitrate (EHN) is the most widely used cetane number im-
prover. It is also sometimes called, "octyl nitrate". EHN is thermally unstable and
decomposes rapidly at the high temperatures in the combustion chamber. The
products of decomposition help initiate fuel combustion and, thus, shorten the
ignition delay period as compared with that of the fuel without the additive.
The increase in cetane number from a given concentration of EHN varies
from one fuel to another. It is greater for a fuel whose natural cetane number is
already relatively high. The incremental increase gets smaller as more EHN is
added. Thus, there is little benefit to exceed a certain concentration. EHN typically
is used in the concentration range of 0.05 to 0.4 mass % and this may yield a 3 to 8
cetane number benefit. A disadvantage of EHN is that it decreases the thermal
stability of the fuels.
Other alkyl nitrates as well as ether nitrates and some nitroso compounds,
have also been found to be effective cetane number improvers. However, they are
not currently used commercially. Di-tertiary butyl peroxide has recently been
introduced as a commercial cetane number improver.
Injector cleanliness additives and crankcase lubricant can form deposits in
the nozzle area of injectors. The extent of deposit formation varies with engine
design, fuel composition, lubricant composition, and operating conditions. Exces-
sive deposits upset the injector spray patterns and these hinder the fuel-air mixing
process. In some engines, this leads to increased emissions and fuel utilization.
Ashless polymeric detergent additives can clean the fuel injector from deposits.
These additives are composed of a polar group that bonds to deposits and deposit
precursors and a non-polar group that dissolves in the fuel. Thus, the additive can
redissolve deposits that already have formed and reduce the opportunity for de-
posit precursors to form deposits.
Lubricity additives are used to compensate for the poor lubricity of severely
hydrotreated diesel fuels. They contain a polar group that is attracted to metal
surfaces, causing the additive to form a thin surface film. The film acts as a
boundary lubricant when two metal surfaces come in contact. Two additive
chemicals, fatty acids and esters, are typically used for this purpose.
Smoke suppressants are combustion catalysts. This class of additives is
usually composed of organometallic compounds. Adding these compounds to fuel
can reduce the emissions of pollutants that result from incomplete combustion.
Smoke suppressants that are based on organometallic compounds of iron, cerium,
platinum are in common use.
The following additives belong to the fuel handling additives:
Antifoam additives prevent formation of foam. Diesel fuels tend to be prone
to foam formation when they are pumped into the tanks. Most antifoam additives
are organosilicone compounds and are typically used at very low concentrations
(about lOppm).
De-icing additives prevent ice formation from the free water in diesel fuel. If
free water in diesel freezes, the resulting ice crystals can plug fuel lines and filters.
Low molecular weight alcohols or glycols can be added to diesel fuel to prevent
ice formation. The alcohols/glycols preferentially dissolve in the free water, giving
the resulting mixture a lower freezing point than that of pure water.
Low temperature operability additives lower a diesel fuel's pour point and
improve its cold flow properties. Most of these additives are polymers that interact
with the wax crystals that form in diesel fuel when it is cooled below the pour
point. The added polymers mitigate the adverse effect of wax crystal formation on
fuel flow by modifying their size, shape, and degree of agglomeration. The poly-
mer-wax interactions are fairly specific. As such, a particular additive generally
will not perform equally well in all fuels. Unfortunately, the best additive for a
particular fuel cannot be predicted; it must be determined experimentally.
Drag reducing additives are used by pipeline companies to increase the
volume of product they deliver. These high molecular weight polymers reduce
turbulence in fluids flowing in a pipeline. This can increase the maximum flow
rate by up to 40%. When the additive modified product passes through a pump,
the additive is broken into smaller molecules that have no effect on product per-
formance in engines.
Fuel stability additives prevent the formation of gums that can lead to injec-
tor deposits or particulates that can plug fuel filters and the fuel injection system.
The need for a stability additive varies widely from one fuel to another. Stability
additives typically work by blocking one step in a multi-step reaction pathway of
gum formation. Because of the complex chemistry involved, an additive that is
effective in one fuel may not work as well in another. If a fuel needs to be stabi-
54 Chapter 1
lized, it should be tested to select an effective additive and treatment rate. The best
results are obtained when the additive is added immediately after the fuel is manu-
factured.
Antioxidants prevent the oxidation of the fuel. Antioxidants work by inter-
rupting the chain in free radical chain reaction by blocking the free radicals. Phen-
ylenediamines are the most commonly used antioxidants.
Stabilizers prevent acid-base reactions in the diesel fuel. Basic amines are
usually used as stabilizers. They react with weakly acidic compounds with the
formation of products that remain dissolved in the fuel and do not react further.
Metal deactivators prevent the catalytic influence of the metals on reactions
that can lead to its instability in diesel fuel. They are typically used in concentra-
tions of up to 15 ppm.
Dispersants disperse the formed insoluble products in diesel fuel, preventing
them from clustering into aggregates large enough to plug fuel filters or injectors.
Dispersants are typically used in concentrations of up to 100 ppm.
Biocides prevent the growth of bio-organisms. The best choice is an additive
that dissolves in both the fuel and the water such that it can attack the microbes in
both phases. Biocides are typically used in concentrations of up to 600 ppm. A
biocide may not work if a heavy biofilm has accumulated on the surface of the
tank or other equipment, because then it does not reach the organisms living deep
within the film.
Demulsifiers aid in the separation of fuel from water. Normally, hydrocar-
bons and water separate rapidly and cleanly. But if the fuel contains polar com-
pounds that behave like surfactants and if free water is present, the fuel and water
can form a stable emulsion. Any operation that subjects the mixture to high shear
forces, like pumping the fuel, can stabilize the emulsion. Demulsifiers are surfac-
tants which can destabilize the emulsions and allow the fuel and water phases to
separate. Demulsifiers are used in concentrations of up to 30 ppm.
Corrosion inhibitors prevent the oxidation of the metal pieces in diesel en-
gines. Since most petroleum pipes and tanks are made of steel, the most common
corrosion is the formation of rust in the presence of water. The fuel is thus con-
taminated with rust particles, and these can plug fuel filters as well as increase fuel
pump and injector wear. Corrosion inhibitors attach to metal surfaces and form a
film that prevents attack by corrosive agents. They typically are used in concentra-
tions of up to 15 ppm.
Modem diesel fuel can be produced from sources other than petroleum.
Recently, attention has been focused on biodiesel. This is a cleaner-burning fuel
made from natural and renewable sources such as vegetable oils. Just like petro-
leum diesel, biodiesel can operate in combustion-ignition engines. Essentially no
engine modifications are required, and also biodiesel maintains the payload capac-
ity and range of diesel.
The use of biodiesel in a petroleum diesel engine results in substantial re-
duction of unburned hydrocarbons, carbon monoxide, and formation of participate
matter, i.e. in reduction of emission of pollutants. Emissions of nitrogen oxides are
either slightly reduced or slightly increased depending on the duty cycle and test-
ing methods. The use of biodiesel decreases the solid carbon fraction of particulate
matter (since the oxygen in biodiesel enables more complete combustion to CO2)
and eliminates sulfate fraction (as there is no sulfur in the fuel), while the soluble
and hydrocarbon fraction stay the same or are increased. Therefore, biodiesel
works well with new technologies such as catalysts (which reduce the soluble
fraction of diesel particulate but not the solid carbon fraction), particulate traps,
and exhaust gas recirculation (leads potentially to longer engine life due to less
carbon).
Biodiesel has physical properties that are very similar to those of petroleum
diesel. As mentioned earlier, emission properties, however, are better for biodiesel
than for petroleum diesel.
Biodiesel is produced by a process called "trans-esterification". Vegetable
oil or animal fat is first filtered, then pre-processed with alkali to remove free fatty
acids. It is then mixed with an alcohol and a catalyst. The oil's triglycerides react
to form esters and glycerol, which are then separated from each other and purified.
Much of the current interest in biodiesel production comes from vegetable
oil sources such as soybean (in the USA), canola oil (in Canada) and rapeseed oil
(in Europe) because the vegetable oil producers are faced with excess production
capacity, product surpluses, and declining prices.
Waste animal fats and used frying oils (known as 'Fellow grease') are also
potential feedstocks. These are cheaper than soybean oil and are being considered
as a way to reduce feedstock costs.
1.3.4 Residual Fuel
Many marine vessels, power plants, commercial buildings and industrial

facilities use residual fuels or combinations of residual and distillate fuels for heat-
ing and processing. The two most critical specifications of residual fuels are vis-
cosity and low sulfur content for environmental control.
Furnace oil is one kind of residual fuel. These are blended with other suit-
able gas oil fractions in order to achieve the viscosity required for convenient
handling. As a residue product, fuel oil is the only refined product of significant
quantity that commands a market price lower than the cost of crude oil.
Because the sulfur contained in crude oil is concentrated in the residue mate-
rial, residual fuel sulfur levels naturally vary from less than 1 to over 6%. The
sulfur level is not a critical factor for the combustion process as long as the flue
gases do not impinge on cool surfaces. However, residual fuels may contain large
quantities of heavy metals such as nickel and vanadium; these produce ash upon
burning and can foul the burner systems. Such contaminants are not easily re-
moved and usually lead to lower market prices for fuel oils with high metal con-
tents.
56 Chapter 1
In order to reduce air pollution, most industrialized countries have restricted

the sulfur content of residual fuel. Such regulations have led to the design and
construction of residual desulfurization units or cokers in modern refineries to
produce fuels that meet these restrictions.
The standardized properties of residual fuels are:
• Density at 15°C ranging from 0.975 to 1.01 g/cm3.
• Kinematic viscosity at 100°C ranging from 10 to 55 mm2/s. The viscosity of
an oil is a measure of its resistance to flow. Over the years different units have
been used for viscosity (Engler Degrees, Saybolt Universal Seconds, Saybolt
Furol Seconds and Redwood No. 1 Seconds). Nowadays, a majority of resid-
ual fuels are traded internationally on the basis of viscosity measured in centi-
stokes (one centistoke = 1 mm2/sec). The value for viscosity should be given
together with the temperature at which it is determined. Accepted tempera-
tures for viscosity determination of residual fuels are 40°C for distillate fuels
and 100°C for vacuum residues. If a fuel contains an appreciable amount of
water, testing for viscosity determination at 100°C is impossible. In this case,
viscosity is determined at a lower temperature (usually 80-90°C). It is then re-
calculated to obtain viscosity at 100°C. Due to the variability of the composi-
tion of residual fuels, calculations for viscosity at another temperature from
that measured at one temperature may not be accurate. Therefore, such calcu-
lated results should be treated with caution. The viscosity result is used first to
ensure that the fuel is correctly heated in storage and made ready for pump-
ing. The maximum viscosity for efficient pumping is considered to be around
600 cSt. However, lower viscosity should be maintained if long pipelines are
installed.
• Flash point has to be over 60°C for residual fuels. The flash point is consid-
ered to be a useful indicator of the fire hazard associated with the storage of
residual fuels. The flash point is determined by using the Pensky Martens
closed cup tester. It should be remembered that results can be affected if the
fuel sample contains a significant amount of water. There is one difficulty en-
countered by laboratories, which are requested to carry out a wide range of
tests on one sample of residual fuel, including flash point. To ensure that a
fuel sample is fully homogeneous, it should be heated for a period of time and
shaken or preferably homogenized before it is split to perform individual
tests. This preheating and homogenization may release some of the vapors
from the sample thereby affecting the flash point result.
• Pour point varies from 0 to 45 °C depending on the kind of fuel. Pour point is
defined as the lowest temperature at which an oil will continue to flow when
it is cooled under prescribed standardized conditions. If fuels are held at tem-
peratures below their pour points, wax will begin to crystallize. This wax
causes blocking of the filters and can deposit on heat exchangers. Generally,
high viscosity fuels need to be heated well above the pour point to achieve the
desired pumping viscosity. However, these fuels should be stored at a tern-
perature of around 10°C above the pour point if wax deposition is to be

avoided. Some waxy residual fuels have pour points between 40 and 45°C.
• Carbon residue varies from 10 to 22% depending on the residual fuel. The
carbon residue provides information on the coke or carbonaceous deposits
which result from combustion of the fuel. Fuels which are rich in carbon
prove more difficult to burn fully, resulting in increased deposits in the com-
bustion and exhaust spaces. Fuels produced from thermal cracking residues
show a higher carbon/hydrogen ratio and, hence, high percentage carbon resi-
due. Carbon residue can only be an indicator of potential deposit-forming ten-
dency of the fuel. Thus, operating experience with different fuels at different
engine loadings and conditions should be recorded to determine individual
engine tolerance levels to high carbon fuels.
• Ash ranges from 0.1 to 0.2%. The ash content of a fuel is a measure of the
amount of inorganic noncombustible material it contains. Some of the ash-
forming constituents occur naturally in crude oil; others are present as a result
of refining or contamination during storage or distribution. For instance, it
could be due to the presence of compounds of the following elements: vana-
dium, sodium, calcium, magnesium, zinc, lead, iron, nickel.
• Water content varies from 0.5 to 1%. Water is introduced into residual fuels
by poor storage. The standards allow water up to a maximum of 1% in resid-
ual fuels. However, the majority of fuel deliveries have water contents below
0.5%. The problems with high water levels in fuel can be complex and in-
clude sludging of fuel tanks, filter blockage, corrosion of fuel injection
equipment, exhaust valve corrosion, etc.
• Sulfur ranges from 3.5 to 5%. The main problem resulting from the use of
high sulfur fuels is corrosion. During the combustion process, sulfur dioxide
(SO2) and sulfur trioxide (SO3) are produced. Depending upon engine condi-
tions such as excess air, temperature and pressures, these gases will convert to
sulfurous acid (H2SO3) and sulfuric acid H2SO4), to some extent. These acids
are formed when the gases exist below their dew points. For the formation of
sulfurous acid, the favorable temperature should range between 50 and 60°C
whereas for sulfuric acid, it should range between 110 and 150°C. These ac-
ids cause corrosion in the low temperature zones of engines and boilers.
Hence, their effect is often referred to as "cold end corrosion".
• Vanadium content ranges from 150 to 600 mg/kg. The vanadium content of
fuels from different countries varies considerably and is directly related to the
crude oil source. Problems associated with high vanadium have been ad-
dressed under ash, sodium and sulfur. These problems are largely overcome
by good engine design, and correct fuel treatment. To prevent these problems
additives are widely used.
58 Chapter 1
1.3.5 International Standards for Fuels
MS ISO 8216/0 — 8216/4 have been developed as standards for fuel classi-
fication in the framework of international standardization.
MS ISO 8216/0 establishes the general classification of petroleum fuels
(fuels of class F). There are five categories of products which are included in class
F. These categories depend on the type of fuel.
A detailed classification of fuel groups with regard to conditions of applica-
tion, type, properties and characteristics establishes the groups of products for each
category and these are provided by separate parts of ISO 8216. Thus, parts desig-
nated as ISO 8216/1, ISO 8216/2, ISO 8216/4 which have been developed are
based on these standards. The Russian standards are included in the international
standards system:
• ISO 8216/0-86 - Classification. Part 0. This is a general classification of pe-
troleum fuels (Class F). The Russian equivalent for this standard is COST
28577.0-90.
• ISO 8216/1-86 - Classification. Part 1. This covers the categories of fuels for
sea engines. The Russian equivalent for this standard is COST 28577.1-90.
• ISO 8216/2-86 - Classification. Part 2. This covers the categories of fuels for
gas turbines for applications in industry and for sea engines. The Russian
equivalent for this standard is GOST 28577.2-90.
• ISO 8216/4-86 - Classification. Part 3. Group 1. This covers liquefied petro-
leum gases. The Russian equivalent for this standard is GOST 28577.3-90.
Table 1.4 shows the international classification of petroleum fuels.

The fuel classification used for jet planes deserves special attention. In a
majority of countries, the quality for these fuels is defined in the basic specifica-
tions developed in ASTM and DERD (the British Defense Ministry). The national
specifications of the countries of manufacture of the jet fuel have insignificant
deviations from the ASTM and DERD specifications.
To avoid confusion in interpreting fuel marks for delivery and storage of jet
fuels, their basic manufacturers and the suppliers have developed a general speci-
fication covering the restrictive requirements of the basic specifications. These are
used in the countries in which consumption of the jet fuels is greatest. This docu-
ment is known as "The Requirements for the quality of jet fuel for common used
systems" or AFQRJOS.
In the USA, the requirement for quality of jet fuels (list of the physical-
chemical parameters and operational properties) for civil aircraft are made out as
the ASTM D 1655 specification. Accordingly, the following fuels are made:
• Jet A - Fuel of the kerosene type with maximal freezing temperature of -40°C
• Jet A-1 - Similar to Jet A with freezing temperature of -47°C
Table 1.4: Classification of petroleum fuels (class F).

Category Characterization
G Gas.
Gas of petroleum origin consisting basically of methane and ethane
L Liquefied Gas.
Liquefied gas of petroleum origin consisting basically of propane, propene and both
butane and butene
P Liquid Fuels.
Fuels of petroleum origin excluding liquefied petroleum gases. They include gaso-
line, jet fuels, gas oil and diesel fuel.
Heavy distillates can contain small quantities of residues
R Residual Fuels.
Petroleum fuels containing residual fractions of a distillation process
C Petroleum Coke.
Hard fuels of petroleum origin produced in cracking processes, and consisting
basically of only carbon
The requirements for British jet fuels for civil aircraft are established by the
specification D, Eng. RD (DERD) 2494. Previously, it was developed for military
aircraft. This is fuel of the kerosene type with a freezing temperature of-47°C.
The list of control operations (AFQRJOS) is a basis for the international
requirements for jet fuels.
Fuel for turbines that are made and delivered according to AFQRJOS should
correspond to the most rigid requirements of the following specifications:
• The standard of the British Defense Ministry DBF STAN 91-91/ Editions 2
(DERD 2494) from May, 1996
• The standard specification ASTM D 1655
• The managing material of the international association of air transport (IATA)
from December, 1994
The jet fuel that corresponds to the requirements of AFQR-JOS in the

documents is marked as Jet A-1.
In the CIS (former USSR), jet fuels are made with regard to GOST T 10227.
The main marks are TS-1 and RT.
Fuel classification as the normative document is absent in Russian practice.
Concrete requirements are reflected in the documentation for the various kinds of
fuel (e.g. GOST and OST), and also in various specifications.
1.4 LUBRICATING OILS AND LUBRICANTS
Lubricants are of multiple importance in the forging process. They serve as

the cooling agent of the forging parts, support the filing of parts and prevent the
60 Chapter 1
fusion of work piece and tool. The main functions of lubricating oils and lubri-
cants are:
• Reducing friction. Putting lubricating oil between moving metal surfaces
decreases friction. This results in energy conservation and significantly less
wear.
• Reducing wear. Lubricating oils reduce mechanical wear (caused by abrasion
and erosion) and chemical wear (corrosion caused by combustion acids and
water). Wear is influenced by various factors which can be divided into the
fields of tool, rough part, forming machine, lubricant and actual contact area.
Possible ways to reduce wear lie in the increase of annealing durability as
well as in the hardness of the surface, for example through nitriding, and ap-
plication of mostly ceramic wear resistant layers on the tool surface. Also,
massive wear reduction can be achieved by lowering the tool temperature.
• Cooling. Lubricating oil cools the mechanical components by helping to
remove heat and decreasing the amount of heat produced (by reducing fric-
tion).
• Ensuring leak tightness. Lubricants ensure leak tightness between the me-
chanical components such as the cylinder and the piston, improving compres-
sion and producing better engine performance.
• Removing impurities. Lubricants keep engine components clean by prevent-
ing the formation of deposits and suspended impurities (dust, combustion
residue, engine wear particles) that then build up on the oil filter.
Properties differ from one lubricant to another. However, the one compo-
nent that lubricants have in common is that they are composed of a main ingredi-
ent called the lubricating base. The lubricating base may be petroleum derived or
synthetic. The lubricating base accounts for 75 to 85% of the lubricant. There are
three different classes of lubricating bases that are used in modern oil industry:
• Mineral bases are manufactured from petroleum that has undergone a variety
of complex separation processes. They are the most commonly used for both
automotive and industrial applications.
• Synthetic bases or synthetics are products created by the chemical reaction of
several ingredients. Two main classes are used for lubricants: esters and syn-
thetic hydrocarbons (in particular polyalphaolefms manufactured from ethyl-
ene). These products have excellent physical properties and exceptional ther-
mal stability.
• Semi-synthetic oils are obtained from mixing both types of bases (generally
70 to 80% of mineral oil and 20 to 30% of synthetic oil).
The development of modern lubricants and their correct use are especially
important as these have substantial economic consequence on the use of these
devices. Optimally chosen lubricant brings saving of energy needed for machine
work, conserves the parts of these devices, reduces wear and tear, reduces the
maintenance time and shortens the overhaul intervals, which can take away mil-
lions of dollars from industry. The characteristics of lubricants are improved by
special substances called additives. In the current industrialized society, the use of
lubricants without these enhanced characteristics is no longer conceivable. Lubri-
cating oil additives are synthetic active substances, which are added to the basic
oils in order to give the products the desired characteristics or properties. This is
why, additives are the next main compounds of the oils (15 to 25%).
The following main classes of additives are available:
• Viscosity index improvers. These make the oil a sufficiently low viscous fluid
when cold (to facilitate starting) by lowering the pour point to between -45
and -45 °C (depending on the oil), and to viscous fluid when hot (to prevent
the contact between moving mechanical components). This class of additives
are polymers which are introduced into a lubricating base to produce a rela-
tive greater increase in viscosity when hot than when cold.
• Antiwear additives. These reinforce the antiwear action of the lubricant. The
main family of antiwear additives are alkyl-zinc dithiophosphates and numer-
ous phosphorus derivatives.
• Antioxidants. These eliminate or slow down lubricant oxidation, increasing
the time between oil changes through improved resistance to high tempera-
tures. Dithiophosphates that are used as antiwear additives are also excellent
antioxidants. Other chemical families such as substituted phenols and aro-
matic amines are also used.
• Detergents. These prevent the formation of deposits and varnish on the hottest
areas of the engines (such as ring grooves). Calcium or magnesium metal salts
from main chemical families such as alkylaryl-sulfonate, alkylphenate and al-
kylsalicylate are used as detergents.
• Dispersing agents. These maintain in suspension all the solid impurities
formed during engine operation. The solid impurities include unburned resi-
due, gums, sludge, diesel soot, deposits cleaned by detergents. Usually polar
compounds from the alkenylsuccinimides, succinic esters or their derivatives
are used as dispersing additives.
• Alkalinity additives. Those that neutralize combustion acid residue from fuels
are made primarily for diesel engines. The main compounds of this class of
additives are phenols and salicylates (which are natural alkaline), and sul-
fonates. In the case of sulfonates, their neutralizing property can be reinforced
by adding basic salts such as carbonates or hydroxides.
• Corrosion inhibitors. These prevent the corrosion of ferrous metals under the
combined effects of water, atmospheric oxygen and a number of oxides
formed during combustion. Mainly alkaline or alkaline-earth sulfonates, neu-
tral or alkaline (Na, Mg, Ca) salts, fatty acids or amines, alkenylsuccinic acids
and their derivatives are used as corrosion inhibitors.
• Antifreeze agents. These enable lubricating oils to retain good fluidity at low
temperatures (from -15 to -45°C). The main classes of this type of additive are
62 Chapter 1
polymethacrylates, maleate-styrene copolymers, naphthalene waxes and vi-

nylacetate-fumarate polyesters.
Foaming inhibitors. Oil foaming can be caused by the presence of other addi-
tives. For example, detergent additives act in the same way as soap in water;
they clean the engine, but tend to foam. Foaming can also be caused by lubri-
cating system design for which the major aim is to facilitate air-oil mixing.
Such designs can cause turbulence during lubricant flow as well as formation
of bubbles in the oil. Very small amounts of silicon oil or alkyl acrylates can
be used as an antifoaming additive.
Extreme-pressure additives. These reduce friction torques and, as a result,
conserve energy and protect the surfaces from heavy loads. The most com-
mon classes of this additives are organometallic derivatives of molybdenum
and some compounds derived from fatty acids, phosphorus-sulfur molecules,
borates, etc.
It can be seen that the main functions of additives are to improve the lubri-
cating properties of the lubricant and to make the lubricant as stable against ad-
verse effects such as oxidation, corrosion, etc. It is important to know the mecha-
nisms of the various effects that each additive is trying to inhibit in order to make
the right choice of the additive or mixture of various additives to select. The most
important function of all lubricants is to lubricate the surfaces in order to prevent
friction between them.
As shown in Figure 1.8, there are four different kinds of friction.
fluid friction mixed friction hard surfaces friction film friction
Fig.1.8: Four kinds of friction.
In fluid friction, there is no contact between two surfaces. It is obvious that

wear and tear is minimal in this type of friction. However, there is still very high
need for lubricants for fluid friction, even though it is economically unjustifiable
to use this type of friction in big industrial devices. The most popular types of
friction in industrial devices are mixed and film friction. Mixed friction is present
as a combination of fluid friction and hard surface friction. The tear by mixed
friction is obviously higher than by fluid friction, because there is contact between
surfaces at some points. The optimal for the industry is the so-called film friction.
In this kind of friction, a thin film of surface-active substance is formed. This film
protects the surfaces from direct contact and high wear and tear.
It is possible to make the film for film friction artificially. Such a modifica-
tion in the lubricant and the friction surfaces is carried out by addition of special
additives called anti-wear (AW) and extreme pressure (EP) additives. The name
EP additives is derived from the need to endure extremely high pressure at the
points of contact between two surfaces. The most popular AW and EP additives
are made from zinc dialkyldithiophosphate. This zinc complex with general
chemical structure Zn[(RO)2PS2]2 belongs to the group of film forming surface
active substances. However, zinc dialkyldithiophosphate does not form the pro-
tecting film for film friction, but the products of their decomposition during fric-
tion do form the protecting film. The final film mostly contains hydrocarbons.
However, there are inorganic compounds such as iron sulfides, iron oxides, zinc
oxides, amorphous polyphosphate and so on. An example of film formation on the
friction surface is shown in Figure 1.9.
One more important requirement for lubricating oils, which can be improved
by adding additives, is the ability to keep their properties for a long time. One of
the most important additives used to improve this ability of oils is antioxidants.
Oxidation is a radical chain reaction promoted by alkyl and peroxide radi-
cals. This means that it is necessary to add radical acceptors to the oil to prevent its
oxidation. It is possible to classify most of the modern antioxidants in six groups:
oil, additives, wear and tear products

hydrocarbons Amount of inor-
and additives ganic substances
increases,
amorphous poly-
from 100 amount of or-
phosphate and,
nmupto ganic compounds
MeO, MeS
lOOOnm decreases
inorganic film
Iron surface
Fig.1.9: Formation of the film in film friction.
1. Antioxidants, which prevent oxidation by reaction with peroxide radi-

cals. Such additives often contain aromatic compounds in their struc-
ture with relatively weak O-H and N-H bonds. Examples of such com-
pounds are phenols, naphthols, aromatic amines, aminephenols, and di-
amines. This type of additive has strong reducing properties and reacts
quickly with peroxide radicals.
2. Antioxidants which prevent oxidation by reaction with alkyl radicals.
The additives react quickly with alkyl radicals. Examples of such addi-
tives are hynones, iminehynones, methylhynones, stable nitrogen oxide
radicals, and molecular iodine. Alkyl radicals react quickly with oxy-
64 Chapter 1
gen. This is why antioxidants of this type are effective under conditions
of oils with low concentration of oxygen.
3. Antioxidants which destroy hydroperoxides. This type of additive re-
acts quickly with hydroperoxides without free radical formation. The
following substances are good examples of such additives: sulphide,
phosphite, arsenate and so on, and also thiophosphate and carbonates of
various metals, and various complexes.
4. Antioxidants which deactivate the surface of metals. Some compounds
of metals with variable valency react with hydroperoxides with the
formation of free radicals, which strongly promotes oxidation. This
type of catalytic oxidation can be prevented by adding a "complex for-
mer", which forms with a metal complex that is rendered inactive to
hydroperoxide. Examples include diamines, hydroacids and other com-
pounds that form strong complexes with metals.
5. Antioxidants with repeated action. During the oxidation of some
classes of substances such as alcohols and aliphatic amines, peroxide
radicals are formed, which have both oxidizing and reducing functions.
In such systems, additives that prevent oxidation are regenerated again
in the reducing reaction. This involves a catalytic breakage of the chain
in the radical chain reaction. The number of chain breakages depends
on the reaction ratio of additive regeneration and its consumption in the
reversible reaction. Examples are aromatic amines, nitrogen oxide
compounds, compounds of metals with variable valency, etc.
6. Antioxidants with combined function. Some additives prevent oxida-
tion by simultaneous reactions with many compounds that promote
oxidation. For example, it can react with both alkyl and with peroxide
radicals (anthracene, methylhynon), or can destroy hydroperoxides and
break off the reaction chain with RO2- radicals (carbomate and thio-
phosphate of metals). Such compounds are referred to as antioxidants
with combined function. The parallel reactions can occur with the same
group in one additive. For example, R- and RO2' radicals react with the
double bond of methylhynon. Frequently, two or more functional
groups exist in one molecule, each of which is responsible for an ap-
propriate reaction. For example, phenolsulphide reacts with hydroper-
oxide with the sulfide group and with RO2- with the phenol group. In a
different type of reaction, it can take part in the initial reaction with an-
tioxidant and products of its transformation. Often the mixtures of addi-
tives have combined function. For example, adding phenol and sul-
phide to the oil first prevents oxidation by breaking the reaction chain
with RO2- radical, and second reduces the reaction rate for branching
reactions by destroying the hydroperoxide. Synergy may be obtained if
two antioxidants strengthen the action of each other. Also, it is possible
for the action of two or more antioxidants to be additive. However, if
the action of a mixture is less than the sum of the actions of each anti-
oxidants, antagonism results.
In the last type of antioxidants we learn that an important property of anti-

oxidants is synergy. It is to be understood that by synergy one can mix antioxi-
dants each with a weak action against oxidation and obtain a strong antioxidant
action as a combination. That may sound strange but this effect really occurs dur-
ing the preparing of many industrial additives. This is why it is especially impor-
tant to understand the nature of synergetic effects in order to be able to use the
maximum possible potential of additives. How to obtain synergistic effects can be
classified in three groups:
1. One antioxidant breaks the reaction chain and the second reduces the
ratio of initiation by destroying ROOH groups or by deactivating the
catalyst that promotes the formation of the ROOH.
2. Two initial substances (antioxidants or not) react with each other and
form an effective antioxidant.
3. The transformation products of antioxidants strengthen the antioxidant
function.
The main properties of lubricants and lubricating oils are determined by

carrying out the following specific tests:
• Oxidation tests. The combined effects of ambient oxygen and temperature
affect lubricant aging; this phenomenon is known as oxidation. In laboratory
oxidation tests, temperatures are selected in accordance with those encoun-
tered during equipment operation.
• Corrosion tests. One of the lubricant's main functions is protection against
corrosion. Accordingly, the reactions between the lubricant and various metal
surfaces need to be determined and, where appropriate, modified.
• Chemical compatibility tests. These tests are used to determine the behavior
of various materials when they are in contact with oil. For example, specific
tests are conducted to ensure the compatibility of a lubricant with seals.
• Storage stability tests. Some lubricant combinations are formed by the asso-
ciation of products that are not fully miscible in oil. In this case, the final sta-
bility that represents changes during storage needs to be verified.
• Dispersion tests. The purpose of these tests is to determine the ability of an oil
to maintain in suspension solids that are likely to form during operation. For
example, combustion engines produce carbon residues, some of which are
found in the oil. The latter must be able to maintain the soot in suspension and
prevent deposits that could result in fouling or even clogging.
• Shear tests. These tests determine how well lubricants withstand mechanical
loads that can cause the molecules of some components to break up.
• Pressure tests. There is currently no device available that can directly measure
the ability of an oil film to withstand pressure. Various properties (film
66 Chapter 1
strength, high pressure, extreme pressure) can only be assessed using bench
tests in the laboratory to determine their effects on other oil properties. The
same types of tests are carried out for greases as for oils, using special de-
vices: four-ball machine, Timken, etc.
• Laboratory tests are supplemented by bench tests on machines very similar to
real ones and which operate under controlled conditions.
• Engine tests are designed to determine the behavior of oils on either gasoline
or diesel engines. Each test is performed in such a way as to highlight one or
more lubricant properties. No single engine test is available that enables all
properties to be tested simultaneously.
• Bench tests are carried out either on standard automotive multi-cylinder en-
gines or on single-cylinder engines.
• Gear tests check the internal cohesion and pressure withstanding properties of
lubricants on real gears. Various methods are used depending on the type of
gear and test conditions.
1.4.1 International Standards for Lubricating Oils
1.4.1.1 Industrial oils
The most fully developed standards system of classifications of industrial

oils is the series MS ISO 6749 "Lubricant materials, industrial oils and related
products (Class I). Classifications of groups".
The classification includes 18 groups of products into which this class is
divided according to the area of application (Table. 1.5).
The use of the international classification according to lubricant material
application allows us to group lubricant materials that are made in different coun-
tries in the classes of the application area. This considerably facilitates the task of
selecting the lubricant materials for the specific equipment.
Interchangeability of lubricant materials produced in different countries and
intended for specific equipment can be established by the complex estimation of
their functional properties, by the laboratory devices and installations, by stands
with model and natural friction units, by the real engines, in real machines, and
mechanisms at the operating conditions.
The principles and criteria for estimating these properties and also equip-
ment used to perform tests of all kinds for these oils in different countries are
basically identical. However, concrete laboratory, stand, motor and operational
methods can differ appreciably. Besides, there are differing viewpoints among
experts even from the same country regarding the classification of the methods,
i.e. this classification is substantially conditional.
Table 1.5: Classification of lubricant materials, industrial oils and related prod-
ucts. Division into groups according to area of application.
Group Application
A Open systems
B Formless systems
C Gear wheels
D Compressors (including cooling)
E Engines of internal combustion
F Spindles, bearings and couplings connected to spindles

G Gear wheels
H Hydraulic systems
M Metal treatment
N Electrical isolation
P Pneumatic tools
Q Heat transfer
R Temporary protection against corrosion
T Turbine
X Applications requiring greasing
Y Other applications
Z Cylinders for steam machines
1.4.1.2 Motor oils
The classifications of motor oils according to SAE and API have been ac-
cepted worldwide.
Motor oils are classified according to their viscosity and operational proper-
ties. Besides, motor oils are subdivided in terms of energy conservation and ability
to reduce fuel charge in comparison with a reference oil.
68 Chapter 1
The classification according to viscosity is based on the standard SAE J 300

"Classes of viscosity of motor oils" in which the designation of the oils is given
according to their viscosity at 100 °C and at a temperature < 0 °C (Table 1.6).
The class of the oil according to SAE characterizes only the viscosity of the
oil and does not give information about its operational properties.
The area of application is defined by the operational properties of the oil.
The most widespread classification by operational properties and areas of
application of motor oils is the API classification (Table 1.7).
Universal oils have a double designation (SF/CD, CE/SG).
During the operation of automobiles, the classification of oil according to
SAE is recommended whereas the classification according to API is applied with
respect to operational properties.
Table 1.6: Classification of motor oils by viscosity — SAE J 300 (April, 1997)
Viscos- Viscosity at low temperature Viscosity at low temperature
ity pumpability, Mpa-s, at pumpability, Mpa-s, at Kinematic viscosity, Kinematic
class the temperature (°C) the temperature (°C) mm 2 /s,atlOO°C viscosity,
ASTM D 5293 ASTM D 4684 min max mm2/s, at
150°C
OW 3250 at -30 6000 at -40 3.8 - -
5W 3500 at -25 6000 at -35 3.8 - -
10W 3500 at -20 6000 at -30 4.1 - -
15W 3500 at -15 6000 at -25 5.6 - -
20W 4500 at -10 6000 at -20 5.6 - -
25W 6000 at -5 6000 at -1 5 3.3 - -
20 - - 5.6 <9.3 2.6
30 - - 9.3 <12.5 2.9
40 - - 12.5 <16.3 2.9
40. - - 12.5 <16.3 3.7
50 - - 16.3 <21.9 3.7
60 - - 21.9 <26.1 3.7
The CCMC (ACEA) Classification of motor oils has been developed for
European engines. The CCMC classification is developed separately for gasoline
and diesel engines, similar to what pertains for API (Table 1.8).
Each class of CCMC oils is comparable with the corresponding class of API
oils and is defined by a set of complex laboratory and motor tests, according to
ASTM, CBC, IP or DIN standards.
Table 1.7: API classification for motor oils by its operational properties and
areas of application.
Class Application area

Category S (Oils for gasoline engines)
SA Engines working at light conditions
SB Engines working at moderate conditions
SC Engines working with high loadings (models released before 1964)
SD Engines working at heavy conditions (models released before 1968)
SE Engines working at heavy conditions (models released before 1 972)
SF Engines working at heavy conditions reformed gasoline
SG Engines released since 1989
SH Engines released since 1 994
SJ Engines released since 1 997
Category C (Oils for diesel engines)
CA Engines working at moderate loadings with low sulfuric fuel
CB Engines working at high loadings with sulfuric fuel
CC Engines working in heavy conditions
CD Engines working in heavy conditions with high sulfuric fuel
CD-II The same for old diesel engines
CE Engines working in heavy conditions
CF-4 Engines released since 1 990
CF-2 Improved characteristics of CD-II
CG-4 Engines released since 1 994
Table 1.8: CCMC classification for motor oils by its operational properties and
areas of application.
Class | Area of application
Oils for gasoline engines
Gl Engines, working in usual conditions
G2 Engines of modern cars working in hard conditions
G3 Engines of modern cars, with high viscous properties
04 Engines of modern cars, used for driving with high-speed
G5 Engines of sports high-speed automobiles
Oils for diesel engines
Dl Engines working under usual conditions
D2 Engines working under heavy conditions
D3 Engines working under especially heavy conditions
PD-1 Diesel engines of the cars
D4 Engines working in heavy conditions
D5 Engines working in especially heavy conditions
PD-2 Engines with turbo-pressurization for cars
70 Chapter 1
Since January of 1996, the ACEA classification has practically replaced the
CCMC classification. The ACEA classification was developed as an integration of
standards of European organizations: CEC, ATC and ATIEL. It was adopted in
1998.
The ACEA classification is applicable to different oil products for different
gasoline engines (classes Al-96, A2-96, A3-96), diesel engines (classes Bl-96,
B2-96, B3-96) and diesel trucks (classes El-96, E2-96, E3-96). After the changes
and additions, new classes Al-98 and A3-98 for gasoline engines, Bl-98, B2-98,
B3-98 and B4-98 for diesel engines of cars and E4-98 for diesel engines of trucks
have been included.
A new system known as the European monitoring system of the qualities of
motor oils (EELQMS) has been developed to cover the requirements for European
motor oils. EELQMS includes the requirements of registration of tests, data col-
lecting and change of compositions. All tests should be registered in the European
registration center (an independent organization, possessing experience in the
control of the order of the performance of tests) before they are performed.
The car firms in the USA and Japan cooperating with ILSAC have formu-
lated requirements for motor oils for gasoline engines of cars. In ILSAC classifica-
tion, there are two classes which are designated as GF-1 and GF-2. They are close
to API classes SH and SJ, respectively.
1.4.1.3 Transmission oils
The requirements for quality of transmission oils intended for various tasks
are numerous. This is why there is the need for classification.
Similar to motor oils, there are two systems of classification: SAE with
regard to viscosity and API with regard to operational properties.
According to SAE classification, tractor transmission oils are divided into 6
classes (Table 1.9) with regard to viscosity.
A hyphenated viscosity class implies that the oil is suitable for all seasons
for the specific climatic zone. For example, the oil with SAE 75W-90 classifica-
tion has the low temperature properties of the viscosity class SAE 75W (i.e. dy-
namic viscosity of the oil does not exceed 150 Pa*s at the temperature of -40°C).
At a positive temperature, the kinematic viscosity corresponds to the viscosity of
the class SAE-90, (i.e. at 100°C the kinematic viscosity is 13.5-24 mm2/s).
The distinctions in designs of transmission units and conditions of their
operation create distinctions in the requirements for operational properties of the
oil.
The development of API classification was based on this principle. As such,
the oils are divided according to the type and loading degree of the gears where the
oil is applied (Table 1.10).
Table 1.9: The SAE classification for transmission oils with regard to viscosity.
Viscosity class The maximum temperature Kinematic viscosity
of the achievement of the Min Max
dynamic viscosity of 150
Pa*s, °C
winter oils
75W ^0 4.1
SOW -26 7.1
85W -12 22.1
summer oils
90 13.5 24
140 24 41
250 41
The SAE and API classifications give only the general characteristic of oils
without consideration of all parameters of quality. The complete requirements for
physical, chemical and operational properties of the oils and their allowable limit-
ing values are given in the specifications. In the countries of Western Europe and
the USA, transmission oils are produced with two types of specifications:
• Specifications of firms making automobiles
• Military specifications for oils for supply to the armed forces of both the USA
and NATO are made
Both specifications include the requirements for physical, chemical and

operational properties of the oils as well as a definition of the number and methods
for their tests.
Table 1.10: API classification of transmission oils with regard to area of appli-
cation.
Class Application area
GL1 Cylindrical and spiral-conic gears, working at low speeds and loading
G12 Cylindrical gears, working at low speeds and loading
G13 Usual transmissions with spiral-conic gears, working in hard conditions
GL4 Transmissions, working at normal speeds and high loading
GL5 Transmissions, working at high and low speeds and high loading
G16 Transmissions, working at extreme high speeds and normal loading
MT1 Mechanical transmissions
According to API classification, industrial specifications are applied to all

kinds of oils from GL-1 up to GL-6. On the other hand, military specifications are
only applied to GL-4 and GL-5.
These specifications provide the check for all parameters of quality require-
ments that are specified.
72 Chapter 1
In the USA and the countries of Western Europe, the widest application has
been achieved by the military specifications from the USA:
• MIL-L-2105 (1959 is replaced by MIL-L-2105B)
• MIL-L-2105B (1973 is replaced by MIL-L - 2105C)
• MIL-L-2105C (1987 is replaced by MIL-L-2105D)
• MIL-L-2105D (since 1987)
In USA in 1995, a new military specification MIL-PRP-2105E that unites

the MIL-L-2105D and API MT-1 requirements was developed.
The military specifications give the descriptions of almost all requirements
for lubricant oils that are available at gas stations in the USA and in a majority of
other countries.
However, the requirements of some manufacturers are higher than guaran-
teed by these specifications. Therefore, manufacturers of automobiles have their
own specifications for transmission oil for the first filing. These oils need these
additional requirements to ensure specific characteristics such as cleanliness of
details, serviceability of synchronizers, etc.
Nevertheless, for the first filing, oils are frequently recommended according
to the MIL-L-2105D specification.
1.4.1.4 Hydraulic oils
In the framework of international standardization, hydraulic oils are classified by

the ISO 3448 standards for viscosity classes and ISO 6074 for operational proper-
ties. According to ISO 6074, liquids from mineral raw material used in hydraulic
systems are incorporated in group H, which in turn is subdivided into four catego-
ries depending on the structure of the oils and the application area:
• HH — mineral oil without additives
• HL — mineral oil with antioxidizing and anticorrosive additives
• HM — oil of the HL type with antideterioration additives
• HV — oil of the HM type with improved viscous-temperature properties
Modern Characterization and Analysis
Techniques for Crude Oil
2.1 CHROMATOGRAPHIC METHODS
Chromatography is probably the oldest and most important analytical

method in crude oil chemistry as well as general analytical chemistry. The first
record of the use of the principle of chromatography can be traced back to ancient
times when the ancient philosopher, Aristotle, wrote about the use of the adsorp-
tive action of special substances for the purification of seawater. However, the first
scientific use of chromatography was at the end of the nineteenth century when in
1895 the German scientist Ferdinand F. Runge described for the first time a
chemical separation method based on the chromatography principle. The method
used by Runge can be classified or called paper chromatography or a very simple
form of thin film chromatography. At the time, the German scientist did not real-
ize the importance of the method, but merely described it as a type of scientific
game. At the end of the nineteenth century, R. T. Day, for the first time, attempted
to separate crude oil by filtering it through a lime filter. Unfortunately, the scientist
did not recognize the main principle on which this method was based but de-
scribed it as a new filtration technique. The first inventor of chromatography to
describe its main principles was the Russian scientist M. S. Zwet, who used the
chromatography method in 1903. Zwet was a botanist and used chromatography
for the study of chlorophyll. A. J. P. Martin and R. L. Synge received the 1955
Nobel Prize in Chemistry for the development of a new chromatographic analyti-
cal method. These scientists were the first to separate amino acids by the chroma-
tographic method. Perhaps this year could be marked as the birth year of modern
chromatography.
73
74 Chapter 2
The main idea behind chromatography is the separation of a mixture of two

or more compounds by using two auxiliary phases; one of which is the static phase
and the other the mobile phase. The physical state of the static or stationary phase
can be solid or liquid whereas the mobile phase can be liquid or gaseous. All
chromatographic methods can be classified into four main classes based on the
combination of the physical state of the mobile and static phases:
1. Mobile phase is liquid and static phase is solid. The main principle of the
separation by this method is adsorption on the static phase.
2. Mobile phase is liquid and static phase is liquid. The main principle of
the separation by this method is absorption on the static phase or distri-
bution of the compounds analyzed between the two phases.
3. Mobile phase is gas and static phase is solid. The main principle of the
separation by such method is adsorption on the static phase.
4. Mobile phase is gas and static phase is liquid. The main principle of the
separation by such method is absorption on the static phase or distribu-
tion of the analyzing compounds between the two phases.
2.1.1 Gas Chromatography
In gas chromatography, the mobile phase is gas and the static phase is usu-
ally a liquid, or a solid in special cases. The main application of gas chromatogra-
phy is in the analysis of complicated mixtures of many components. The high
popularity of gas chromatography is due to its requirement of small sample
amounts for analysis and the possibility to analyze compounds in trace amounts.
The biggest disadvantage of this method is that all the compounds analyzed must
be in the gaseous phase or can be evaporated into the gaseous phase.
In gas-liquid chromatography, the stationary phase is a liquid which is cov-
ered on an indifferent (inert) solid substance called the carrier. The carrier is either
a porous adsorbent or the wall of a capillary. This analytical method corresponds
to the principle of classical distribution chromatography, in which a liquid is used
as the mobile phase. In gas adsorption chromatography, solid granulates with an
active adsorptive surface, such as activated coal or silica gel, are used as the sta-
tionary phase.
Gas chromatography has been well known as a separation method for a long
time. After they had invented the principle of distribution chromatography, A. J. P.
Martin and R. L. Synge suggested the use of a flowing gas as mobile phase. The
reason is that gas makes it possible to carry out distribution chromatography with
high flow velocity, because of its low viscosity as opposed to the viscosities en-
countered in the liquid phase.
The rapid development of the method in the last few years has substantially
contributed to the relatively simple and extremely sensitive measuring methods of
gas chromatography. This makes it easy to operate continuously with connections
between the separating column and the detector. Thus, separation, identification
Characterization and Analysis Techniques 75
(qualitative) and quantitative detection can be made practically in one processing

step. A temperature of analysis of 350°C has already been achieved for special
purposes. This means that substances with a boiling point up to approximately
400°C can be analyzed by gas chromatography.
One of the advantages of gas chromatography that needs to be mentioned is
that the analysis can be carried out quickly. With the correct choice of analysis
conditions, it often needs only a few minutes, or in rare cases about one hour, to
complete a gas chromatography analysis. However, the time needed for gas chro-
matography strongly depends on the complexity of the mixture being analyzed. It
was shown in chapter one that crude oil is a very complicated mixture of organic
substances. This is why it is hardly possible to analyze crude oil directly by this
method. It becomes necessary to separate crude oil into different fractions before
analysis is performed by the gas chromatography technique. This separation can
be undertaken by using different methods, including distillation, solution analysis,
etc. Usually such preparation of crude oil fractions for chromatographic analysis
makes the results of analysis more accurate and saves a lot of time during both the
analysis and the evaluation of the analysis results.
With the use of modern instruments for gas chromatography, the amount of
material needed for analysis is very little. For gas analysis, the gas sample needed
is usually under 0.5 cm3, and for liquid mixtures it is under 0.5 g. There are special
gas chromatographs that can handle a sample amount of under 0.01 g.
However, the biggest advantage of the gas chromatography and every other
chromatographic method is that the compounds in the mixture that is being ana-
lyzed (i.e. sample) are not destroyed during the analysis.
Before starting separation for any type of analysis, it is important to under-
stand what type of compounds (components) can be analyzed by the method. Just
as in any analytical method, gas chromatography has specific requirements for the
properties of components that can be analyzed. These requirements are as follows:
1. The components in the sample analyzed must be gaseous or it is possible
to evaporate the sample at a temperature under 350°C.
2. In the case of analysis at a high temperature, it is required that the com-
ponents be thermally stable at the analysis temperature.
3. It is still possible to analyze a sample mixture which contains thermally
unstable compounds. However, in this case, the reaction mechanisms of
the thermal destruction of these compounds must be defined as exact as
possible; in this way, the native compounds of the sample mixture is
analyzed by analyzing their cracking products.
4. The separation of the sample components must be possible on the col-
umn or columns installed in the gas chromatograph. It is important to
point out that every column used in a gas chromatograph is earmarked
only for a specific class of compounds. As such, the column can be used
to analyze only the designated class or classes of compounds. However,
using most modern instruments, it possible to install more than one col-
umn to improve the analyzing capabilities of the gas chromatograph.
76 Chapter 2
It is obvious from the stated requirements that there are a lot of materials
that can be analyzed by gas chromatography. However, the requirement that the
material be gaseous or vapor at the column temperature provides a restriction in
the crude oil compounds that can be analyzed. Actually, with the requirement for
the boiling temperature to be under 350°C, it is only possible to analyze the light
fractions from petroleum such as gasoline, kerosene and diesel. However, these
fractions are very important for their industrial use as fuels. This makes gas chro-
matography one of the most popular analysis techniques in crude oil chemistry.
A simplified scheme of a gas chromatograph is presented in Figure 2.1.
.gas flow controller
detector
sample input
data evaluating
column /
carrier gas thermostat
Fig. 2.1: Scheme of a gas chromalograph.
The detector and column are the most important parts of a gas chromato-
graph. Usually, separation by gas chromatography is carried out at higher than
room temperature. As such, Ihcrmostatic heating of the column is necessary.
There are many types of columns used for gas chromatography and they are
made from different materials. Usually, these are glass, plastics and metals such as
copper or steel. All these materials have advantages and disadvantages for differ-
ent types of analysis. For example, glass columns are thermally and chemically
very stable, and normally these are relatively cheap columns in comparison to
columns made from other materials. The disadvantage of the glass column is that
it is very fragile, and thus it is an easily breakable material that is relatively diffi-
cult to install. Plastic columns are not easily breakable. They are very flexible but
chemically stable. However, the disadvantage of such columns is that they are not
thermally stable. As such, they can be used only for analysis at a low temperature.
The metal columns are now the most popular columns for gas chromatography.
They are not breakable, and are thermally and chemically stable. They only have
the disadvantage that they may not be used for the analysis of acid rich or corro-
sive mixtures, because the metal can be oxidized and this can falsify the results of
the measurement. However, metal columns are now the most robust and stable,
and therefore the most popular types of columns. However, they are also the most
expensive columns. The length of columns used now varies from 1.5 m up to 4.5
m whereas the diameter can vary from 2 mm up to 10 mm.
The most important part of the column is the filling or fill material or pack-
ing. Based on the type of filling, the columns can be classified into packed col-
umns, adsorption columns, distribution columns and capillary columns.
The packed columns are the simplest and at the same time most modest
columns for gas chromatography. The configuration of these columns depends on
the gas chromatograph in which it is used. The most recommended configuration
of packed columns is the U-form, because this makes it simple to clean the column
or change the filling or packing. However, the biggest disadvantage of packed
columns is that they are very sensitive to shaking and the packing can be easily
broken. This type of column is, however, recommended for experimental work in
gas chromatography.
An adsorption column is usually filled with adsorptive active substances,
which could be, for example, oxidized alum, activated coal, silica gel or various
types of molecular sieves. The idea in separation using the adsorption column is
the separation of a mixture of compounds into a number of fractions according to
the adsorption ability of the fill material for the compounds. It is important at this
point to understand what adsorption is. Adsorption is the deposition of a gaseous
or liquid substance on the surface of the adsorbent whereby the substances adhere
to the surface of the adsorbent. The binding or adsorption power or the affinity of
the adsorbent for different compounds has to be different in order for separation to
take place. This allows for the separation of the compounds according to their
different adsorption powers. Adsorption columns are especially effective for
analysis at room temperature. This is why the use of this type of column is rec-
ommended for analyzing gas mixtures. The type of filling must be chosen de-
pending on the nature of the gas compounds; a polar adsorbent must be used for a
gas mixture with a large fraction of polar compounds, whereas non-polar adsorb-
ents must be used for non-polar gases such as hydrocarbons. Since natural gas and
most gases formed during crude oil treatment are hydrocarbons, it is reasonable to
use non-polar adsorbents as filling for analyzing the gases formed during petro-
leum treatment. However, many gas mixtures have complicated compositions
containing hydrocarbons as well as many types of polar gases such as hydrogen
sulfur or carbon monoxide. This is why it may be necessary and it is indeed possi-
ble to have a series of two or more columns in one instrument for most modern
gas chromatographs. This enables the analysis of complicated mixtures of gases in
one step.
The analysis of evaporated liquid mixtures using gas chromatography is
possible as well. For this purpose, filling poisons such as a non-volatile liquid are
used. The purpose of this poisoning is to block the most active adsorptive centers
78 Chapter 2
of the filling. In the absence of filling poisoning, high molecular compounds in the
mixture would be adsorbed so strongly on the active centers of the filling that the
transport of the mixture through the column is practically impossible. This leads to
the formation of zones called tailing zones. Good separation and reproducible
analysis in this case is impossible. A second method to analyze liquid samples
using this type of column is to increase the temperature of the column. However,
this method is useful only for mixtures of compounds with relatively low boiling
temperatures or which can be easily desorbed from the filling at high tempera-
tures.
In the event that the filling of the column must be changed or filled for the
first time, it is important to ensure that the filling is as homogenized as possible. In
order to achieve homogeneity, the packing material is fractionated by sieving into
narrow particle size ranges. Good filling requires only a narrow particle-size range
fraction with the appropriate average particle size. The column must be repeatedly
shaken during the filling of packing material in the column to prevent the forma-
tion of voids in the column. The column should be blown through by high-
pressure air after the column is completely filled with packing. It is done for im-
proved homogenization of the packing. After the column is packed in this way, it
is plugged at both ends and it can be used for analysis after conditioning.
The other type of column used in gas chromatography is the distribution
column. The idea in this column is the separation of compounds of the mixture
according to their solubility in the filling of the column. This type of columns is
recommended especially for the analysis of evaporated mixtures of liquid com-
pounds.
The filling of the distribution column contains a material called carrier,
which is coated with a liquid absorbent. Zeolites or glass spheres are usually used
as carriers whereas non-volatile liquids such as silicone oil or poly-ethylene glycol
are used as the absorbents in distribution columns.
The filling must be custom prepared for every mixture if the appropriate
filling for the particular mixture is not available in the market. The filling for dis-
tribution columns must be as homogenized as possible. This is why sieve fraction-
ating is necessary before the column is filled and absorbent introduced on the
carrier. Fractionation is carried out in the same manner as in the case of filling for
the adsorption column. After the fraction with the appropriate particle size range is
obtained, the liquid absorbent is adsorbed on the surface of the carrier. The oils or
high molecular weight liquids usually used for this purpose are highly viscous
liquids, and it is very difficult to uniformly cover the surface of the carrier with
such viscous liquids. In this case, the absorbent is solved in a small amount of
solvent before covering the carrier. The carrier is then soaked in the solution and
intensively mixed. The excess solvent is removed from the prepared filling by
evaporation at a high temperature. The packing material prepared in such a way is
introduced into the column in the same manner as that in the adsorption column.
The last type of column for gas chromatography is the capillary column or
Golay-column. This type of column is especially interesting because they present
the highest resolution in comparison to all other types of column. Resolution is a

very important requirement of every column. It shows the ability of the packing in
the column to separate the compounds in the sample mixture as completely as
possible. The difference between a packed column and a capillary column is that
the latter has no packing. Instead, it is open on both ends of a column capillary.
The fact that the capillary is open on both ends allows the column to work with
very low gas flow resistance. This is why this type of column usually has a length
of from 20 to 100 meters. The diameter of capillary columns is usually between
0.1 and 1 mm.
The majority of the capillary columns available in the market are made from
glass, steel or quartz. The glass columns are often covered with a thin film of alu-
minum in order to make them less fragile and less breakable. Glass columns are
rarely used nowadays. They have been replaced with columns made from fused
silica. The biggest advantage of such columns is that it is possible to make col-
umns with very thin walls, which are not as easily breakable as the glass columns.
The most important feature of the capillary column, which makes it differ
from other types of columns, is that they have no carrier in their configuration.
There are two types of capillary columns: thin film columns and thin layer col-
umns.
The inner wall of the thin film column is covered with a thin film of the
liquid phase. The thickness of this film can vary from 1 to 3 (im. One example of
the inner arrangement of the thin film column is shown in Figure 2.2.
Fig. 2.2: Inner arrangement of the thin film column.
The thin layer column, also called the analytical column, is ideal for all
types of quantitative and qualitative analysis, because they provide the best possi-
ble resolution in comparison to other gas chromatographic columns. A thin layer
80 Chapter 2
of the carrier is impregnated into the inner wall of the thin layer column. A thin
film of the absorbent is then placed on the impregnated carrier and not on the inner
wall of the column, as in the case of the thin film column. The carrier material is
usually oxidized aluminum or silica gel. During analysis with thin layer columns,
it is important to ensure that all the connections used in instrument, from the in-
jection port to the detector, have the same size as the inner diameter of the column.
Any differences in size can result in the formation of zones where the separated
compounds can be mixed again, leading to the formation of wide peaks on the
chromatogram and bad resolution of the column. The inner arrangement of the
thin layer column is shown in Figure 2.3.
.Impregnated carrier
Fig. 2.3: Inner arrangement of the thin layer column.
The next important part of the gas chromatograph is the detector. The de-
tector is the part of the gas chromatograph which detects the compounds leaving
or exiting the column. It is a very important part of the gas chromatograph in the
sense that even with the best column, if the detector is not able to exactly detect
the compound as it exits the column, then the analysis is incomplete. There are
many methods to detect the compounds present in the sample mixture. For exam-
ple, in the case when the carrier gas is hydrogen, the analyzed sample can be
burned as it exits from the column. The majority of compounds have unique colors
of their burning flames, allowing for the detection of the compounds according
their flame colors. This is just one of the simplest examples of the possibilities for
detection.
Even though there are many types of detectors used in gas chromatographs,
it is possible to classify them as integral and deferential detectors. The latter class
of detectors is currently the most well developed class of detectors. If only the
carrier gas flows through the column, modern deferential detectors will show a
direct zero base line. When analyzing real sample mixtures by gas chromatographs
with such detectors, the detector detects the compound immediately as it exits
from the column and sends a signal to the evaluating computer. After the particu-
lar component or compound has exited the column completely, the detector sends
a zero signal to the evaluating computer. These types of detectors are known as
exact detectors.
The signal sent from the detector is usually too weak to be directly analyzed
by the evaluating computer. This is why this signal is normally amplified. How-
ever, it must be ensured that the signal coming from the detector is strong enough
to be measured but too strong to be off scale. Often, it is not possible to measure
all the compounds of the sample mixture at the same level of amplification of the
signal. This is the reason why attenuators are often installed in gas chromato-
graphs. There are two types of attenuators: input and output attenuators. The input
attenuator is installed before the amplifier, and it can attenuate the signal by 101 up
to 105. The output attenuator is installed right after the amplifier, and this can
reduce the signal sent to the evaluating computer by a factor of from Vi up to
1/4096.
There is one further classification of detectors. Detectors can analyze the
molecules of the mixture with and without destroying of the molecule of the com-
ponent. These two classes of detectors are called destructive and non-destructive
detectors, respectively. The latter type of detector is very sensitive to the concen-
trations of the different compounds in the mixture. Also, the volume of the meas-
urement cell is important for this type of detector.
Currently, there are over a hundred different types of detectors used in gas
chromatographs. In this chapter, only the most popular and probably the most
important detectors will be described.
An important property of each detector is the sensitivity. Sensitivity shows
the ratio between the output signal of the detector and the amount of substance that
is passing through the detector. This characteristic of the detector corresponds to
the gradient of the amount/signal curve. One example of such a curve is shown in
Figure 2.4.
amount
signal
Fig. 2.4: Amount/signal curve.
This curve is defined by the minimal detectable level amount of the sub-
stance that enters the detector. Usually, this level is accepted as two or three times
higher than the magnitude of the normal noise of the detector. The area where the
82 Chapter 2
dependence of the detector signal on the amount of the component or substance

analyzed is reproducible is defined as the dynamic range.
This makes dynamic range an important characteristic of the detector. It is
usually necessary to compare different detectors. The dynamic range shows the
amounts of the substance analyzed needed for reproducible analysis. For some
types of detectors, this area can be relatively small, for example for flame photo-
metric detectors. A relatively wide dynamic range is typical for flame ionization
detectors. Special attention must be given to the dynamic range in the choice of an
appropriate detector for quantitative analysis, because this characteristic of the
detector determines the minimum and maximum concentration of the different
components in the mixtures, which is being analyzed by the gas chromatograph.
Examples of approximate areas (dynamic ranges) for eight most popular detectors
are shown in Figure 2.5.
lfg/S Ipg/S Ing/S 1 mg/S
Fig. 2.5: Dynamic ranges of different detectors:

1 - thermal conductivity detector
2 - flame ionization detector
3 - electron trap detector
4 - nitrogen / phosphor thermo ionic detector for nitrogen compounds
5 - nitrogen / phosphor thermo ionic detector for phosphor compounds
6 — flame photometric detector for sulfur compounds
7 - flame photometric detector for phosphor compounds
8 - photo ionization detector
S - attitude of the signal
The last important property of the detectors is the selectivity. This charac-
teristic of the detector shows which compounds in the sample can be analyzed by
gas chromatograph with each detector. There are universal detectors which can be
used for almost every compound in any sample mixture. For example, by con-
necting a gas chromatography to a mass spectrometer, where the mass spectrome-
ter plays the role of a detector for the gas chromatograph, even the most compli-
cated mixture of compounds can be analyzed. The disadvantage of this hybrid
system is the strictness of the analysis by such detectors such that a full library of
compounds is required at the evaluating computer for this detector. Also, experi-
ence is required of the scientist making the analysis. Universal detectors are the
most used detectors in modern chromatography. If a detector is peculiar for a
particular class of compounds, then it is referred to as a selective detector. Usually,
such detectors are more exact than universal detectors, but the disadvantage of
such detectors is that only mixtures of particular classes of compounds can be
analyzed.
The most popular detector is the flame ionization detector. Using this type
of detector, the component analyzed that is eluting from the end of the column is
mixed with hydrogen and burned in synthetic air. It is necessary to use synthetic
air to achieve a clean burning of the hydrogen and the component analyzed. Ion
formation during the clean burning of hydrogen is hardly possible whereas ions
are formed during the burning of all organic substances according to the following
reaction:
CH + O -> CHO+ + e'
Electrons formed in this reaction are dropped onto the collector electrode.
These electrons form the electrical signal of the detector. It is important to ensure
that synthetic air contains only oxygen and nitrogen and that the collector elec-
trode is very clean from the burning residue or other pollutants. Otherwise, this
can lead to a high deviation of the measured values from the real values. One
example of the flame ionization detector is shown in Figure 2.6.
Actually, the flame ionization detector is restricted to only the analysis of
organic substances. As such, gases like CO2, SO2, NH3 and CO cannot be ana-
lyzed by gas chromatographs with this detector type. However, analyzing inor-
ganic gases in the petroleum chemistry becomes necessary only in some special
cases such as ecological analyses of the gas formed during crude oil treatment.
The Janak detector is probably the simplest detector that exists for gas
chromatography. With this detector, carbon dioxide must be used as the carrier
gas. Both the carrier gas and the sample analyzed go through a vessel containing
concentrated Ca(OH)2 solution after exiting the column. In this way, the carbon
dioxide is separated from the gas analyzed. All the gases not dissolved in the
Ca(OH)2 solution are collected in a special collector. The volume of the com-
pounds is automatically measured in this collector. It is obvious that this collector
cannot be used for analyzing gases that are soluble in Ca(OH)2 solution.
84 Chapter 2
synthetic air
electrode
- , Analyzing
V = and carrier
+
1
<3 ik
hydrogen
Fig. 2.6: Example of the flame ionization detector.
The next and probably most important detector in gas chromatography is the
thermal conductivity detector. This detector contains four cells, which are installed
in a thermostat. Two of the cells are the measurement or analysis cells. The ana-
lyzed gas and carrier gas flow through these cells. The remaining two cells are
called the reference cells. Only the pure carrier gas flows through both these cells.
Inside of all the four cells are platinum or wolfram electrodes. All the electrodes
are heated up using exactly the same electrical stream. As such, the differences in
temperature of the electrodes are only due to the difference in the thermal conduc-
tivities of the gases flowing through them. If a difference in temperature in the
electrodes in the measurement and comparison cells is detected, the detector sends
a signal to the evaluating computer.
The temperature difference is measured by measuring the electrical conduc-
tivity of the electrodes in the cells. All these electrodes are connected in a special
bridge circuit. This circuit is in equilibrium as long as the temperature of all the
electrodes is the same. The electrical conductivity depends strongly on the tem-
perature of the electrodes. If a different gas in the carrier gas flows through the
measurement cells, then this circuit is immediately out of equilibrium.
The different electrical conductivities of the electrodes lead to a change of
voltage. This change is sent as the measured detector signal. One example of the
cells and the bridge circuit are shown in Figure 2.7.
It is obvious from the functioning principles of the detector that the thermal
conductivity detector is suitable for all types of chemical compounds. This is why
its use is recommended for analyzing complicated mixtures such as crude oil frac-
tions or products.
Another type of detector that is used relatively often for gas chromatography
is called the ion trap detector. In some cases, this detector is called a mass selec-
tive detector. Gas chromatographs with this detector are called gas chromatogra-
phy / mass spectroscopy hybrid units. This detector is very popular especially for
the ecologists.
analyzing gas carrier gas
a) b)
Fig. 2.7: a) Scheme of two cells of thermal conductivity detector; b) bridge circuit
The mass spectrometer serves for the exact determination of the masses of
atoms and molecules as well as for the registration of the mass spectra from parti-
cle mixtures to mass and relative proportion. The first ion trap detector was devel-
oped in 1919 by F.W. Aston.
An example of the ion trap detector is shown in Figure 2.8.
The ion trap detector is operated all the time under vacuum. The measure-
ment cell consists of two rotating symmetric pole caps and a ring electrode. The
molecules of the sample are usually analyzed in the measurement cell. They are
ionized by an electron beam that is only switched on for a brief period of time. The
ions in the space between the pole caps and the ring electrode are captured or
caught by a sturdy high-frequency field. By varying the high-frequency field, the
ions leave the space between the pole caps and the ring electrode in the order of
their mass to electrical charge values, and arrive at the amplifier.
It is obvious from the working principle of the ion trap detector that this is
equally a universal detector as is the thermal conductivity detector. The analysis of
the mixtures of compounds with this type of detector is possible not only by reten-
tion time of the compound in the column, but also by the composition of the ions
of this compound. Usually, libraries of the compounds for the ion trap detector are
much more extensive than the libraries for the thermal conductivity detector.
However, the more extensive possibilities for knowing which compound exited
the column makes this detector an excellent detector for the specialist, but intro-
duces many difficulties for beginners.
86 Chapter 2
column
bottom pole cap
electron source
Fig. 2.8: Scheme of the ion trap detector.
The next detector to mention in this book is called the electron capture de-
tector. The electron capture detector is a detector which possesses a special sensi-
tivity for substances that can catch slow electrons. These include halogen organic
compounds. The electron capture detector is much more sensitive for this com-
pound class than, for example, the flame ionization detector. One example of such
a detector is shown in Figure 2.9.
Ni"
Se
anode cathode
+
Fig. 2.9: Scheme of the electron capture detector:
e" - slow electron
P - P - particles (fast electrons)
S e - analyzing substance molecule with caught slow electron
The electron capture detector has a layer of Ni63 as a P-radiation source. The
radioactivity of the radiation source amounts from 10 up to 15 mC (370 to 550
MBq).
First, the carrier gas, which usually contains 90% argon and 10% methane
for this detector type, is ionized by the P-radiation. Slow electrons are formed in
this way, and are caught by the collecting electrode (anode). As long as no com-
pounds arrive into the detector room which can react with the slow electrons, the
electrical current stream remains constant. This gives rise to the zero stream. A
recombination of the slow electrons with the positive feed gas ions is not possible,
since the accumulation energy is equal to the dissociation energy.
If molecules of the component analyzed come into the detector together with
the carrier gas, and these molecules can catch slow electrons, then recombination
of the electrons with these molecules can take place. The molecules catch slow
electrons. Fewer electrons arrive at the collecting electrode. This change of elec-
tron stream forms the signal stream. Negatively charged ions are formed from
molecules of the component analyzed; they can transfer their electrons to the posi-
tive carrier gas ions. The high sensitivity of this detector can be decreased consid-
erably by contaminating the electrodes. This is why cleanliness of the electrodes
must be constantly checked.
The next and last type of detector discussed in this chapter is called the
thermo ionic detector. This detector is also called a phosphorus / nitrogen detector.
Actually, this type of detector is a modified form of the flame ionization detector,
which has its special field of application with organic nitrogen and phosphorus
compounds. The thermo ionic detector is structured in the same way as a flame
ionization detector with only a small rubidium containing glass bead at a platinum
wire as source of alkali located between the burner nozzle and the collecting elec-
trode. The alkali bead always has a negative potential. One example of the detec-
tor constructed for the detection of phosphorus compounds is presented in Figure
2.10.
For the analysis of phosphorus compounds, the flame burns in the same way
as with the flame ionization detector. A nozzle is installed in such a way that elec-
trons formed by burning the organic compounds can flow out from the burner but
not to the collecting electrode. If the nozzle is not grounded as is indicated in Fig-
ure 2.10, electrons which formed during the burning of the hydrocarbons could
pass up to the negatively charged alkali bead. In such a situation, the reactions
cannot occur at the alkali bead. By grounding, the electrons at the nozzle can flow
off. The reactions take place at the alkali bead, and this makes the detector espe-
cially sensitive for phosphorus compounds.
The electrons formed in the reactions on the alkali bead go to the positively
charged collecting electrode and form the signal stream.
88 Chapter 2
synthetic air
electrode
Analyzing compound
and carrier gas
Ill hydrogen
Fig. 2.10: Scheme of the thermo ionic detector for the analysis of phosphor compounds.
The alkali bead consists of rubidium glass, which has semiconductor prop-
erties. If it is cold, it is an insulator, and in the hot state, it has some conductivity.
If there are alkali ions (Me+) in the hot alkali bead, then they react with electrons
into alkali atoms, which surround the alkali bead as a cloud. The alkali atoms can
become thermally innervated and react under light rays into innervated atoms Me .
Radicals (R-), which are formed from the burned component analyzed, react with
innervated alkali atoms by electron transfer from the alkali atom to substance
radical. The innervated alkali atoms change their electrical charge and form posi-
tively charged alkali ions, whereas the sample radicals react to form negatively
charged ions R . The positive alkali ions are caught by the negatively charged
alkali bead again, and react immediately to alkali atoms again. Also, they are
ready for further reactions with the sample radicals again. The anions (negative
charged ions) react to form a neutral final product. Electrons are captured or
caught by the collecting electrode and the detector signal is thereby formed.
The main reactions taking place in the detector with phosphorus compounds
can be shown in the five reactions given below. All these reactions are written
under the assumption that only reactions with the phosphorus oxides such as PO or
PO2 occur in the detector room, since the organic substance is completely burned
in the burner.
O=P + Me* -> O=P- + Me+

O=P=O + Me* -> O=P=O + Me+
O=P + OH* -> HPO2 + e
O=P=O + OH* -> HPO3 + e
HPO3 + H2O -> HPO4
Nitrogen has an odd number of electrons on the outer shell just like phos-
phorus. However, the nitrogen oxide radicals formed similarly to the phosphorus
oxide radicals are cracked very quickly in the hot analyzing chamber in compari-
son to phosphorus oxides. Therefore, the thermo ionic detector can be recon-
structed in such a way that it can be more sensitive for organic nitrogen com-
pounds instead of the phosphorus compounds. A reducing flame condition must be
created for analyzing nitrogen compounds such that instead of nitrogen oxide
radicals, cyanide or cyanate radicals are formed. These react at the alkali bead in a
manner similar to phosphorus oxide radicals.
During the analysis of organic nitrogen compounds, one reduces the hydro-
gen and air supply to the extent that the flame at the burner nozzle is turned out. At
the same time, the bead is electrically heated. The hydrogen is ignited on the
glowing alkali bead and burns in the form of cold plasma around the alkali bead.
An example of the thermo ionic detector reconstructed for organic nitrogen com-
pounds analysis is shown in Figure 2.11.
synthetic air
electrode
Analyzing compound
and carrier gas
I I
hydrogen
Fig. 2.11: Scheme of the thermo ionic detector for the analysis of nitrogen compounds.
The reaction mechanism of the reactions running in the analysis room of the
detector can be presented by the following reactions:
— C— C=N (cracking)
• C=N + Me* -> -C=N +Me +

"C=N+-H ->HCN + e
This type of detector is very specific and can be used in petroleum chemistry
only in specific cases for the analysis of nitrogen or, very rarely, phosphorus com-
pounds. Some of such cases are shown in the last chapter of this book. These are
cases where crude oil is treated or coprocessed with other feeds that contain het-
90 Chapter 2
ero-atoms. An intensive study of this area of crude oil chemistry just started some
decades ago. This is why an intensive study of the chemical mechanism for such
systems is essential.
The gas chromatograph can be used for meaningful analysis only after the
appropriate column and detector have been selected. However, there is still an
important aspect of gas chromatographic analysis that needs to be mentioned. This
involves the introduction of the sample into the column. Sample introduction is
achieved by using special injectors. There are five techniques to introduce sample
into the column.
The first technique is called the filled needle technique. In this technique,
the needle of the injector is fully filled. This is the simplest method but its biggest
disadvantage is that its reproducibility is very bad especially for volatile sub-
stances. Since most crude oil products (such as gasoline) are volatile substances,
this method is not recommended for their analysis.
The next method is called the empty needle technique. In this method, the
sample is sucked out from the needle. The reproducibility of this method is higher
than that by the full needle technique.
Another method is the air bubble technique. In this technique, a little amount
of air is sucked in the injector. The reproducibility of this method is higher than
that of the first two methods.
The next two methods are called the solvent methods. In the first solvent
method, the solvent is sucked into the injector directly after the first air bubble is
sucked in. The reproducibility of this method is the best in comparison to all
methods shown before.
The second solvent method is called the sandwich method. In this technique
the sample is sucked into the injector followed by air bubble and then the solvent.
After the solvent, the sample is sucked in one more time. The reproducibility of
this method is the best. However, its disadvantage is that a high amount of the
sample is introduced in the column. It is not every column that can function with
high sample loading or large amount of the sample.
All these methods are presented in Figure 2.12 for a better understanding of
the techniques they represent.
In addition to the availability of different methods of sample introduction
into the column in gas chromatography, there are two different types of injectors
that can be used to input the sample. These are the splitless injector and the split
injector.
Splitless injectors are used in cases where the column can work well with
high amounts of sample. In this case, the sample is fully injected into the column
and is pushed through the column by carrier gas.
However, for capillary columns, the amount of sample is very important.
This is why there is the second type of injectors: split injectors. With these injec-
tors, it is possible to input just a fraction of the evaporated sample in the column.
The other part of the evaporated sample can be pushed directly over a special split
into the atmosphere. This type of injector is used only for capillary columns.
^ 1
i?v?\>
L
Fig. 2.12: Main techniques for the input of the sample in the column:
1 - full needle technique
2 - empty needle technique
3 - air bubble technique
4 - solvent technique
5 - sandwich technique
When all the preparation work has been completed and sample is introduced
in the column, analysis can begin. The analysis result consists of a chromatogram
with many peaks that correspond to the compounds present in the sample mixture.
At the beginning of this chapter, it was mentioned that the main idea of chroma-
tography is the differential adsorption or absorption of the components in a sample
mixture followed by desorption. However, what is observed in the chromatogram
are wide peaks instead of thin lines that should represent the compounds of the
sample. Why do we have wide peaks? One of the possible theories used to explain
this occurrence is the theory of resistances. The main idea of this theory is pre-
sented in Figure 2.13.
Fig. 2.13: Peak formation.

92 Chapter 2
It is seen from Figure 2.13 that three molecules of the same component
introduced in the column entrance at the same time pass to the end of the column
using different routes. The length differences are specific to the filling or packing
of the column. The peak for the same substance can be wider or thinner depending
only on the type of column filling. The longer it takes the molecules to pass
through the column, the shorter and wider the peak is for this component.
Despite that chromatography is a relatively exact method, it has some draw-
backs such as the presence of anomalies, just like any known analytical method.
The anomalies that arise from chromatography are very difficult to classify. How-
ever, an attempt will be made in the following discussion to highlight the main
types of anomalies in chromatographic analysis.
Spikes can arise due to physical or chemical contamination of the column or
detector. For flame ionization detectors, these contaminants can come from the air.
However, the simplest possible reason for the presence of spikes is the mechanical
vibration of the instrument during analysis. Typical appearance of spikes is shown
in Figure 2.14.
Fig. 2.14: Example of the spikes.
Noise is represented by all fluctuations that arise during the measurement.

There are many reasons for noise. However, the most important ones are the
wrong choice of gas flow rate or leaky connections between different parts of the
instrument. One more problem that arises from the wrong choice of gas flow rate
or bad control of gas flow is peak migration. Evaluation of the results of chroma-
tograms with peak migration is practically impossible. Another reason for peak
migration is poor temperature control in the column.
Some chromatograms may contain what is referred to as ghost peaks. These
correspond to the components that are actually not present in the sample. The most
common reason for ghost peaks is that the column was contaminated before the
analysis started. This shows the importance of a cleanliness check before the
analysis.
The last interesting problem arises from the wrong choice of column for
analysis of the sample. It is called shared peak. An example of a shared peak is
shown in figure 2.15.
There are a lot more anomalies that can arise in the use of chromatographic
methods. It is not possible to discuss all of them in this short chapter. This chapter
has been restricted to providing the reader highlights of the scientific and technical
fundamentals of gas chromatography. However, a list of recommended literature

has been provided at the end of this chapter for readers who are interested in pur-
suing the subject further.
Fig. 2.15: An example of shared peaks.
It was shown earlier that there are many reasons for the occurrence of
anomalies during gas chromatographic analysis. This is why everything needed for
analysis must be chosen very accurately. After the gas chromatograph for analyz-
ing a specific sample is selected, the next step is to select the carrier gas. Every gas
can theoretically be used as a carrier gas. However, there are some important char-
acteristics that every carrier gas must have. The carrier gas must be chemically and
physically inert to the filling or packing of the column. Also, it must not react with
the compounds in the sample mixture. The last property of a good carrier gas is its
level of purity. It is very important for the analysis that the carrier gas introduces
no impurities into the gas chromatograph. Even very small amounts of foreign
substances in the carrier gas can falsify the results very seriously. Presently, three
gases are the most popular carrier gases used in gas chromatography. These are
hydrogen, nitrogen and helium.
The use of hydrogen as a carrier gas has only one disadvantage. The high
tendency of hydrogen to diffuse and permeate through the smallest splits in the
connections between parts of the gas chromatograph makes hydrogen relatively
dangerous. If the leakage in the system is inside the thermostat, it can result in
explosion because of the presence of a dangerous mixture of hydrogen and air.
This is why the use of hydrogen as the carrier gas must be related to ensuring that
there are no leaks between connections of parts in the gas chromatograph. Conse-
quently, a very thorough leak check is a must before the start of every experiment.
The next possible carrier gas is nitrogen. This is probably the cheapest and
least dangerous carrier gas. However, it must be noted that nitrogen is also used as
an inert atmosphere in many experiments in crude oil chemistry. This means that
gas coming to the analysis contains nitrogen. The analysis of nitrogen in the gas
mixture would be impossible if the carrier gas is the same as one of the compo-
nents of the sample mixture.
Nowadays, helium is the most popular carrier gas used in gas chromatogra-
phy. The use of helium as inert atmosphere in thermal or catalytic treatment ex-
94 Chapter 2
periments is, in most cases, not rational because of the high cost of this gas in
comparison to nitrogen. The formation of helium from crude oil or crude oil prod-
ucts is absolutely impossible too. This is why helium can be recommended as the
optimal carrier gas for analyzing crude oil fractions or gases formed during the
thermal or catalytic treatment of crude oil.
One important factor influencing the resolution of the column is the velocity
of the gas flow. This value must be chosen optimally for every column or column
system used in gas chromatography. Too high a velocity of the gas in the column
can lead to very bad separation of the compounds in the column. This means that it
is possible for many components of the mixture to exit the column at the same
time, thus making the evaluation of the results cumbersome and prone with error
or practically impossible. Too low a velocity of the gas in the column leads to the
formation of adsorption-desorption equilibrium, resulting in a poor resolution of
the column as well. The gas flow in any modern gas chromatograph is usually
controlled by a special controller called the mass flow controller. These devices
are very exact. However, they need to be calibrated. There are three most popular
devices to measure the gas flow and to calibrate the mass flow controller.
Soap bubble measurement is carried out in the device shown in Figure 2.16.
soap bubble
gas
elastic bubble with
soap solution
Fig. 2.16: Gas flow measurement device using the soap bubble principle.
The principle of this gas flow measurement device is simple. A push on the
gummy bubble leads to soap bubble rising in the measurement cylinder. The gas
flow pressures up the soap bubble. The time it takes for the bubble to pass through
a defined volume of the measurement cylinder is measured by a timer. The princi-
ple of soap bubble gas flow measurement is the direct measurement of the average
gas flow velocity. The advantage of this device is that a very accurate average
value for the gas flow velocity can be calculated from the measurements. This
device is the most accurate for the calibration of gas flow controllers. And this
method is strongly recommended to measure the gas flow in the case when there
are no full automatic calibration devices for the gas flow controllers.
The next method uses the principle of floatation of a heavy sphere in the gas
flow. The scheme of the device using such a principle is shown in Figure 2.17.
The flowing gas makes the sphere float. The higher the velocity of the gas flow,
the higher the sphere is pushed. This device must be accurately calibrated before
use. The biggest disadvantage of this device is that the gas flow velocity defined
by this method at every moment is instantaneous velocity. All mass flow control-
lers, including the most modern ones, have certain errors, and gas flow can be
permanently changed within the limits of these errors. It is difficult to determine
gas flow velocity with controllers with relatively large errors. However, this de-
vice can be recommended for calibrating modern mass flow controllers with low
errors.
T
gas
Fig. 2.17: Gas flow measurement device using principle of heavy sphere floatation.
The last device for measuring gas flow and for calibrating mass flow con-
trollers that is discussed in this chapter is called the capillary gas flow measurer.
The principle of this device is used in many modern automatic calibration devices
for mass flow controllers. The scheme of such a device is shown in Figure 2.18.
The main idea of this method is that the pressure needed to force the gas
through the capillary is directly proportional to the gas velocity. The pressure can
be measured by the method shown in Figure 2.18, by measuring the height of the
liquid, which can be mercury or water or, for special cases, highly viscous liquids.
However, this measurement is also possible by using other pressure measuring
devices as well.
After all the preparations and experiment are over comes to the time to
evaluate the experimental data. There are many methods to evaluate the gas chro-
matogram. Usually, every gas chromatograph is calibrated for each specific
method.
The most popular and simplest method is called the peak height method.
The method is applicable only if the chromatographic column is not overloaded. In
96 Chapter 2
this case, a linear dependence between peak height and the quantity of the respec-
tive component in the sample exists for constant analysis conditions. If the maxi-
mum possible load of the column is exceeded, the separation ability of the column
decreases. As a result, a linear dependence between peak height and the quantity
of the respective component is not presented any more. Deviations from linearity
can occur with column that is not overloaded as well, if the compounds of the
mixture have very different physicochemical properties.
capillary
pressure measurement
Fig. 2.18: Gas flow measurement device using principle of the capillary pressure.
This method of evaluation of gas chromatograms is suitable especially for

recurring analyses with an internal standard. For example, the gas formed by
thermal treatment of crude oil can be permanently analyzed by gas chromatogra-
phy. However, it must be ensured that the analysis parameters are kept constant
for all the analyses. In this case, all influences that affect the height of the peak are
excluded.
The next evaluation method is based on the multiplication of the peak height
by general retention time. This evaluating method is preferred for use with chro-
matographs that have detectors that are sensitive to a change in the carrier gas flow
velocity. With these detectors, the magnitude of the signal increases with increas-
ing gas flow velocity, in which case the total retention time of the compound is
reduced. On the other hand, the result of the multiplication of the peak height and
total retention time of the compounds remains approximately constant.
Temperature changes, which may occur if the temperature-programmed
mode of the analysis is used, cannot be corrected by this method. This is why this
evaluation method is applicable only for isothermally executed chromatography.
The main advantages of the method are as follows:
The analysis values obtained are very similar to the real concentrations of the
compounds even in chromatograms with numerous peaks.
Bad separated peaks can be evaluated, if the peak height and the total reten-
tion time are measurable.
Thin peaks, which can arise frequently with capillary column chromatogra-
phy, are easy to evaluate.
With wide peaks, the peak height can be relatively accurately assessed.
The error obtained with this evaluation method is due mainly to the fact that
the total retention time of the individual components depends linearly on the peak
height only approximately. The amount of the component in the sample is often
judged as too small for thin peaks and too high for wide peaks. The linear depend-
ence is well suitable for homologous classes of compounds in the sample mixture
analyzed.
The next evaluating method is based on the multiplication of the peak height
by the width of the peak at half its height. With this evaluation method, the total
area of a peak, which corresponds to a Gauss distribution curve, is determined as
an area of an equal-leg triangle. The height of the triangle is equal to the maximum
of the detector signal. The area of the triangle is the result of the multiplication of
the triangle height with its width at the half height.
This method used frequently in comparison to all the other methods dis-
cussed previously because it is less sensitive to the influence of temperature,
change of pressure and carrier gas flow.
However, this method can be used only for the evaluation of chromatograms
with symmetric peaks. The advantage of the method is that the chromatogram can
have symmetric peaks even if, like in some cases, the column of the gas chro-
matograph is overloaded.
The last method of evaluation of a gas chromatogram is called the mix
method. With this method the compounds analyzed must be known. The pure
compound that is to be evaluated is mixed with the sample mixture. Analysis of
the sample mixture is performed twice in this method. One is in the absence of the
pure compound whereas the second is a mixture with the pure compound. Evalu-
ating the concentration of the component proceeds with a comparison of the peaks
from both chromatograms. The advantage of this method is that this method is
very accurate. On the other hand, the disadvantage is that the evaluation of the
pure compounds is needed, and also there is the need of at least two chroma-
tograms, which makes this method longer and more expensive than every other
method discussed before.
More information about gas chromatography can be found in references 54-
59 at the end of this chapter.
2.1.2 High Performance Liquid Chromatography
High performance liquid chromatography is also called high-pressure liquid

chromatography. This method of chromatography was developed in the 1960s
98 Chapter 2
from column chromatography. The main difference between this method and gas
chromatography is that non-evaporating samples can be analyzed by this method.
This difference is also the biggest advantage of high performance liquid chroma-
tography. The reason is that some crude oils contain over 80% of heavy fractions
that cannot be evaporated at temperatures below 350°C. Such materials cannot be
analyzed by gas chromatography but are readily analyzed by high performance
liquid chromatography. The samples being analyzed by high performance liquid
chromatography must have the important property that they are soluble in the
solvent selected as the mobile phase for the chromatographic analysis.
It was mentioned earlier that high-pressure liquid chromatography was de-
veloped based on column chromatography. This method is very rarely used nowa-
days and only for special cases. However, this method is good to demonstrate the
functioning principle of modern high-performance liquid chromatographs. The
scheme of a column chromatograph is presented in Figure 2.19.
solvent
Fig. 2.19: Scheme of the classical column chromatography.
The setup shown in Figure 2.19 is the simplest example of liquid chroma-
tography. The column diameter for such chromatographs usually varies from 1 to
5 cm. The column is filled with fine adsorbent particles. The top of the column is
open for the entire duration of the experiment. The sample dissolved in a small
amount of the solvent is introduced first in the column. After this, the solvent is
introduced slowly but continuously into the column and separated compounds or
fractions of compounds exit the column at the bottom. In this method, the solvent
flows only under the influence of gravitational force. The disadvantage of this
method is that a single experiment can take hours for the separation and the col-
umn packing must be prepared specifically for each experiment. The compounds
exiting the column are often detected by optical methods. In the example shown in
Figure 2.19, the sample was separated into three compounds or three fractions.
These fractions can be detected by the difference in color. The need of a long time
for every experiment is the reason why column chromatography was developed
into high performance chromatography. However, the old classical column chro-
matography can still be found in many research petroleum laboratories even now.
This method is used for the separation of heavy oil fractions into fractions of com-
pound groups, as for example paraffinic, naphthenic and aromatic compounds.
Fractionating by this method can be carried out to obtain more fractions of petro-
leum than was shown in this example. However, the analysis of individual com-
pounds of crude oil is impossible by this method. But some individual compounds
of heavy petroleum fractions can be analyzed by high performance liquid chro-
matography.
The main principles in the high-performance liquid chromatography tech-
nique are the same as for the gas chromatography technique. However, the mobile
phase in the high-pressure liquid chromatography is a liquid solvent, which is
forced through the column under high pressure. This is why no gas tank but a
solvent reservoir is used in liquid chromatography. The new accessories needed in
liquid chromatography are high-pressure pumps. Depending on the chromato-
graph, these pumps can achieve pressures up to 500 bar. One example of a high-
pressure liquid chromatograph is shown in Figure 2.20.
high pressure pump

manometer ^detector
' r
column /
data evaluating
^. . thermostat -,.
solvent reservoir collector
Fig. 2.20: Scheme of the high performance chromatograph.
Some notable differences between the high-pressure liquid chromatograph

and the gas chromatograph can be seen clearly in Figure 2.20. For example, the
columns used for liquid chromatography are shorter than the columns used for gas
chromatography. The packing material used for the columns in liquid chromatog-
100 Chapter 2
raphy is usually very fine: 3-50 um. The biggest advantage of high-pressure liquid
chromatography in comparison to the classical column liquid chromatography is
that a very precise analysis can be performed in a very short time.
As in the case for gas chromatography, the column and detector are the heart
of the high performance liquid chromatograph. There are many types of columns
used for liquid chromatography. These are classified as guard, derivatizing, capil-
lary, fast, and preparatory columns.
The guard columns are placed anterior to the main separating column. This
serves to protect the separation column from impurities or contaminants, which
could be present in the sample. Usually, these columns have a length of 5 cm, and
the diameter of the guard column must be the same as that of the separating col-
umn. There are many types of guard columns designed for the different purposes.
For example, there are guard columns to filter the particulates from the sample or
separate ions that can influence the analysis. The use of these columns by petro-
leum chemists is important, because the composition of petroleum is so compli-
cated that it is very possible for the sample to contain insoluble particulates, which
can damage the separation column and make it unusable. These columns must be
changed frequently in order to optimize their protective function. The size of the
packing varies with the type of protection needed.
Derivatizing columns serve to chemically change the initial compounds. The
use of these columns can give accurate data for the sample in the case where the
analysis of the initial mixture resulted in doubtful data.
Capillary columns are used in the current high performance chromato-
graphs. The functioning principle of this type of column is the same as was de-
scribed for gas chromatography. There are three types of capillary columns used in
liquid chromatography: open tubular, partially packed, and tightly packed. The
advantage of these columns is that they allow us to work with very small amounts
of sample.
Fast columns are designed specifically to decrease the time needed for
analysis. Usually, these columns are shorter than the usual separating columns; the
packing material of such columns consists of a very fine material with particle size
of about 3 jam. The advantages of using these columns are decreased analysis time
and increased sensitivity of the column.
Preparatory columns serve to prepare the bulk sample for laboratory pre-
paratory applications or further analysis. A preparatory column usually has a large
diameter designed to facilitate large volume injections into the chromatograph.
There are more types of columns used in liquid chromatography designed
for special cases or for specific chromatographs. However, the most important part
of the column is the parking of the column. The high-pressure liquid chromatogra-
phy can be classified as adsorption, distribution, gel permeation, affinity and ion
pair chromatography according to the type of fillings or packing.
The principle of adsorption chromatography is the same as for gas chroma-
tography, which was discussed in some detail in a previous section. Another de-
scription is not very essential at this point. The most popular filling or packing for
adsorption liquid chromatography is silica gel. There is only one difference as

compared to the case for gas chromatography. This concerns the particle size of
the packing material. Usually, high performance liquid chromatography makes use
of packing material with the smaller particles sizes.
The main principle of distribution liquid chromatography is the same as for
gas chromatography as well. However, the stationary phase for liquid chromatog-
raphy is in most cases a non-polar liquid. Non-polar stationary phase is called
reverse-phase and the method used for chromatography with such a stationary
phase is called reverse phase technique.
Gel permeation chromatography is distinct from every other type of chro-
matography. There is no physical interaction between the sample and the station-
ary phase in this method. The stationary phase in gel permeation chromatography
is usually a highly porous material with particle sizes in the range from 6 um to 10
jam. Separation proceeds according the sizes of the components in the sample.
This means that the sample is separated into fractions with regard to the molecule
size or molecular weight of the components.
The main principle of the gel permeation chromatography is as simple as
shown in Figure 2.21.
Fig. 2.21: Principle of gel permeation chromatography.
During gel permeation chromatography, the solution flows through the

chromatographic column filled with porous packing material. The velocity distri-
bution of the solution and its components depends on the pathway through which
the components or particles of the solution pass. The particles that move around
the packing particles are the fastest because this is the shortest possible route.
Components or particles that flow through the pores of the porous packing mate-
rial are slower since they also have a longer distance to cover (through the pores).
Small molecules shown in the example in Figure 2.21 as black circles are
distributed in the whole volume of the column and their average moving velocity
is very slow. Bigger molecules, gray circles, do not go through the smallest pores
in the same way as the lightest compounds of the sample. Instead, they are only
able to pass through the bigger pores. As such, the flow velocity of this set of
molecules is higher than that for small molecules. The biggest molecules, white
circles, cannot pass through the pores of the column packing and move through
102 Chapter 2
the column around the particles with the fastest possible velocity. As a result, the
biggest molecules exit the column first, and the smallest ones come out last.
The gel permeation chromatographic column is characterized by the mini-
mum and maximum sizes or molecular weights of molecules that can be analyzed
by that column. This is because all the molecules with molecular weight higher
than maximum analyzable molecular weight cannot pass through the pore and all
move with the same velocity. The result is that they cannot be separated. The same
problem arises with the molecules smaller than the smallest analyzable molecule.
They all pass through the smallest pores of the packing material with the same
velocity.
The affinity chromatography is a chromatographic method which uses spe-
cific interactions between the sample molecules and the stationary phase. Affinity
means the tendency of the molecules to react with each other. The first component
in this case is the one bounded to the stationary phase. The other component is the
component in the sample. This is adsorbed from the solution onto the ligand. The
components, which have no affinity for the ligand, are transported by the mobile
phase through the column. In order to desorb the analyzed component molecules
from the stationary phase, a solvent with greater affinity for the ligand in compari-
son with the stationary phase is introduced into the column. In some cases, it is
sufficient to change the pH value of the solution to desorb the components being
analyzed from the stationary phase.
The last type of column used in liquid chromatography is the column used
for ion pair chromatography. In this method an ionic solvent, which has the oppo-
site charge to the sample compound, is used as the mobile phase. The use of such a
mobile phase leads to the formation of an ion pair, which is the material eventually
analyzed in this method. Samples which cannot be analyzed by adsorption or
distribution chromatography because of the high electrical charge of ions, should
be analyzed by this method.
An important part of the high performance liquid chromatograph is the de-
tector. The main tasks of the detector for this type of chromatography are the same
as for gas chromatography. However, the detectors used in liquid chromatography
are different from those used in gas chromatography, because of the necessity to
perform analysis with liquid samples.
One of the most popular detectors in high-pressure chromatography is the
ultra violet (UV) detector. Compounds that can absorb ultra violet light, are de-
tected using this detector. The UV detectors have a relatively large dynamic range.
The great advantage of UV detectors is that they are only minimally sensitive to
temperature changes during analysis. An example of the UV detector is shown in
Figure 2.22.
After leaving the column, the mobile phase flows through a quartz cell,
which acts as the analysis cell. The analysis cell and a reference cell (which con-
tains the mobile phase) are irradiated with the same source of UV light. A low-
pressure mercury lamp or deuterium lamp is usually used as the UV light source.
The UV light intensity is measured with photoresistors. Before starting the real
analysis, it is necessary to carry out an electronic calibration of the photoresistors

of the analysis and reference cell. The pure mobile phase flows thorough both cells
during the calibration. The mobile phase should be optically permeable with the
wavelength generated by the UV light source. During the real analysis, a compo-
nent of the sample mixture eluting from the column into the detector absorbs the
UV light, and changes the resistance of the photoresistor. The difference in resis-
tances between the photoresistors of the analysis and reference cell produces a
detector signal, which is sent to the evaluating computer.
solved
compo-
nent
photo
resistor
Source of
reference
UV light lens UV filter
mobile cell
phase
Fig. 2.22: UV detector.
Photodiode array detectors are a class of UV detectors. The main difference

of this type of detectors from the classical UV detector is that photodiode array
detectors scan the entire spectra from UV all the way to visible light. This detector
type is very beneficial in the sense that with well-designed software, it is possible
to select the best wavelength for every component in the sample analyzed. As
such, the analysis can be carried out more accurately.
The next detector often used in liquid chromatography is the refractive index
detector. This detector uses the property of the sample molecules to bend or refract
light. The disadvantage of these detectors in comparison to UV detectors is that
refractive index detectors are less sensitive than the UV detectors. Refractive in-
dex depends strongly on the temperature of the sample. This is why the refractive
index detector must be well thermally insulated. A scheme of the analysis cell of
the refractive index detector is shown in Figure 2.23.
The refractive index detector contains two cells: one analysis cell and one
reference cell just as UV detectors. Light from the lamp goes through the analysis
and reference cell at the same time. The pure mobile phase flows thorough the
104 Chapter 2
reference cell and the sample dissolved in the mobile phase flows through the
analysis cell. If the light in the analysis cell is bent differently compared to the
light in the reference cell, the detector produces a signal, which is sent to the
evaluating computer.
prism photo-
rejistor
lamp f VS^/v
/
lens
i - *' -~'\
solved X
substance
Fig. 2.23: Analysis cell of refractive index detector.
The most modern but not especially popular refractive index detectors are
those that use a laser as the light source. The use of lasers brings many advantages.
First of all, the resolution of a laser refractive index detector is much higher than
by using classical detectors. However, the price for such detectors is relatively
high and it is used only for special analytical cases.
The next type of detector used in liquid chromatography is fluorescence
detectors. These detectors use the ability of components in the sample analyzed to
absorb and re-emit light at defined wavelengths. Each compound has a character-
istic fluorescence. Ultra violet lamps are usually used as the light source in such
detectors. The technique of fluorescence detectors is different as compared to the
usual detectors. They contain only one flow cell. The light goes through this cell.
The photoresistor measures the intensity of the light passing through the cell and
the monochromator measures the re-emitted light, i.e. fluorescence.
Electrochemical detectors are a very interesting example of detectors used in
liquid chromatography. These detectors can detect only compounds that are able
to react by oxidation or reduction reactions. Usually, this technique functions by
measuring the gain or loss of electrons from the flowing sample as it passes be-
tween two electrodes maintained at an electrical potential difference.
The last two popular detectors in liquid chromatography are nuclear mag-
netic resonance and mass spectrometers. The mass spectrometer as a detector was
described in the section in this chapter on gas chromatography. On the other hand,
the principles of the nuclear magnetic resonance are described in chapter 5 of this
book because of its important in asphaltene chemistry.
It was indicated that most detectors used in high-pressure liquid chromatog-

raphy are optical detectors that use ultra violet, visible or laser light sources. It
stands to reason that the solvents that can be used as the mobile phase for liquid
chromatography must have special properties. The most important properties of
the mobile phase for high performance liquid chromatography are:
Transparency for ultra violet light.
The boiling point of the mobile phase must be between 40°C and 100°C. The
limit of 100° is important only for distillation of the solvent after the analysis.
The limit of 40°C is important for the analysis, because a lighter solvent can
by evaporated in the pump leading to the formation of vapor bubbles in the
pumps.
Miscibility is important in case a mixture of many solvents is used as the
mobile phase for the elution.
Polarity indication of which compounds can be used in a given mobile phase.
Mobile phase must be free of all solved gases. Nitrogen and oxygen have
good solubilities in most solvents used in liquid chromatography. There are
three methods to degas the mobile phase: to degas the mobile phase by he-
lium stream, to degas the mobile phase by treatment of the solvent with ultra-
sound and to degas the mobile phase by distillation.
In degassing the solvent with a helium stream, helium gas is bubbled con-
tinuously through the solvent until all the solved gases are removed. In this
method, it is important that the mobile phase does not come in contact with air
during the degassing. This is the simplest and most popular method.
In degassing with ultrasound, a glass with solvent is placed in the bath with
the source of ultrasound. During the treatment with ultrasound, bubbles of the gas
removed can be seen issuing from the solvent. The ultrasound treatment must be
carried out until no more gas bubbles are issuing from the solvent.
The last method, the distillation method, is the most effective but also the
most complicated in executing. In this method, the solvent is evaporated in an
inert atmosphere and then condensed again. It is important to ensure that no gas is
dissolved in the solvent during the condensation. For this reason, the distillation
unit must be evacuated before degassing and then filled with a gas that is insoluble
in the mobile phase.
Elution with the selected and degassed solvent as mobile phase can be done
in two different methods. The first method is simplest, but cannot be used for all
samples especially those containing complicated mixtures of compounds in crude
oil fractions. As such, this method is only rarely used. It is called isocratic elution.
In this method, the same composition of mobile phase is used during the entire
analysis time. The main property of samples that can be analyzed by this method
is that the components in the sample have approximately the same polarity. The
second elution method is called gradient elution. This method can be used for
complicated mixtures of compounds which have different polarities and which
106 Chapter 2
cannot be analyzed by only one solvent. However, this method demands the use of
special pumps to support the stepwise mixing of the various solvents.
From the last shown elution method, it is clear that the pump is a very im-
portant accessory for high-pressure liquid chromatography. There are three main
types of pumps used in modern chromatographs:
membrane pumps
reciprocating piston pumps
syringe type pumps
constant pressure pumps
In the membrane pump, a disk brings the piston to a reciprocating move-

ment. Special hydraulic oil passes the impulse from the piston onto the membrane.
The functioning principle of the membrane pump is presented in Figure 2.24.
3 mobile / phase
mobile phase form container
to column
Fig. 2.24: Functioning principle of the membrane pump.
On the back stroke, the separation column valve is closed, and the piston
pulls in solvent from the mobile phase container. On the forward stroke, the pump
pushes the solvent out to the column from the hydraulic chamber. A wide range of
flow rates can be attained by altering the stroke frequency. As shown, the func-
tioning principle of the membrane pump is relatively simple. However, there is the
disadvantage that the pumping of the mobile phase is only done discontinuously or
intermittently. A schematic showing the pulsating pumping of the solvent by a
membrane pump is illustrated in Figure 2.25.
The problem with discontinuous pumping can easily be solved by using two
pumps functioning at the same time such that if one pump sucks in the solvent
another pump presses the solvent to the column (out of phase with each other).
This type of pump system is significantly smoother because one pump is filling
while the other is in the delivery cycle. Such connections of two membrane pumps
are relatively often used in liquid chromatography.
Fig. 2.25: Example of discontinuous pumping.
The working principle of the reciprocating piston pump is similar to that of

the membrane pump. The difference is that the reciprocating piston pump has no
membrane. The solvent is pumped directly by the piston. This is why the piston of
such pumps must be made from special chemically and mechanically stable mate-
rials. A reciprocating piston pump consists of a small motor driven piston, which
moves rapidly back and forth in a hydraulic chamber that may vary from 35-400
pi in volume. The reciprocating piston pumps have the same disadvantage as the
membrane pumps and the same principle is used to prevent intermittent pumping.
Dual and triple head pumps are used to make the pumping continuous, and this
arrangement consists of identical piston-chamber units which operate at 180 or
120 degrees out of phase.
Syringe type pumps are usually used for chromatography with capillary
columns because this pump can deliver a finite volume of mobile phase before it is
refilled. These pumps have a volume of hydraulic chamber between 250 to 500
ml.
The mobile phase is pressed by gas continuously at constant pressure into
the column by constant pressure pumps. The big advantages of this type of pump
are really the constant pressure and the continuous pumping of the mobile phase.
Pumps are the last important part of high performance liquid chromatogra-
phy. In principle, if the column, detector and pump are appropriately selected and
installed in the chromatograph, analysis can commence. The chromatograms of
the high-pressure liquid chromatography are similar to the chromatograms of gas
chromatography and can be evaluated by using of the same techniques, which
were described in detail in the section on gas chromatography.
More about high performance liquid chromatography can be found in refer-
ences 60-62 at the end of this chapter.
2.1.3 Thin Layer Chromatography
Thin layer chromatography, often called film-development chromatography,

is the simplest, quickest to perform, and cheapest type of chromatography, in
comparison to gas chromatography and liquid chromatography. However, this
method can only be used for qualitative analysis. This type of chromatography is
very popular with crude oil geologists, because it can be used conveniently for
108 Chapter 2
field investigations. The method does not need any special or complicated acces-
sories. Thin layer chromatography is also used in the laboratories by crude oil
chemists. Usually, this is only for quick screening research of many samples. This
method is recommended for field analysis of organic substances in ground sam-
ples during crude oil prospecting.
Thin layer chromatography differs from all other types of chromatography
discussed before by the simplicity of the technique used. Thin layer chromato-
graph has a stationary phase and a mobile phase just like every other chroma-
tographic method. However, the stationary phase for thin layer chromatography is
not located in the column as in gas or liquid chromatography. Instead, it is fixed on
a glass, aluminum or plastic plate as a thin layer.
Thin layer chromatography is very similar to paper chromatography. Thin
layer chromatography has a wide variety of possibilities depending on the choice
of the stationary phase. Adsorption, distribution and ion chromatography can be
carried out in thin layer chromatography.
The preparation of the experiment for thin layer chromatography begins
with the preparation of the analysis chamber. The analysis chamber for this chro-
matographic method is a glass filled with a small amount of the mobile phase, and
a filter paper is introduced. The analysis chamber is prepared by dipping the filter
paper in the mobile phase for circa half hour. This time is needed for the chamber
to reach vapor formation in equilibrium with the mobile phase. The fact that the
mobile phase vapor in the analysis chamber is saturated and in equilibrium with
the mobile phase liquid is especially important for executing the analysis, because
it has a great influence on the velocity of the mobile phase during the analysis. An
example of the analysis chamber that has been prepared correctly is shown in
Figure 2.26.
3 - 5 mm
Fig. 2.26: Analysis chamber for thin layer chromatography.
The humidity that comes with the mobile phase filter paper ensures the
evenness of the vapor pressure in the analysis chamber and acts as an accelerator
for the achievement of saturated vapor with the mobile phase. The filter paper can
also act as an indicator; if the solvent front reaches the upper limit of the filter
paper, it is usually postulated that the analysis chamber is ready for the com-
mencement of the analysis.
It is important to select the appropriate mobile phase for the analysis (i.e. for
the separation of components in the sample). The right choice of the mobile phase
has a great influence on the resolution during analysis. The most popular solvents
used as mobile phase for thin layer chromatography are n-hexane, tetrachloro
methane, benzene, dichloro methane, trichloro methane, acetic acid ethyl ether,
dioxane, acetone, i-butanol, i-propanol, ethanol and methanol. Despite a good
choice of solvent for the mobile phase, it is often required to use a mixture of
solvents, because no single solvent has all the properties needed. There is a simple
method used to select the most appropriate solvent for thin layer chromatography.
It is called the spot test. This method is presented in Figure 2.27.
Fig. 2.27: Spot test.

In the spot test, the sample is spotted on the chosen thin layer plate and a
drop of the mobile phase tested is dropped in the center of the sample spot. The
solved sample begins distribution over the thin layer. The best solvent is chosen
based on evaluation of the spot formed after the radial distribution of the sample
has stopped. Solvent 1 in Figure 2.27 is the most appropriate solvent and has the
best resolution in comparison to solvents used on spots 2 and 3. Solvent 2 moves
the compounds of the sample too fast and the spot is clearly overdeveloped. In
contrast to the second solvent, the solvent used on spot 3 moves the compounds of
the sample too slowly. The spot is therefore clearly underdeveloped.
As the next step, the sample must be prepared for the analysis. The sample is
usually dissolved in a volatile solvent. The concentration of the sample in the
solvent can vary form 1 to 10% or higher for special cases. The solved sample is
introduced with a pipette on a spot (i.e. spotted) at a point approximately 15 mm
from the bottom part of the thin layer. The right choice of the material for the thin
layer is important for the analysis. The most popular thin layer material is silica
gel. It can be covered with various highly viscous liquids to enable distribution
chromatography. The principle in the choice of thin film material is the same as
the choice of the packing material for columns used in gas or high-pressure liquid
chromatography. However, the thin layer can be impregnated for special purposes
with various solids, which can react with the sample. Phosphates and borates are
popular for use as impregnated solids.
Analysis can start after the right mobile phase and thin film plate have been
chosen. Before the thin layer plate is placed in the analyzing chamber, the excess
110 Chapter 2
solvent used in solving the sample must be removed slowly to avoid touching the
thin layer plate. The analysis chamber is then placed on a sturdy table to prevent
vibrations during analysis. This is important for accurate analysis results. Then,
the thin layer plate is placed in the analysis card in the analysis chamber. The
analysis chamber with the thin film plate is shown in Figure 2.28.
thin film plate
3-5 mm
Fig. 2.28: Working analysis chamber.
The development of the sample begins due to the capillary action of the
mobile phase on the thin layer plate, after the thin film plate has been placed in the
analysis chamber. Usually, the time needed for the analysis varies from twenty to
sixty minutes. However, the analysis proceeds until the solvent reaches the upper
limit of the thin film. In the case where appropriate resolution is achieved earlier
than when the solvent front reaches the upper limit of the plate, analysis can be
stopped early to save time.
Evaluation of the analysis results proceeds by measurement of the differ-
ences in the distance from the start line until the analyzed spot and front of the
mobile phase, as presented in Figure 2.29.
After measuring the distances di and 62, a special factor Rf is calculated
according to the formula (2.1) (see Figure 2.29). The Rf values depend on the
solid absorbent, the compound polarity, and the eluting solvent polarity. The
factor Rf for constant analysis conditions is a characteristic property of the sub-
stance. If the thin-film card is calibrated for permanently analyzing similar sam-
ples, the substance analyzed can be detected just by the Rf value.
Rf = d 2 / d , (2.1)
The evaluation can also be carried out visually as shown in Figure 2.29 or
by transferring the data into digital form by a scanner and evaluating the results in
a computer. Fluorescence active impregnation can be used in the case of analysis
of almost transparent samples. The spots of such samples are hard to see in the
visible spectra of light. However such substances can be easily detected by view-
ing the thin film with UV light and observing the fluorescence picture.
front of the mobile phase

A i.
d, analyzed spot
i'femin1! M
iL
d2
^•^^
start line
y^r'O---.^.*»». rf**
Fig. 2.29: Evaluating the results of the thin film chromatography.
The evaluation of some samples is sometimes not possible after the first
development. This can be caused by a wrong choice of solvent or by special prop-
erties of the sample. However, it is possible to develop the thin film one or more
additional times. There are two methods for developing the thin-film card more
than one time: one-dimensional and two-dimensional development. The thin-film
card must be dried so that there are no residues of the mobile phase on the thin
film before the development in the second step.
After drying, the thin film is placed in the analysis chamber in the same way
as was done for the first analysis. The analysis can be repeated until an appropriate
resolution of the card is achieved. The Rf value for one-dimensional analysis is
calculated by the formula in equation (2.2), with regard to the number of times (n)
it was repeated.
"Rf =!-(!-R f ) n (2.2)
Two-dimensional developing of the thin film cards is needed only in special

cases. In this method the card is placed in the analyzing chamber the second time
but turned by an angle of 90° in comparison to the first analysis. The advantage of
this method is that the spots are located diagonally on the thin film plate and are
easy to evaluate. Usually in this method, two different solvents are used. However,
this method is relatively complicated in comparison to the one-dimensional devel-
oping and it is recommended only for the analysis of samples which cannot be
separated by only one solvent.
112 Chapter 2
The qualitative evaluation of the spots discussed above is possible only in

some cases. Often, a more accurate analysis of the separated substances is needed.
For this purpose, the spot of the sample analyzed must be accurately removed
from the plate. Then, the substance is extracted from parts of the thin film by using
appropriate solvents and analyzed by spectral or other methods, which will enable
the identification of the structure of the compound.
It was already mentioned that thin film chromatography is used firstly as a
qualitative analysis method. There is no accurate quantitative analysis that is pos-
sible by thin film chromatography. However, there is an empirical formula, equa-
tion (2.3), which allows the approximate calculation of the weight of the substance
(W) from the spot area (A). This method is very inaccurate and can be used only
for gross estimation.
A"2 =logW (2.3)
The thin film chromatography is the last chromatographic method discussed

in this chapter. More about this method can be found in references 63-66 at the
end of part I of this book.
2.2 SPECTROSCOPIC METHODS
2.2.1 Infrared Spectroscopy
Infrared red spectroscopy is based on the ability of the substances to absorb

light of a given wavelength. Infrared spectroscopy is today one of the most im-
portant spectral analytical methods in the crude oil chemistry, because of its high
information content and the variety of possibilities for sample preparation.
The direct analysis of the structure of sample components without calibra-
tion with reference substances is impossible. However, defined chemical groups in
the sample absorb infrared light in defined areas of the spectra. The direct predic-
tion of the structure of the sample or components, in this case, is possible with the
use of special empirical tables for infrared spectroscopy.
In order to predict the structure of the sample analyzed, it is important to
understand the principle of analysis. Infrared spectroscopy is based on the meas-
urement of the absorbed infrared light by the sample analyzed.
When a beam of infrared light of intensity I0 is passed through a sample, it
can either be absorbed or transmitted, depending upon its frequency and the
structure of the molecules. The final intensity I of the infrared light that passes
through the sample can be calculated by the Lambert-Beer law (2.4) which is
applicable to all types of electromagnetic radiation.
I = I0-10-E-cd (2.4)
Where c is the concentration of the component analyzed in the sample and d

is the thickness of the sample layer. The factor E is a specific characteristic value
of the component analyzed. This coefficient however depends weakly on the con-
centration of the component (c) in the sample. Therefore, it is important to cali-
brate the spectrometer for all the possible concentrations of the component ana-
lyzed before the analysis.
The infrared light, a type of electromagnetic radiation, is energy and hence
when a molecule absorbs radiation it gains energy and undergoes a quantum tran-
sition from one energy state (Einitiai) to another (Ermai). The frequency of the ab-
sorbed radiation is related to the energy of the transition by Planck's law, which is
presented by equation (2.5).
- Einitial = E = (2.5)
Thus, if a transition exists which is related to the frequency of the incident

radiation by Planck's constant (h = 6.626-10"34), then the radiation can be absorbed.
Conversely, if the frequency (v) does not satisfy Planck's expression, then the
radiation will be transmitted. A plot of the frequency of the incident radiation
against some measure of the percent radiation absorbed by the sample provides the
absorption spectrum of the compound or component. The absorption spectrum is
characteristic for the compound and this spectrum is often called the fingerprint of
the compound. Infrared spectroscopy is based on the measurement of the absorp-
tion of electromagnetic radiation that arises from the altering of the vibration level
of the component's molecule. An example of the adsorption and transmission of
the infrared radiation is shown in Figure 2.30.
energy molecule
quanta of light
absorption
transmission
Fig. 2.30: Absorption of infrared radiation.
As stated above, the absorption of infrared radiation takes place by altering

the vibration level or movement energy of the component's molecule. There are
several types of motion that a molecule may undergo. First, the molecule may
move through space in some arbitrary direction and with a particular velocity. This
type of motion is called translational motion, and the translational kinetic energy
114 Chapter 2
of the molecule is associated with it. The energy of the translational motion can be
calculated by equation (2.6).
E = mv2/2 (2.6)
where v is the velocity of the center of mass of the molecule
m is the mass of the molecule
The velocity with which a molecule translates may be resolved into compo-
nents along each of the three axes of the Cartesian coordinate system, as shown in
Figure 2.31.
Fig. 2.31: Translational motion of a molecule.
If the molecule motion is observed as is shown in Figure 2.31, then the energy of
the translational motion is calculated by equation (2.7).
E = mv2/2 = mvx2/2 + mv y 2 /2 + mvz2/2 (2.7)

where vx is the x-component of velocity
vy is the y-component of velocity
vz is the z-component of velocity
m is the mass of the molecule
This equation shows that the total translational energy of the molecule can
be made up of three parts, each of which represents the kinetic energy of the mole-
cule along one of the reference directions. Any translation of the molecule may be
considered to arise from the vector sum of its motions along the three axes. Thus,
the kinetic energy may always be broken up into the sum of three contributions,
one arising from motion along the x axis, one from motion along the y axis, and
one from motion along the z axis. It means that the molecule has three transla-
tional degrees of freedom, one corresponding to each axis.
The next type of motion of the molecule is the rotational motion. The mole-
cule can rotate about some internal axis. This axis may be resolved into compo-
nents of the x-, y-, and z-axes of the coordinate system, so that any rotation of the
molecule may be resolved into three mutually perpendicular components. The
energy of the rotational motion can be calculated by an analogous method to the

transformational motion. This is given by equation (2.8).
E = IxCGx2/2 + IycOy2/2 + Izo^2/2 (2.8)

where Ix is the moment of inertia about the x axis
Iy is the moment of inertia about the y axis
I2 is the moment of inertia about the z axis
(Ox is angular velocity about the x axis
(Oy is angular velocity about the y axis
C0z is angular velocity about the z axis
The final type of the motion of molecules is called vibrational motion. This
type of molecule motion is very important in infrared spectroscopy since the ab-
sorption of infrared radiation by this motion forms the fingerprint of the sample
analyzed. There are many types of vibrational motions, and these are shown be-
low. It is important to know the right number of degrees of freedom for the vibra-
tional motion of the sample molecule. This can be calculated by using the follow-
ing general equation (2.9).
Z=3-N-6 (2.9)
where N is number of centers of mass in the molecule
As was shown for translational and rotational motions, there are three de-
grees of freedom for vibrational motion for every center of mass in the molecule.
The number six on the right hand side term of equation (2.9) arises from the total
number of degrees of freedom for translational and rotational motion, which do
not belong to vibrational motion. It should be known that for linear molecules,
there are only two degrees of freedom for rotational motion. This is why for this
case there is a special equation for the calculation of the degrees of freedom for
vibrational motion (2.10).
Z = 3-N-5 (2.10)
The number of the degrees of freedom for the vibrational motion (Z) calcu-
lated by the equations (2.9) and (2.10) is called degrees of freedom of normal
vibrations.
For example one three-atom linear molecule has four degrees of freedom for
normal vibrations (2.11):
Z = 3-3-5 = 4 (2.11)
This means that four types of vibrational motion are possible for such a molecule.
The first motion is the symmetric vibration of the atoms in the direction of the
center of mass as shown in Figure 2.32. Since this vibration is symmetric, it does
116 Chapter 2
not lead to the altering of the dipole moment of the molecule. This means that
electromagnetic radiation cannot be absorbed by this type of motion. Such vibra-
tions are called infrared inactive vibrations
Fig. 2.32: Symmetric vibrational motion of the linear molecule.
Both end atoms move asymmetric to the central atom during the second type
of vibrational movement. Such a movement leads to the altering of the dipole
moment of the molecule, and this type of vibration is active for infrared analysis.
An example of this movement is shown in Figure 2.33.
Fig. 2.33: Asymmetric vibrational motion of the linear molecule.
The next two types of vibrational movement are called deformation vibra-
tion. The end atoms move vertical to the central atom. The first type of vibrational
movement is shown in Figure 2.34.
Fig. 2.34: First type ofdeformational vibrational motion of the linear molecule.
This type of motion leads to the altering of the dipole moment of the mole-
cule as well as to an asymmetric vibrational motion. Thus, this vibration is active
for infrared analysis.
The last type of vibration for the molecule shown is principally the same as
the third type of motion. However, the vibration proceeds horizontally to the cen-
tral atom. This type of motion is shown in Figure 2.35
Fig. 2.35: Second type of deformational vibrational motion of the linear molecule.
This type of motion is shown as an extra motion because the motion pro-
ceeds in different coordinates in comparison to the first shown deformational
motion. However, the vibration frequency and the altering of the dipole moment
by these last two vibrations are the same. Such type of motions, where the vibra-
tion frequency of two or more motion types is the same, is called downgraded
motion. A special value, called degradation number, is given for characterization
of such motions. This value shows the number of molecules that have the same
vibration frequencies. For example, the degradation number for the linear mole-
cule shown above is two.
A three-atom nonlinear molecule is shown as the next example. Nonlinear
molecules are more popular in petroleum chemistry, because most organic sub-
stance are nonlinear. The number of degrees of freedom of normal vibrations for
three-atom nonlinear molecule is calculated using equation (2.12).
Z=3-3-6= 3 (2.12)
This means that three vibrational motions are possible for this type of molecule.
The end molecules vibrate symmetric to the central atom by the first possi-
ble motion. In opposition to the linear molecule this motion by a nonlinear mole-
cule leads to the altering of the dipole moment. This means that this vibration is
active for infrared analysis. An example of such a vibration is shown in Figure
2.36.
Fig. 2.36: Symmetric vibrational motion of the nonlinear molecule.
As an analogue to the linear molecule the second vibrational motion for the
non linear molecule is asymmetric vibration. This type of motion is shown in
Figure 2.37.
118 Chapter 2
O O
Fig. 2.37: Asymmetric vibrational motion of the nonlinear molecule.
The asymmetric vibration leads to the altering of the dipole moment as well,
and as a result this motion is active for infrared analysis.
The last possible vibrational motion is the deformational motion. This type
of vibration is presented in Figure 2.38.
Fig. 2.38: Deformational vibrational motion of the nonlinear molecule.
From Figure 2.38, it is easy to see that for nonlinear molecule, only the type
of deformational motion shown is possible, because the deformational motional in
different coordinates other than the ones shown in figure 2.38 are analogues to the
rotational motion of the molecule. Thus, a three-atom nonlinear molecule has only
three degrees of freedom of normal vibrations whereas a three-atom linear mole-
cule has four degrees of freedom of normal vibrations.
There are many types of vibrational motion of atoms in molecules. However
the intention of this chapter is to show the fundamentals of infrared spectroscopy.
In the list of references at the end of this chapter, many books and articles are
recommended for a more detailed study of this type of analysis.
Each of the vibrational motions of a molecule occurs with a certain fre-
quency that is a characteristic value for the groups in the molecule analyzed. The
energy involved in a particular vibration is characterized by the amplitude of vi-
bration, so that the higher the vibrational energy, the larger the amplitude of the
motion. According to the results of quantum mechanics, only certain vibrational
energies are allowed for the molecule, and thus only certain amplitudes are al-
lowed. Associated with each of the vibrational motions of the molecule, there is a
series of energy levels. The molecule may change from one energy level to a
higher one by absorption of a quantum of electromagnetic radiation. This can be
calculated by equation (2.5). In undergoing such an energy of transition, the mole-
cule gains vibrational energy, and this is represented by an increase in the ampli-
tude of vibration. The frequency of light required to cause an energy transition for
a particular vibration is equal to the frequency of that vibration, so that it is possi-

ble to measure the vibrational frequencies by measuring the frequencies of light
which are absorbed by the molecule. So, infrared spectroscopy deals with energy
transitions between vibrational energy levels in molecules, and is therefore also
called vibrational spectroscopy. An infrared spectrum is generally displayed as a
plot of the energy of the infrared radiation.
Infrared spectra are measured by special instruments called infrared spec-
trometers. These instruments measure the differences in the intensity of the infra-
red light of a certain wavelength that penetrates into the sample and goes out from
the sample. The most important parts of the infrared spectrometer are:
light source, which produces an intensive infrared radiation
monochromator
detector
A schematic of the infrared spectrometer is presented in Figure 2.39.
n
Fig. 2.39: Infrared spectrometer:
1 - infrared light source
2 - sample chamber
3 - monochromator
4 - detector
5 - amplifier
6 - evaluating computer
The most frequently used source of infrared light for infrared spectrometers
is so called the Nernst stick. This stick is about two to four centimeters long and
one to three millimeters thick, and is made from zirconium oxide with additions of
yttrium oxide and oxides of other metals. This mixture of oxides has a negative
temperature coefficient of electrical resistance. This means that its electrical con-
ductivity increases with an increase in temperature. At room temperature, the
Nernst stick is a non-conductor. Thus, an auxiliary heating is necessary for igni-
tion of the Nernst stick. Even if the Nernst stick is red-hot, it can be heated further
by electricity. The normal operating temperature of this infrared light source is
approximately 1900 K.
120 Chapter 2
Because of its high operating temperature and the energy distribution in the
middle infrared spectrum area the Nernst stick is the most used infrared radiation
source. However, it is mechanically very sensitive and can be deformed by heat-
ing. This can change the optical characteristics of the spectrophotometer.
The next source of infrared light that is relatively often used is silicon car-
bide stick, called the glowbar. The glowbar is usually 6-8 mm in diameter and is
thicker than the Nernst stick. This gives the high mechanical firmness to the
glowbar. Due to its electrical conductivity at room temperature, the glowbar can
be ignited directly by electricity. The disadvantage of the glowbar is its low oper-
ating temperature (approximately 1500 K). The lower intensity of infrared radia-
tion produced by the glowbar as compared with the Nernst stick is a result of the
low operating temperature.
Ceramic infrared light sources are used in some spectrometers. A ceramic
stick is heated by a metallic conductor, made from platinum or a platinum alloy,
and wound around the ceramic stick. The conductor is surrounded with a sintered
layer of aluminum, thorium oxide, zirconium silicate or a similar material. The
heating conductors made from chrome nickel or tungsten wire are preferably suit-
able for short-wave spectral analysis.
The next important part of an infrared spectrometer is the sample chamber.
The sample chamber is used for placing the cuvette that contains the sample or for
placing any other accessory that contains the sample. The sample chamber is in-
stalled between the infrared light source and the monochromator.
It is very important to make the right choice of the cuvette material for liq-
uid and gas samples. This material must be transparent to the infrared light. So-
dium chloride is the most often used material for the cuvettes and the optics of the
infrared spectrometer. Other material such as special types of glass, quartz, alu-
minum oxide, calcium chloride, potassium bromide and so on are also used for
special purposes.
Another component part of the infrared spectrometer is the monochromator.
This is the most important accessory of infrared spectrometer. The function of the
monochromator is to split polychromic infrared light into many monochromic
light wavelengths. However, this splitting does not go strictly into monochromic
wavelengths, but the infrared radiation is split into very narrow wavelength inter-
vals. The splitting in strictly monochromatic light, as it is for radiation of individ-
ual emitted spectral lines by vacuum mercury lamp or radiation emitted by a laser,
cannot be achieved by a monochromator. The grated part of the infrared radiation
is lost due to splitting of the infrared light by the monochromator. This leads to
the requirement of a high sensitivity of the detectors used in infrared spectrome-
ters.
Modern monochromators consist of a rift system, the optics and the infrared
radiation splitting system, which is usually presented by prism or diffraction grid.
The following two types of monochromators are most popular in modern infrared
spectrometers:
Littrow monochromator
Ebert monochromator
The Littrow monochromator has a prism as a splitting system while the Ebert
monochromator has a diffraction grid for the same purpose. The principles of the
schemes of both monochromators are presented in Figures 2.40 and 2.41, respec-
tively.
output rift
parabolic mirror
input si
mirror
Fig. 2.40: Littrow monochromator.
The diverged infrared radiation from the input slit is directed to a parabolic
mirror and returned toward the splitting system (prism or gird). Depending on the
type of optical principle, the parallel reflected infrared light passes through the
prism or split by the diffraction gird. It is then reflected back by a plane mirror at
the same parabolic reflector for the Littrow monochromator or at a second para-
bolic reflector for the Ebert monochromator. After this, the monochromic infrared
radiation is directed to the output slit.
The most important part of the monochromator is the infrared radiation
splitting system. One of the most popular splitting systems is the prism. The
function of a prism is based on having various refraction angles for radiation with
various wavelengths. The function principle of a prism is shown in Figure 2.42.
122 Chapter 2
parabolic mirror
input slit
parabolic mirror
output slit
Fig. 2.41: Ebert monochromator.
monochromic
polychromic kht
light
wavelength
Fig. 2.42: Functioning principle of the prism.
The material of the prism is important in infrared spectroscopy, since it must

be transparent to infrared light. The material most frequently used for analysis in
the middle wavelength region is sodium chloride. Prism materials for the analysis
of short and long wave infrared light are usually potassium bromide, cesium bro-
mide, and cesium iodide.
The prism is made from a faultlessly grown single crystal. The most impor-
tant values for the resolution ability of the prism are the base size and the refrac-
tive index. Both must be selected to be as large as possible in order to get a good
resolution. The refraction angles depend upon the value of the refraction index
and usually vary from 35° to 72°. The base length is limited by technical reasons.
It varies depending on the type of spectrometer from 60 mm to 100 mm.
Almost all old commercial spectrometers had only prisms in the monochro-
mators. Refraction grids are relatively popular in modern infrared spectrometers.
Some of the unfavorable properties of the prism materials that relate to hygro-
scopy, reflection, light absorption and the need to change the prism in order to
analyze in different wavelength areas could be prevented by using refraction
grids. At the same time, a substantially better and constant resolution for wide
wavelength areas can be achieved by using refraction grids.
Furrows scratched in an even glass or metal surface or a thin wire is applied
to produce refraction grids. Infrared light is split into individual wavelengths by
these furrows or wire.
The next component part in the infrared spectrometer is the detector. The
most important types of detectors used in infrared spectroscopy are the thermal
detectors. In this type of detector, radiation energy is first absorbed and then con-
verted into heat energy. The actual measured value is an electrical voltage, which
is produced or changed by the heating. Despite their higher sensitivity, photo
electric detectors have a lower popularity due to the limits they have of the ana-
lyzable wavelength area.
The detectors used in infrared spectroscopy are generally delicate but small
in order to make the thermal capacity of the detector as small as possible. This
leads to a very high mechanical sensitivity of the detector. Since thermal detectors
are influenced not only by the radiation energy that has to be measured, but also
by changes in the temperature of environment, the measured radiation is modu-
lated. This means that it is modulated by periodic interruption of the light beam
usually with the frequency 13 Hz. Infrared radiation, in such a situation, produces
an alternating voltage. This is then magnified in an alternating voltage amplifier
and then sent to the evaluating computer.
The most important characteristics of a detector are its sensitivity and the
relation of measuring signal to noise level.
The last component part of an infrared spectrometer other than the evaluat-
ing computer is the amplifier. The purpose of the amplifier is to amplify the signal
coming from the detector to enable the computer to evaluate the signals.
The first step in carrying out an infrared spectroscopic analysis is the prepa-
ration of the sample. The types of samples analyzed by infrared spectroscopy in
crude oil chemistry are solid or liquid samples.
A simple method to prepare a solid sample is called the potassium bromide
pressing technique. The prerequisite for this method is that the particles of the
solid sample are smaller than the wavelength, which must be measured. Larger
particles lead to the unwanted Christiansen effect.
In the potassium bromide pressing technique, a mixture consisting of ap-
proximately 300 mg potassium bromide and 1 mg of sample is put into a press
under vacuum. The sample/potassium bromide mixture is pressed to tablets by a
pressure of about twelve tons for a duration of two minutes. The material under
124 Chapter 2
this high pressure has the characteristic of a cold fluid. It becomes viscous and
encloses the sample particles completely.
The next method of the preparation of solid samples is called the film tech-
nique. In this method, the sample is solved in an appropriate solvent and smeared
on a glass plate in the form of a thin film.
The preparation of solid sample by the film technique is the same as the
preparation of liquid samples. In the two cases, there are many special require-
ments for the solvent used. The most important of them are as follows:
solvent must be chemically inert to the sample analyzed
solvent must be chemically and physically inert to the material of the
cuvette
solvent must be as transparent as possible with regard to infrared radia-
tion
For the analysis of liquid samples, the cuvette material must chosen so that
the sample is physically and chemically inert to this material.
The result of an infrared spectroscopy is the spectrogram or spectrum. A
typical example of the infrared spectrogram (i.e. spectrum) is shown in Figure
2.43.
Usually, the infrared spectrum is drawn in terms of wave number / absorp-
tion or wave number / transmittance coordinates as shown in Figure 2.43. The
wave number is a characteristic value of the electromagnetic radiation, and can be
calculated by equation (2. 13).
(2.13)
where f is frequency of the light wave

c is velocity of light
The prime value characterizing the interaction of infrared radiation with

sample analyzed is called transmittance (Tr). It is defined as relation between
intensity of the infrared radiation at the input in the sample and the intensity of the
output radiation from the sample. Transmittance is calculated by equation (2.14):
Tr = I / I 0 (2.14)
where I0 is input intensity of infrared radiation

I is output intensity of infrared radiation
The concentration of a component in the sample analyzed can be calculated

by the Lambert-Beer law, which is shown in equation (2.4). In order to evaluate
quantitatively an infrared spectrum, equation (2.4) should be rewritten as equation
(2.15).
absorption [%] transmittance [%]

0 100
100.
4400 3900 3400 2900 2400 1900 1400 900 400
1
wave number [cm" ]
Fig. 2.43: Infrared spectrum:
1 - basis line
2 - background absorption
3 - absorption peak
4 - shoulder
5 - analysis start point
6 - spikes
= -E-C-d (2.15)
where E is extinction coefficient, which is characteristic for substance

C is concentration of the substance in the sample
d is thickness of sample layer in sample chamber
It can be seen that the concentration of the substance in the sample can be
calculated by comparing the input and output intensity of the infrared radiation.
However, the input intensity is actually not a constant value. It varies depending
on the frequency or wave number of infrared radiation. This means that the initial
intensity of infrared radiation must be measured for every frequency before ana-
lyzing the sample. However, this problem is solved in modern infrared spec-
trometers by using a double beam technique. In this method, the beam of infrared
126 Chapter 2
radiation from the radiation source is split into two beams by a system of reflec-
tors. One beam passes through the sample and is then analyzed. The second beam
is directed directly to the monochromator and then analyzed.
Every infrared spectrum obtained from analysis has six elements as shown
in Figure 2.43. First is the baseline. The baseline shows the transmittance line of
the spectrometer if there is no sample in the sample chamber. Usually, this line is
not registered during analysis as it is a characteristic for the instrument and not of
the sample. Number 2 in figure 2.43 represents the background absorption area.
This area shows the absorbed infrared radiation in the absence of the sample in the
sample chamber. A peak of a typical chemical group in the sample is shown with
in number 3. This peak is characteristic of every chemical group or substance, and
they give the information for quantitative analysis of the sample. The peaks of
some chemical groups or substances present in the infrared spectrum may not be
well defined. This may lead to the formation of a shoulder, which is shown as
number 4 in Figure 2.43. The shoulder represents poorly resolved peaks. However,
shoulders are not the only cause of inaccuracies in infrared spectroscopy. Spikes
are shown in Figure 2.43 in number 6. Spikes are caused by undesired fluctuations
in the voltage. They lead to the formation of false signals from the detector or
amplifier.
Quantitative evaluation of the infrared spectrum is done with regard to the
empiric tables or digital libraries. So this can be estimated quickly. For example, if
sample contains aromatic groups, information can be collected in the infrared
spectrum by looking for the peaks typical of the aromatic carbon.
The most important samples for analysis by infrared spectroscopy for crude
oil chemists are organic substances. For organic molecules, the infrared spectrum
can be divided into three important regions. First is the absorption of infrared
radiation within the wave number range of 4000 and 1300 cm"1 which is caused by
functional groups and different bond types. Second is the absorption between 1300
and 909 cm"1 that is typical for more complex interactions in the molecules. And
last is the absorption between 909 and 650 cm"1, which is usually associated with
the presence of aromatic compounds in the sample.
Infrared spectroscopy is used for the analysis of almost all the fractions and
products of crude oil. However, in the last century, a very interesting purpose of
the infrared spectroscopy has been developed. It is the dynamic monitoring of the
changes in the structure of lubricating oils as it undergoes degradation. Many
processes such as oxidation or polycondensation in oils can be studied by infrared
spectroscopy.
More detailed information on infrared spectroscopy can be found in refer-
ences 67-70 at the end of this chapter.
2.2.2 Raman Spectroscopy
Raman spectroscopy gives results similar to those from infrared spectros-

copy. This is why Raman spectroscopy is often used together with infrared spec-
troscopy in order to receive additional information about the sample analyzed. The
motions of the molecule involved in the analysis of the sample in Raman spectros-
copy are similar to those by infrared spectroscopy. These include rotational and
vibrational motions. However, the physical causes of the resulting spectrum are
different.
The Raman effect used in Raman spectroscopy arises from the interactions
of monochromatic radiation with the shell atom. In contrast to infrared spectros-
copy, these interactions are independent of the wavelength of the light used for the
analysis.
For Raman spectroscopy, an intensive monochromatic laser radiation is
directed towards the sample. A major part (99.99 %) of the laser light passes
through the sample while a very small part is strewn from the substance in all
directions. This is the elastic scattering of the light quanta at the molecules other-
wise called Raleigh scattering. This has the same frequency as the laser used. A
much smaller part of the used radiation (approximately 10~6 %) is scattered non-
elastically. This is called Raman scattering. This light scattering contains informa-
tion about the sample molecule. It is also called Raman fingerprint of the sub-
stance. The scattering process in Raman spectroscopy can be explained by the
scheme shown in Figure 2.44.
EL
E,
1 2 3
Fig. 2.44: Light dispersion process in Raman spectroscopy.

128 Chapter 2
In step one shown in Figure 2.44, the molecule is brought by laser light from
the base energy level E, to the higher energy level E2. The higher energy level is
an unstable state for the molecule. The molecule migrates quickly from the higher
energy level to the end energy level. This can proceed in two different ways. The
first way is given as picture 2 in Figure 2.44 which indicates that light quanta is
being emitted. The energy of the resulting light quanta can be calculated by equa-
tion (2.16). This type of scattering is called stokes scattering.
EL = E,-E 3 (2.16)
The second possibility of the light quanta emission is shown as picture 3 in

Figure 2.44. In this case, part of the vibrational energy of the molecule is trans-
mitted to the emitted light quanta. Radiation with a shorter wavelength is emitted
in this case. The energy of the light quanta emitted in this case can be calculated
by equation (2.17). This type of light scattering is called anti-stokes scattering.
EL=E]+E3 (2.17)
The results of Raman spectroscopy are usually given as a difference in the

wave numbers between the used laser and the scattered light, whereby the wave
number for the laser (in presentation of the results) is set to zero, and this point on
the spectrogram is called the Raman shift. In this case, stokes scattering is marked
by a plus sign and anti-stokes scattering is by a negative sign. The results of the
Raman spectroscopy of the molecule presented in Figure 2.44 could look as shown
in Figure 2.45.
Stokes scattering is usually more intensive than anti-stokes scattering if the
analysis is carried out at room temperature. However, polar groups as -O-H or -S
-H are strongly active for infrared spectroscopy whereas non-polar groups and
compounds such as -C=C- are strongly active for Raman spectroscopy. There is a
simple rule for linear symmetric molecules; infrared active motions cannot be
Raman active at the same time. Hence, Raman spectroscopy complements infrared
spectroscopy in giving additional information for clarification of the molecular
structure. Accordingly, both the methods used on a sample can exactly clarify
whether a molecule has linear or nonlinear structure.
Raman spectrometers are used to carry out Raman spectroscopic analysis.
The scheme of a Raman spectrometer defers from that of an infrared spectrometer.
First of all is the sequence of light source and detector. These are not arranged in a
parallel format as was done in infrared spectrometers. Instead the light source is
built perpendicular to the detector. The scheme of the Raman spectrometer is
shown in Figure 2.46.
intensity [%]
100^
400 300 200 100 0 -100 -200 -300 -400

stokes scattering Raman shift anti-stokes scattering
Fig. 2.45: Raman spectrogram.
Most of the component parts used in Raman spectroscopy such as the

monochromator and sample chamber have the same functioning principle as in
infrared spectrometers. All these were described in detail in section 2.2.1.
Samples of all physical states can be analyzed by Raman spectroscopy.
However, analysis of gas samples is difficult because of the low density of the
sample.
In order to implement Raman spectroscopy, a reference sample is firstly
installed in the sample chamber in moveable cuvette. Sulfur is usually used as the
reference sample because of its high Raman activity. The reference sample is
moved in the sample chamber until an optimum position is found. The optimum
position is marked by maximum scattered radiation recorded by the detector. After
the optimum position has been found, the reference sample is replaced with actual,
sample. It is important to note that the geometrical characteristics of the actual
sample must be the same as those of the reference sample. Calibration with regard
to wavelength of the light used for the analysis depends on the actual sample and
Raman spectrometer used. Different methods can be found in handbooks for a
given Raman spectrometer.
130 Chapter 2
4
I
Fig. 2.46: Raman spectrometer:

1 - laser, light source
2 - transmitted light
3 - sample chamber
4 - scattered light
5 - monochromator
6 - detector
The Raman spectroscopy can be used for analyzing temperature sensitive

and color samples. However, following problems could arise:
heating up of the sample by laser radiation
fluorescence of the sample
All these problems can be prevented as much as possible by using modern

lasers as light source for Raman spectroscopy, for example, Neodymium-YAG
laser. The intensity of the light can often be around 0.5 Watts. This laser device
is installed in most modern Raman spectrometers.
Qualitative evaluation of the Raman spectrograms proceeds in the same way
as was shown for infrared spectroscopy. On the other hand, quantitative evaluation
in Raman spectroscopy is executed by using calibration curves or tables that are
usually supplied with a given spectrometer in the form of software for the evalu-
ating computer.
There are many possibilities for the use of Raman spectroscopy by crude oil
chemists. Many references, shown at the end of this chapter, describe many differ-
ent investigated areas of the use of Raman spectroscopy. It was shown earlier that
heavy fractions constitute the majority of the problems that can be investigated by
Raman spectroscopy. At the time most of these problems were solved, an inter-
esting use of Raman spectroscopy was the determination of impurities in lubricat-
ing oil. In this analysis, Raman spectroscopy can give more interesting and more
complete results than infrared spectroscopy.
More information on this topic can be found in references 71-75 at the end
of this chapter.
2.2.3 Colorimetry and Photometry
Colorimetry and photometry are the next spectral optical analysis methods.
Both the methods measure absorbed light as was shown for infrared spectroscopy.
However, for both these analyses, light with shorter wavelength is used. Color-
imetry uses light with wavelength of only the visible spectral area and photometry
uses the visible light, ultraviolet, and in some case, infrared area. A comparison of
the different spectral areas is shown in Figure 2.47.
Photometry is similar to infrared spectroscopy; a method for measuring
the light transmitting ability of a solution in order to determine the concentration
of a light absorbing material present in the solution. Crude oil chemists gener-
ally use spectrometry in three ways:
to determine the concentration of a substance which is not undergoing a
chemical change in the spectrophotometer cell
to measure the rate of change in the concentration of a substance which
is participating in a chemical reaction
to determine the absorption spectrum of a substance
1 5 6
in-12 irr10 in"8 1(T6 10"4 10'2 10'6
Wavelength, [m]
Fig. 2.47: Spectrum of electromagnetic radiation:
1 - cosmic rays
2 - gamma rays
3 - X-rays
4 - ultraviolet rays
5 - visible light
6 - infrared rays
7 - microwaves
8 - radio waves
9 - electric power
The visible region of the electromagnetic spectrum consists of electromag-

netic radiation with wavelengths from approximately 400 to 700 nm. It was shown
in Figure 2.47 that this region is very narrow in comparison to all other spectral
132 Chapter 2
areas. The short wavelength cut off is due to absorption by the lens of the eye
whereas the long wavelength cut off is due to the decrease in sensitivity of the
photoreceptors in the retina for longer wavelengths. Light at wavelengths longer
than 700 nm can be seen if the light source is intense. Every color of the visible
spectrum corresponds to a definite wavelength. The distribution of colors in the
visible spectrum is shown in Figure 2.48.
violet blue green- blue- green yellow- yellow orange red

xblue green/ . greer
/^
400 440 480490500 560 580595605 750

Wavelength, [nm]
Fig. 2.48: Colors of visible spectrum.
The motions that are analyzed by colorimetry and photometry are no longer
of rotational or vibrational nature as was shown for all previous spectral analyses.
The motions analyzed at the visible and ultraviolet spectral regions are specific for
each atom or chemical group. In order to understand the nature of these motions, it
is important to understand the structure of the atom.
There are lots of models on the structure of the atom that can help us to
understand the nature of matter. These models are simplified representations of
real atoms. The models can be made by atomic physics to be more accurate but
this makes the model more complicated. Today, it is possible to describe atoms
very accurately by using quantum mechanics. However, the question that cannot
be answered accurately is whether the true model has been found or not.
Which of the models is the best depends on what it is used to describe. For
example, there are applications in which it is sufficient to regard the atoms as
small particles.
The name "atom" derives from the Greek word "atomos" meaning indivisi-
ble or unbreakable. The use of the name "atom" was initiated by Demokrit, a
Greek philosopher, in the fifth century before Christ. Demokrit supported his
theories about atoms through hypotheses that he did not then prove by experi-
ments. His theory of the atomic structure of matter could not become generally
accepted against the competing concept of a continuous universe.
The first experimental verification of the existence of atoms came from
chemists and was based on the clarification of the chemical nature of matter. In the
nineteenth century, English chemist John Dalton formulated a law that now bears
his name; according to this law, all chemical compounds are always formed by a
fixed relation of the individual materials of the compound. Thus, the idea of atom
atom came about that chemical compounds could be formed by the reactions of
individual atoms.
The idea of indivisibility or indestructibility of the atom was disproved by
Joseph J. Thomson, when he discovered the cathode radiation in 1897. He was
able to prove that this radiation consisted of charged particles that originated from
atoms. This meant that atoms could be cracked with the formation of the charged
particles, which are now called electrons.
In 1911, a new idea about atomic structure was described by Ernest Ruther-
ford. In his famous scattering experiments, Ernest Rutherford discovered that
atoms consisted of a major part that contained nothing and that almost all the mass
of the atom was concentrated in a very small core.
Two years later, Danish scientist, Niels Bohr, described a new model of
atomic structure. Nowadays, the Bohr atom model is the most popular model used
by scientists. The electrons fly in the Bohr atom model on circular paths around
the core. The binding energy that holds the electrons in the atom is of an electrical
nature. Opposite charges attract each other, whereas like charges repel or push off
each other. The binding energy between two charged particles becomes smaller
with increasing distance from each other. Since the atom core is positively charged
while electrons are negatively charged, the electrons are attracted to the core. The
planets of our solar system have a similar attraction by the sun. As the planets are
held by the sun in their circular paths, so also are the electrons held by the core in
their circular paths.
In addition to the fact that the electrons fly on circular paths, Bohr also pos-
tulated that only certain orbits are permitted. Transitions between these orbits
occurred immediately or spontaneously without the possibility to take any inter-
mediate positions. It is impossible to understand these postulates with the laws of
classical physics. Only quantum mechanics could explain the second Bohr postu-
lation.
The Bohr atom model was an attempt to understand the presence of individ-
ual lines in the optical spectra of atoms. Since the atomic nucleus attracts the elec-
trons, energy is needed to keep the electrons away from the core. Exactly as the
case with the planet orbits, this energy arises from the rotating motion of the elec-
trons around the core. The further the electron is from the core, the more is the
energy stored by the electron. If an electron moves from a higher orbit to a lower
orbit, then it loses energy, which is radiated in form of a light quantum. An elec-
tron can move to a higher orbit only by the supply of energy. This means by ab-
sorption of a light quantum.
The fact that only light quanta with special energy levels can cause transi-
tions of electrons between orbits, shows that only certain orbits exist in atoms. The
energy levels of the light quanta absorbed can be explained as the energy differ-
ence between different orbits.
In a more exact observation of the optical spectra of different atoms, it was
detected that many of the spectral lines are additionally split up. This means that
the Bohr electron orbits differ somewhat by some type of electron transition that
134 Chapter 2
needs only a small energy for transition. Sommerfeld postulated that there are not
only circular orbits, but also elliptical orbits, which contain approximately the
same energy level as circular orbits. Figure 2.49 shows the Bohr-Sommerfeld
model of a hydrogen atom.
Fig. 2.49: Bohr atom model:

1 - Bohr orbit
2 - Sommerfeld orbit
The instruments which analyze a substance by virtue of the electron shells of

the atoms in the visible area of the spectra are called colorimeters. These instru-
ments measure the difference in the color intensity of a reference solution with a
defined concentration of the component analyzed and the color intensity of the
sample solution.
Colorimeters are constructed based on the principle of continuous ray. That
means the light ray passes continuously from the light source to the detector. The
main elements of every colorimeter are a light source, two cuvettes, a detector and
a monitoring device. One cuvette is used for the reference solution and has the
same thickness of the sample room. Usually, the thickness of the sample room and
consequently the thickness of the analyzing sample can be varied in the analyzing
cuvette. The principle scheme of the colorimeter is shown in Figure 2.50.
Fig. 2.50: Colorimeter:

1 - light source
2 - sample cuvette
3 - reference cuvette
4 - detector
5 - monitoring device
However, colorimeters are very rare to see in crude oil chemical laborato-
ries, because as was indicated earlier, almost all the important functions of the
colorimeter can be reproduced by modern photometers.
There are two important types of photometers: the one-ray photometer and
the two-ray photometer. The construction of the one-ray photometer is very simi-
lar to the colorimeter. The scheme of the one-ray photometer is presented in Fig-
ure 2.51.
Fig. 2.51: One-ray photometer:

1 - light source
2 - monochromator
3 - sample cuvette
4 - detector
Usually, the one-ray photometer has no dynamic change possibility for the
wavelength of the light used for the analysis whereas such a possibility exists for
the two-ray photometers. The main difference between the two-ray photometer
and the one-ray photometer is that the two-ray photometer has two cuvettes in the
sample chamber. These are the sample cuvette and the reference cuvette. The
reference cuvette is filled with pure solvent while the sample cuvette is filled up
with a solution of the sample analyzed in the solvent. The results of photometry
are evaluated by comparison of the intensity of light that passes through the sam-
ple solution and the pure solvent. The scheme of the two-ray photometer is pre-
sented in Figure 2.52.
1 2 3 4 5
Fig. 2.52: Two-ray photometer:

1 - light source
2 - monochromator
3 - sample chamber with reference cuvette and sample cuvette
4 - detector
136 Chapter 2
All the component parts used in photometers have the same working princi-
ple as those already described in other spectrometers, for example, the infrared
spectrometer. The prism and refraction grids are used as monochromators. The
detector is usually made of different types of photoresistors depending on the
instrument type.
Photometry and colorimetry are used by crude oil chemists to determine the
content of different metals and heteroatomic compounds in crude oil and petro-
chemical products. Many references on photometry and colorimetry are given at
the end of this chapter. Many authors have described the successful analysis of
different metals in motor fuels by photometric and colorimetric methods. The
composition of additives used during fuel production can be characterized by
photometric and colorimetric methods because very many additives contain met-
als. It is not only fuels that can be characterized by photometry and colorimetry.
Lubricants, which contain metals as an important component, can be successfully
determined by these methods. These methods can quickly give qualitative infor-
mation on heavy metals and heteroatomic compounds such as oxygen and sulfur
in crude oil. More on this topic can be found in references 76 and 77 at the end of
this chapter.
2.2.4 Fluorescence and Phosphorescence Spectroscopy
Fluorescence and phosphorescence spectroscopy are generally referred to as

fluoremetry. Fluoremetry uses the ability of some materials to emit light at a cer-
tain wavelength. The emitted spectrum by the substance is characteristic for that
specific material alone. The fluorescence effect arises if an electron is moved from
an orbit with a higher energy level to an orbit with a lower energy level. Primarily,
the electron in the atom under analysis is transmitted from the base orbit to the
orbit with a higher energy level by a monochromic light from the light source of
the fluoremeter.
The instruments used for the fluoremetry, fluoremeters, are very similar to
the ones used for Raman spectroscopy. However, the light spectral region used in
fluoremetry is usually the ultraviolet or the visible spectral area. The principle of
the scheme of a fluoremeter is shown in Figure 2.53.
Pulsing lasers are used in most modern flourometers as the light source.
Measurement with such lasers makes it possible to measure the florescence effect
right after the prime transmission of the electron from the base to the higher en-
ergy level and during the transmission. The main advantage of using such a laser
is the possibility to measure the time delay effect of phosphorescence. Measuring
this effect is impossible by application of a continuous light source.
The most popular light sources in modern fluoremeters are gas lasers. At the
present time, nitrogen, XeCl, XeF and KrF are used quite frequently for fluoreme-
try. The reason to use lasers as the light source for fluoremetry is the same as was
given for Raman spectroscopy: lasers emit monochromic light with very high
intensity in comparison to the classical light sources.
4
J_
Fig. 2.53: Fluoremeter:

1 -light source
2 - transmitted light
3 - sample chamber
4 - emitted light
5 - monochromators
6 - detector
Almost exclusively, only diffraction grids are used as monochromators in

fluoremeters. The functioning principle of this device was described in detail in
the section in this chapter devoted to infrared spectroscopy.
The evaluation of the results of fluoremetry can be done both quantitatively
and qualitatively. Qualitative evaluation is done in the same way as for most spec-
tral methods. There are tables of spectra of known compounds or the spectra are
saved in digital libraries, which are delivered together with the instrument. There
are three methods used for quantitative evaluation:
1. direct method for the fluorescence-able samples
2. converting of non-fluorescence-able samples into fluorescence-able
samples
3. fluorescence extinction of the indicator substance
The first method is the most used. The second and third methods are usually
used in connection with high performance liquid or thin film chromatography.
For quantitative evaluation according to the first method, equation (2.17) is
used.
138 Chapter 2
IF = 4 > - I 0 - ( l - 1 0 E C d ) (2.17)
where IF - intensity of the emitted light

<|> - light emission coefficient
ID - intensity of the light entering into the sample
E - specific characteristic value of the component analyzed
C - concentration of the component analyzed
d - sample thickness
If the extinction (E) according to the Lambert-Beer law (see equation 2.4),
which is calculated by equation (2.18), is less than 0.01,
E = E-C-d (2.18)
Then, equation (2.17) can be rewritten as equation (2.19):
IF = 2.3 • <)> • Io • E-C-d (2.19)
In equation (2.19), it is seen that with a solution containing a relatively low

concentration of substances absorbing the light, the concentration of the compo-
nent analyzed depends linearly on the intensity of the fluorescent light. Nonlinear
dependence of highly concentrated solutions having extinction coefficients over
0.01 leads to the filtering effect.
Fluoremetry belongs to the class of relative methods. This means that quan-
titative evaluation by such methods is possible only after calibrating the instrument
by reference solutions with a known concentration. If the factors 0, IQ and d are
constant during calibration and measurement, then the concentration of the sample
or a component in the analyzed sample can be calculated by equation (2.20).
Ca = C c -I F a /I F C (2.20)
where Ca - concentration of the sample or sample component

Cc - concentration of the sample or sample component in the refer-
ence solution
Ipa - fluorescence intensity from the sample solution
IFC - fluorescence intensity from the reference solution
Fluoremetry has two main advantages in comparison to photometry that uses the
same light spectrum for analysis. These are the high sensitivity and the high selec-
tivity of the method. High sensitivity of the method can be explained on the basis
of the absence of such effects as background absorption, which are typical of ab-
sorption spectral methods. High selectivity is due to the difference in wavelengths
between the prime light and the emitted light. By changing the wavelength, the
florescence of single compounds in the sample mixture can be measured.
Fluoremetry is especially useful for the determination of condensed aro-
matic and heteroatomic compounds in crude oil and its products. The use of fluo-
remetry in crude oil chemistry is presently so highly developed that already there
is a special classification of types of fluoremetry typical for crude oil chemists.
These are the qualitative, visible and quantitative methods widely used by crude
oil chemists.
More detailed descriptions of techniques and methods of fluoremetry for
crude oil chemistry can be found in references 78 and 79 given at the end of this
chapter.
2.2.5 Atomic Absorption Spectroscopy and Atomic Emission Spectroscopy
Atomic absorption Spectroscopy and atomic emission Spectroscopy are

based on Kirchhoff s law. According to this law, all atoms are able to absorb light
quanta with the same wavelength that they are able to emit.
A light source which emits a continuous light spectrum produces a black
spot on a photographic plate of a spectrometer over the whole detectable area. If
one installs a burner between the light source and a photographic plate, as it is
usually used for atom absorption spectrometry, and sodium chloride solution is
spattered in the flame, then one receives again a continuous spectrum of appropri-
ate density over the whole detectable area on the photographic plate. There are two
bright lines on the spectrum, presenting the characteristic wavelengths of sodium.
This is a well-known feature from the solar spectrum called Frauenhofer D-line.
The presence of these characteristic lines, or better: these places of smaller density,
can be explained as follows. In the colder, outside zone of the sun, free atoms of
sodium are present, which absorb light with the same wavelength which was
emitted by hot sodium atoms present inside of the sun. In other words, sodium
steam, which is not so highly heated up, that is able to emit light absorbs the light
of exactly the same frequency or wavelength as light which it emits, if it is hot
enough to emit light. This law can be applied to every known metal.
The spectra of atomic absorption are obtained with instruments called
atomic absorption spectrometers. These instruments, as already described for other
types of spectrometers, consist of the light source, monochromator and detector.
However, the atomic absorption spectrometers and atomic emission spectrometers
differ from all other spectral spectrometers by the absence of the sample chamber.
Instead of the sample chamber, they contain a burner. A schematic of the atomic
absorption spectrometer is shown in Figure 2.54.
Two types of lamps are used as source of monochromatic light. These are:
1. Gas discharge lamps. They are manufactured for the determination of sodium,
potassium, mercury, cadmium and thallium atoms. They emit specific mono
or polychromatic radiation for these elements.
140 Chapter 2
2. Cathode lamps. These lamps are used for calcium, magnesium, silver, gold,
chrome, copper, iron, manganese, nickel, zinc and many other elements.
Fig. 2.54: Atomic absorption spectrometer:

1 -light source
2 - burner or atomizer
3 - monochromator
4 - detector
6 - gas fuel
7 - air or oxygen under pressure with solution of analyzing sample
The functioning principle of the gas discharge lamps can be explained based
on Figure 2.55. A small amount of the element that is analyzable by this lamp is
melted under pressure in the quartz chamber. The element emits light of a certain
wavelength by a high frequency electrical stream.
Fig. 2.55: Gas discharge lamp:

1 -quartz window
2 - quartz chamber with meted in element
3 - source of high frequency electricity
The gas discharge lamps have higher intensity of emitted light and can work
for a longer time without being changed in comparison to cathode lamps.
There are many types of light sources often used in modern atomic absorp-
tion spectroscopy. The scheme of such a lamp is represented in Figure 2.56.
Fig. 2.56: Cathode lamp:

1 -quartz window
2 - cathode
3 - anode
The cathode lamps usually consist of one cylindrically arranged cathode

made from a metallic element and an anode. The cathode is protected with a glass
cylinder. The glass cylinder is usually filled with argon or neon. The anode is
represented by wire made from tungsten or nickel. After creation of an electrode
voltage of up to 600 V, positively charged ions are transmitted from the cathode,
followed with transfer of the electrons from the base state to a higher energy level.
The light for analyzing certain metallic elements is emitted by return of electrons
again to the base state.
The next component part in the scheme of the atomic absorption spec-
trometer is the atomizer. Burners are often used as atomizers in atom absorption
spectroscopy. Mixtures of air/acetylene, laughing gas/acetylene or hydrogen/argon
are usually used as the fuel gas. The aim of the burner in atomic absorption spec-
troscopy is to evaporate the solution of the sample and to disintegrate the sample
to the atomic state. Especially important for successful analysis is that the path of
light through the flame of the burner be made as long as possible. Hence, the use
of fissure burners.
Graphite pipe technique is the next method used to atomize the sample. The
graphite pipe filled with sample is used in this method. This pipe is electrically
heated up such that the sample is atomized. The biggest advantage of this method
is that the atoms of the sample can be held in the pipe much longer than in the
flame. It makes the results of the analysis more accurate.
142 Chapter 2
Antimony, arsenic, selenium, tellurium, bismuth and tin are able to form
volatile hydrides by reaction with NaBH4. This property of these metals is used for
the hydride atomizing technique. In this method, the metal hydrides are atomized
in quartz cuvette by electrical heating.
The last method used for atomizing is the cold vapor method. Only mercury
can be analyzed by this method. It is known that mercury is the only metal which
has a relatively high vapor pressure even at 20°C. Mercury can be introduced in
the atomizer at room temperature without prior dissolution.
The next component part shown in Figure 2.54 is the monochromator. The
monochromators used in atomic absorption spectroscopy are the same as for all
the other spectral analytical methods. A detailed description of the monochroma-
tors can be found in the section in this chapter devoted to infrared spectroscopy.
Detectors used in atomic absorption spectroscopy are usually photometric
detectors.
Atomic absorption spectroscopy belongs to a class of relative analysis
methods, meaning that direct quantitative evaluation of the results of this analysis
is impossible. The most popular method of quantitative evaluation of atom ab-
sorption spectroscopy results is the standard addition methods. Certain known
amounts of the element under analysis are added to the analyzing solution many
times, and the intensity of the specific wavelength measured each time, thereby
producing a calibration graph. An example of a calibration graph is shown in
Figure 2.57.
absorption
Concentration, [mol/l]
Fig. 2.57: Calibration graph for atomic absorption spectroscopy:

1 - measured absorption for the sample solution
2 - measured points of the solutions with added element under analysis
3 - concentration of the element in the sample solution
The concentration of the element in the sample solution can be found as the
intersection point of the calibration line with the concentration axis at which point
the absorption equals zero. The concentration of the element in the sample solu-
tion is accepted as zero for the calibration as shown in Figure 2.57.
Atomic emission spectroscopy is very similarly to atomic absorption spec-
troscopy. The difference between these methods can be seen from their names.
Emitted light of the atom under analysis is analyzed by atom emission spectros-
copy. The schematic for the atomic emission spectrometer is very similar to that
for atomic absorption spectrometer. The schematic for the atomic emission spec-
trometer is presented in Figure 2.58.
Fig. 2.58: Atomic emission spectrometer:

1 - burner or atomizer
2 - monochromator
3 - detector
5 - gas fuel
6 - air or oxygen under pressure with solution of analyzing sample
In Figure 2.58 it is seen that the atomic emission spectrometer has no light
source. Atoms emit light by the influence of the thermal energy of the burner.
However, the energy needed to enable the atoms emit the light is much higher than
the energy needed to only atomize them. Hence, the much higher temperature
required for the burner of the atomic emission spectrometer than that for the
atomic absorption spectrometer. This is also the reason why other gas mixtures
such as fuel gas should be used for atomic emission spectroscopy. Mixtures of
methane/air, hydrogen/air, acetylene/air, methane/oxygen and acetylene/oxygen
are usually used as a fuel gas for this analysis.
The next possible way to make atoms emit light is the flashover method. In
this method, flashover is the source of thermal energy. The biggest advantage of
this method is the ability to heat the sample up to 10000K. It is possible to analyze
almost all known metals at this temperature.
In most modern spectrometers, plasma sources are used as source of thermal
energy.
Both methods, atomic absorption spectroscopy and atomic emission spec-
troscopy, are used in modern crude oil laboratories, with atomic absorption spec-
144 Chapter 2
troscopy being estimated as being the more popular, because of the following
advantages:
- better precision of the method
- less spectral divergences
- wider limits of concentrations of the elements analyzed in the sample, by
using the graphite pipe technique
Both methods are used for the determination of the metal content. The de-
termination of the concentrations of heavy metals in crude oil and its products is
an important topic in environmental chemistry. Heavy metals are always present
in crude oil, especially in the heavy fractions such as residual fuel. The control of
the concentration of heavy metals in such fuels is very important for ecological
monitoring in crude oil chemistry. More about the methods, techniques and mod-
ern research results made by atomic absorption spectroscopy and atomic emission
spectroscopy can be found in references 80-82 shown at the end of this chapter.
2.2.6 X-ray Fluorescence Spectroscopy
X-ray spectroscopy can be classified in the same manner as every other type
of spectral analysis into absorption and emission spectroscopy. However, the most
popular method of x-ray spectroscopy in crude oil chemistry is the emission spec-
troscopy, also called x-ray fluorescence spectroscopy. The effect used by this type
of spectral analysis is the same as was described for fluorescence analysis. How-
ever, x-rays are used for this analysis instead of the ultraviolet radiation used for
fluorescence analysis.
The scheme of the x-ray fluorescence spectrometer is similar to that for the
fluoremetry spectrometer. This is presented in Figure 2.59.
X-ray pipes are used as the light source for x-ray fluorescence spectroscopy.
There are very many types of x-ray pipes in the modern market. The functioning
principle of the x-ray pipe is the same as for cathode lamps described in an earlier
section of this chapter. The x-ray pipe contains an electrical heated cathode, anode
and radiation output window. This window is made from beryllium because this
material is transparent to x-rays. The x-rays pipes offered in the market differ
because they have a different anode material, and consequently the spectral char-
acteristics of the emitting radiation are different.
The monochromator for x-ray fluorescence spectroscopy is called the ana-
lyzing crystal. It differs from all the monochromators described earlier for all the
other optical analytical instruments. The effect used in this type of monochromator
is not diffraction, but interference. The wavelength of the analyzing light is
changed by rotation of the analyzing crystal by certain angle.
The homogeneity of the sample is very important for successful x-ray fluo-
rescence spectrometry. Hence, the preparation of solid samples for this analysis by
melting. The samples analyzed by crude oil chemist are, in most cases, liquids or
can be melted at a relatively low temperature. This is why the problem of homo-
geneity does not arise in analyzing crude oil or their products.
Fig. 2.59: X-ray florescence spectrometer:

1 - light source
2 - sample
3 - monochromator
4 - detector
Qualitative evaluation of the results of x-ray fluorescence spectroscopy is

carried out in the same way as for all other spectrometry methods described in this
chapter. This is done based on the table in the literature or on digital libraries sup-
plied with the evaluating software for the specific spectrometer.
X-ray spectroscopy, just like many other spectroscopy methods, belongs to
the class of relative analysis methods. This means that quantitative evaluation is
possible only by comparison of the analysis results with calibration results. The
following methods are used for the evaluation of x-ray fluorescence spectrometry:
- comparison with calibration curves
- standard addition method
- addition of inert substance
- statistical calculation method
The first three methods are very similar to the methods used for other spec-
troscopic methods. Statistical calculation methods can be used only in modern x-
ray fluorescence instruments that come with the appropriate software. Different
manufacturers or companies use different algorithms their instruments. The main
purpose of this software is to minimize the influence of measurement errors when
computing the results. A wide variety of statistical methods are available. The
statistical calculation method saves a lot of experimenting time, because only the
analysis of the sample is needed for every analysis. Calibration or analyses of
sample with added substance is not required in this case.
146 Chapter 2
The x-ray fluorescence analysis is used by crude oil chemists as an express

method for the determination of the metal contents in crude oil and its products.
This is very important because the metals in crude oil are poisons for cracking
catalysts, and are also undesired in the fuels, since they lead to environmental
pollution. All the elements with atomic number greater than eleven in the periodic
table can be analyzed by x-ray fluorescence spectrometry. An important task of
this method in crude oil chemistry is the determination of heteroatoms such as
sulfur, oxygen, and nitrogen. Frequently, x-ray fluorescence spectrometry is used
to verify the presence of certain additives in oils.
More about x-ray fluorescence spectrometry and the evaluating methods can
be found in references 83 and 84 at the end of this chapter.
2.3 OTHER METHODS FOR ELUCIDATING THE STRUCTURE OF

CRUDE OIL
2.3.1 Separation Methods
All the separation methods used to classify physical and chemical properties
of crude oil can be classified into the following classes:
- chromatography
- spectroscopy
- adsorptive methods
- evaporating methods
- extraction
- thermal diffusion
- crystallization
- complex formation methods
The first two methods were described in detail in the first two sections of
this chapter. The adsorptive methods used by crude oil chemists are actually simi-
lar to those described for the chromatographic methods. The setup used for this
type of analysis is the same as was shown for column chromatography (see Figure
2.19). There are two different adsorptive separation methods:
- desorption method
- elution method
The preparation of sample for both methods is done in the same way as was
shown for column chromatography. However, both methods differ in the solvents
used for desorption. In the case of the desorption method, the solvents used should
have a stronger absorption ability than the compounds in the sample mixtures.
Solvents used for analyzing crude oil and its products include alcohols, ketones,
ethers, chlorine-containing solvents, benzene, toluene and so on. It is possible to
use many solvents in this method. It is very popular in analyzing heavy fractions
of crude oil.
Large amounts of solvents with lower adsorption ability than the compounds
of the sample mixture are used in the elution method. Pentane, hexane, heptane
and petrol ether are frequently used by crude oil chemists as solvents for elution
adsorptive analysis.
Evaporation methods can be classified in three types:
- distillation
- rectification
- molecular distillation
The first two methods are described in detail in chapter 5 of this book be-
cause of the high importance attached to these methods for the industrial separa-
tion of crude oil. However, it will be said at this point that both methods use the
difference in the boiling temperatures of the compounds in crude oil for separating
the compounds. Rectification actually involves carrying out the distillation as a
multistage process. The reason to carry out such a multistage process is that dis-
tillation (i.e. in one stage) does not provide a satisfactory separation into the de-
sired fractions. The distillation method is however frequently used, and it is a
standard method in all international standards for characterization of light fractions
of crude oil such as gasoline and diesel. The biggest advantage of this method in
comparison to rectification is that this analysis needs less time to be carried out.
The third method is molecular distillation. This is distillation under very low
pressure. Usually the pressure for this analysis varies from 0.133 Pa up to 0.013
Pa. The heavy fractions of crude oil can be separated with this method. The name
molecular distillation is derived from the fact that the vapor pressure of the high
molecular compounds depends almost linearly on the boiling point of these com-
pounds under vacuum. It means that the separations by this method proceeds ac-
cording to the molecular weight of the compounds in the sample. The quality of
the separation depends on the evaporation velocity of the compounds in sample
mixture.
Extraction methods are based on the different solubility of the compounds of
sample in solvents. Usually, many different solvents or one solvent at different
temperatures are used to separate the sample into fractions according their solubil-
ity in the solvent. This method is important for analyzing the heavy fractions of
crude oil. This is why this method is described in detail in chapter 8 that is devoted
to asphaltene chemistry.
The thermal diffusion method is used rarely in comparison to all the other
analysis methods in crude oil characterization. However, this method is very use-
ful and can be successfully used for the analysis of heavy crude oil fractions. The
setup used for this analysis is really simple. It is represented in Figure 2.60.
The setup for thermal diffusion analysis contains two cylinders installed one
in another as shown in Figure 2.60. The sample is introduced between these two
cylinders. During analysis, the wall of one cylinder is heated up to a temperature
148 Chapter 2
between 100 and 180°C while the wall of the other cylinder is cooled down to a
temperature between 4°C and 20°C. Compounds in the sample are in motion in a
direction towards the top at the hot wall as well as in a direction towards the bot-
tom of the cold wall. Compounds of the sample are thus separated according to
their physical properties (i.e. according to the density and viscosity of the com-
pounds in the sample).
Fig. 2.60: Thermal diffusion analysis setup.
The next method is the crystallization method. This method is very fre-
quently used by crude oil chemists for the classification of lubricating oil fractions.
This method is based on difference in the crystallization temperatures of the com-
pounds in the sample. The samples which are analyzed by this method are usually
highly viscous. This makes it difficult to separate the crystallized substances from
the sample. Consequently, the sample is usually dissolved in a special solvent.
Examples of such solvents are liquefied propane, ethyl ether, and a mixture of
acetone and toluene.
The last method that was mentioned at the beginning of this section was
called the complex formation method. This method is based on formation of com-
plexes of crude oil compounds with other substances. The most popular methods
of complex formation are complex formation with CO(NH2)2 and CS(NH2)2. For
CO(NH2)2, it is typically to form complexes with rc-alkanes and their derivates
with relatively long paraffinic chains with normal structure. The formed com-
plexes are crystallized from the sample. The separation of the n-alkane fraction
from CO(NH2)2 can proceed by adding hot water to the crystallized complex. The
CO(NH2)2 is very soluble in water whereas paraffins are insoluble. This is why
two layers result in this separation: the fraction of aqueous solution of CO(NH2)2
and the paraffin fraction. Because the analysis is done at room temperature where
paraffins are usually solid, the paraffin plate can be easily taken off from the top of
the analysis glass. The analysis with CS(NH2)2 is carried out in the same way as
the analysis with CO(NH2)2. However, CS(NH2)2 forms a complex with iso-
alkanes. By using both of these methods, a relatively exact separation of rt-paraffin
and j'so-paraffin fractions is made possible.
2.3.2 Chemical Analysis Methods of Crude Oil Products: Determination of

Unsaturated Compounds
Unsaturated compounds are not present in crude oil. However, a significant

amount of these compounds can be found in the products of crude oil treatment.
An example is the product of thermal cracking. Many problems are associated
with unsaturated compounds. For example, these compounds tend to undergo
strong oxidation reactions. This can quickly change the quality of the produced
products. The oxidized compounds can react by polycondensation reactions and
form insoluble residues in crude oil products. This can even be dangerous espe-
cially for motor fuels, because this residue plugs the fuel filters and makes engines
not function properly.
All the chemical methods for the determination of the amount of unsaturated
compounds are based on the addition reaction of halogens such as bromine or
iodine to double bonds. Bromine number or iodine number is determined by this
method. The bromine number or iodine number shows the amount of bromine or
iodine needed to saturate all the unsaturated bonds in a hundred grams of the sam-
ple.
Determination of the bromine number or iodine number proceeds generally
in two steps. First bromine, iodine or their derivates are mixed with the sample.
The halogenization reaction is carried out. After this step, the mixture of the sam-
ple and indicator is titrated with sodium thiosulphate. This step shows how much
of the halogen is left in the mixture. The bromine number or iodine number is
determined as the difference between the halogen added and halogen remaining by
equation (2.21).
Nh = w h - 1 0 0 / w s (2.21)
where Nh - bromine or iodine number

wh - weight of bromine or iodine needed for halogenization
ws - weight of sample
The average number of unsaturated bonds in one molecule of the product

can be calculated by equation (2.22).
N = NB-M/160 = Ni-M7254 (2.22)
where N - average number of unsaturated bonds

NB - bromine number
N] - iodine number
W - average molecular weight of the sample
150 Chapter 2
There is a special method for the determination of diolefin compounds. This

method is based on the reaction with moleine anhydride as represented by equa-
tion (2.23).
(2.23)
The formed derivatives of moleine anhydride are solid crystalline com-

pounds and can easily be separated from the liquid sample or solution of the sam-
ple in an appropriate solvent.
2.3.3 Structural Bulk Analysis of Heavy Crude Oil Fractions: n-d-M Method
The main idea of structural bulk analysis of heavy crude oil fractions is
based on the existence of the so-called average molecule. The average molecule
describes the chemical and structural properties of all molecules present in the
sample mixture. It means that the result of structural bulk analysis is not the de-
termined amount of compounds or compound groups, but it is the amount of car-
bon in certain structural groups, for example in aromatic groups, naphthenic
groups and paraffmic groups.
The most popular and simple method for structural bulk analysis for heavy
crude oil fractions is called n-d-M analysis. The main idea behind this method is
the linear dependence of aromatic, naphthenic and paraffmic carbon in heavy
fraction on refractive index, density and value reverse to the molecular weight.
This dependence is described by equation (2.23).
CL = a / M = b • Ad + c • An (2.23)
where CL - amount of aromatic, naphthenic or paraffinic carbon

a, b, c - empiric constants
Ad - density difference between sample density and hypothetical
paraffin density
An - refraction index difference between sample refraction index and
hypothetical paraffin refraction index
The hypothetical paraffin is only theoretically existent n-paraffm with an

endless chain length in liquid state. The density and refraction index were theoreti-
cally calculated for this paraffin:
nD20 = 1.4750 - refraction index at 20°C
nD70 = 1 .4600 - refraction index at 70°C

d20=1.8510 - density at 20°C
d70 = 1 .8280 - density at 20°C
The refraction index, density and average molecular weight of the sample
must be measured in order to use the n-d-M method. Evaluating the results of this
method begins with calculating four factors: v, X, W and Y - according to equa-
tions (2.23), (2.24), (2.25) and (2.26).
v = 2.5 1 • (nd20 - 1 .4750) - (d20 - 0.85 10) (2.23)

X = 2.42 • (tid70 - 1 .4600) - (d70 - 0.8280) (2.24)
W = (d20- 0.85 10) -1.11 -(n D 20 - 1.4750) (2.25)
Y = (d70 - 0.8280) -1.11- (no20 - 1 .4600) (2.26)
The calculation of the amount of carbon in different structural groups begins

after all these factors have been calculated. The amount of aromatic carbon is
calculated first. If the factor v is positive and all the needed values were deter-
mined at the temperature 20°C, then the amount of carbon in aromatic groups can
be calculated by equation (2.27).
CA = 430-v + 3660/M (2.27)
where CA - amount of aromatic carbon
If the factor v is negative, the amount of aromatic carbon is calculated by

equation (2.28).
CA = 670 - v + 3660 / M (2.28)
For the case when all the measurements are carried out at the temperature
70°C, factor X is used. If X is positive, then the amount of aromatic carbon is
CA = 4 1 0 - v + 3660/M (2.29)
If factor X is negative, then equation (2.30) should be used.
+ 3660/M (2.30)
The general amount of carbon in cyclic structural elements of the sample

(CG) is calculated next. The factors W and Y are used for this calculation. The
factor W is used for the evaluation of the measurements made at 20°C. If the fac-
152 Chapter 2
tor W is positive, then the amount of cyclic carbon can be calculated by equation
(2.31).
CG = 820 - W - 3 - S + 10000/M (2.31)
where S - sulfur concentration in the sample
Equation (2.32) should be used for negative factor W.
CG= 1 4 4 0 - W - 3 - S + 1 0 6 0 0 / M (2.32)
Factor Y is used for the evaluation of the measurements made at the tem-
perature 70°C. If this factor is positive then the general amount of carbon in cyclic
groups can be calculated by equation (2.33).
CG = 7 7 5 - W - 3 - S + 1 1 5 0 0 / M (2.33)
For the case of negative factor Y, equation (2.34) should be used.
C G = 1 4 4 0 - W - 3 - S + 12100/M (2.34)
The amount of carbon in naphthenic groups can be calculated by equation

(2.35).
CN = CC-C A (2.35)
Finally, the amount of carbon in paraffinic groups is calculated as a differ-

ence between 100 % and amount of cyclic carbon.
CP = 100 - CG
Average molecules can be drawn based on the results of the structural bulk
analysis. For example, the molecule shown in Figure 2.61 has 33.3% of aromatic
carbon, 13.3% of naphthenic carbon and 53.4% of paraffinic carbon.
It should be noted that the same analysis results could be obtained, for ex-
ample, for a mixture of different derivates with different lengths of the paraffinic
chain or different number of aromatic rings. Now it is obvious that the information
obtained from the n-d-M method describes the average structure of the molecules
in the sample mixture and the amount of carbon in the different groups. This is
why this method is called structural bulk analysis.
The evaluation method described in this chapter was developed by Van-
Ness [85]. More about the n-d-M method and similar methods for the analysis of
heavy crude oil fraction can be found in many references at the end of this chapter.
Fig. 2.61: Average molecule.
2.4 METHODS OF CHARACTERIZATION OF COLLOIDAL

PROPERTIES OF CRUDE OIL AND ITS PRODUCTS
The colloidal properties of the crude oil are important especially for the
chemistry of the heavy fractions of crude oil, which contain high amounts of as-
phaltenes and resins. The main purpose of all these methods is to determine the
size of the colloidal particles in crude oil product, and consequently to estimate the
colloidal stability of these products, meaning how long the product can keep the
physical properties in the bulk volume in equilibrium.
All the methods used for colloidal characterization of crude oil can be classi-
fied as direct and indirect methods.
2.4.1 Direct Methods
All the spectral methods belong to the direct methods. All these methods use
interference or light scattering effect. The spectrum used for this analysis is all the
wavelengths from infrared until x-ray. However x-ray scattering method is the
most popular method of elucidating the colloidal properties of crude oil. The
technical fundamentals of such a measurement are the same as was shown for x-
ray spectroscopy. However, in this measurement, it is the intensity of radiation
scattered at a certain angle that is determined. Equation (2.36) is used for evaluat-
ing the measurements results.
2
T - T -l J /3)
Is = IQ • e(-S
0 /T o/;-.
(2. jo)
where Is - intensity measured by angle factor S

I0 - intensity measured at the angle 0°
S - angle factor
r - particle radius
154 Chapter 2
The angle factor S depends on scattering angle and wavelength of the radia-
tion used for the analysis. It is calculated by equation (2.37)
= 4-n/X-sin(9/2) (2.37)
where n = 3.14159265
A, - wavelength
6 - scattering angle
The next direct method used to characterize the colloidal properties of crude
oil is the sedimentation method. It is obvious from the name of the method that
this method is based on the sedimentation effect. There are two possibilities to
carry out this method: the first is the sedimentation under the influence of gravita-
tional force and the second sedimentation under influence of centrifugal force. The
choice between these methods depends on the viscosity of the sample and the size
of the particles of the disperse phase. Viscous samples or samples with relatively
small particles should be analyzed by the second method.
The setup used for sedimentation analysis is shown in Figure 2.62.
Fig. 2.62: Sedimentation analysis:

1 - measurement cylinder
2 - sedimentation scales
4 - continuous phase of sample
5 - disperse phase of sample
The simplest evaluation method for colloidal systems with similar sizes of
colloidal particles is based on equation (2.38).
9 vH
r= ' (2.38)
[2-(d-d 0 )-t s
where v - viscosity of the sample

H - height of the sample level (see Figure 2.62)
d - density of disperse phase of the sample
d0 - density of continuous phase of the sample
tj - sedimentation time
r = sedimentation rate
The sedimentation time is measured as a time from when the analysis starts
until the time when the weight on the sedimentation scale does not change any
further.
The sedimentation method belongs to the classical methods of characteriza-
tion of the colloidal properties of disperse systems. These methods can be used for
the analysis of colloidal solutions with size of colloidal particles between 1 and
100 micrometer. The analysis of solutions with smaller particles leads to relatively
high errors as a result of Brownian motion.
The next direct method for the determination of colloidal characteristics of
crude oil is the conductive method. This method is based on the measurement of
the electrical conductivity of the sample during the time the colloidal particles pass
through a calibrated microhole. The schematic of the setup used for measurement
by the conductive method is shown in Figure 2.63.
There is a constant voltage between two electrodes (see Figure 2.63). The
sample is sucked out continuously by a pump system shown as 5 in Figure 2.63.
Thus, there is continuous stream of the sample passing through the calibrated
microhole throughout the analysis time. Because of the difference in conductivity
of the discontinuous phase and the continuous phases in the sample colloidal solu-
tion, the measured conductivity of the sample is changed continuously as particles
of discontinuous phase pass through the calibrated microhole. The resulting elec-
trical impulses are registered by a monitoring device. The frequency of these im-
pulses depends on the concentration of the discontinuous phase and their intensity
is influenced by the size of the particles passing through the calibrated microhole.
Evaluation of the measurement results are based on calibration tables.
The biggest disadvantage of the conductive method is that only colloidal
solutions with a low concentration of the discontinuous phase can be analyzed.
This is due to the fact that only a few particles can pass through the calibrated hole
at the same time. This may lead to a wrong record of the particle size and concen-
156 Chapter 2
tration, because these few particles are registered as one particle of a size that is
greater than the size of each of the constituting particles.
Fig. 2.63: Setup for conductivity analysis:

1 - colloidal particles
2 - continuous phase of sample
3 - electrodes
4 - glass cylinder
5 - pipe for sample output
6 - glass
7 - calibrated microhole
The last direct method often used for determination of the colloidal proper-
ties of crude oils is gel permeation chromatography. The principles of this method
were described in section 2.1.2. Normally, this method is used for analyzing the
molecular weight distribution of substances. However, it is possible to use it to
analyze colloidal properties as well if an appropriate solvent is used as the mobile
phase. This solvent must not change the native disperse particles. Almost all the
solvents that can be used in this analysis as a mobile phase change the size of
native particles. This is why this analysis is usually used for estimating the particle
size in the sample solution.
2.4.2 Indirect Methods
All the indirect methods that are based on the determination of the colloidal
properties of crude oil measure macroscopic properties such as density, viscosity,
and molecular weight. An example is that the molecular weight of asphaltene
particles or asphaltene molecules is a result of the determination of the molecular

weight by methods such as osmotic pressure measurement. There are very many
indirect methods developed for certain oil or certain cases. The main idea in all
these methods is the development of models that describe the relation between
macroscopic properties and colloidal properties of the sample system.
2.5 DETERMINATION OF THE PHYSICAL PROPERTIES OF CRUDE

OIL
2.5.1 Density Determination
Density is not only just one of the most important physical parameters of
crude oil and its products, but it is also an important characteristic for measuring
the quality for crude oil and its products. The density of a sample shows its mass
in specific volume. The classical definition of density is presented in equation
(2.39).
d = W/V (2.39)
where d - density
W - weight of the sample
V - volume of the sample
The density that is calculated in equation 2.39 is known as absolute density.

However, this density is rarely used by crude oil chemists and only in special
cases. Relative density is the parameter that is usually used for the characterization
of crude oil and its products. Usually, relative density is measured at a reference
temperature of 20°C. Relative density is calculated by equation (2.40).
da!=d./dw (2.40)
where ds - density of the sample at the temperature 20°C

dw - density of water at the temperature 20°C (0.99821 g/cm3)
Relative density can be calculated by equation (2.40) by using the water

density at 20°C. The absolute density can be compared with water density at 4°C.
Then, relative density should be calculated by equation (2.41).
df=d./d w (2'41>
where ds - density of the sample at the temperature 20°C
dw - density of water at the temperature 4°C (1.00000 g/cm3)
158 Chapter 2
It is obvious that relative density that is calculated with equation (2.41) is

equal to the absolute density that is calculated at 20°C.
There are two methods for the determination of density that are popular with
crude oil chemists. The first is the hydrometer method. The hydrometer is a glass
body, which is dipped into the sample. After a short equilibration time, it will float
vertically at a certain level. This level results from when the mass of the hy-
drometer is equal to the buoyancy effect. The higher the density of the sample, the
less the hydrometers will sink into the sample. The level of equilibrium shows the
density on the calibrated scale. An example of density determination is shown in
Figure 2.64.
The hydrometer method is the simplest and fastest one. This method only
has one disadvantage, and that is that the hydrometer usually has a very small
measuring range. This requires many hydrometers with different measuring ranges
for the determination of the density of a sample with an unknown density.
Fig. 2.64: Hydrometer density determination:

1 - level at hydrometer scale showing density of the sample
2 - hydrometer
3 - cylinder
The second method is called the pycnometer method. A pycnometer is a

glass beaker of defined volume. It is shown in Figure 2.65.
Fig. 2.65: Pycnometer.
Firstly pycnometer is weighed without sample, then filled with the sample
thermostatted and weighed again. The absolute density is then calculated by using
equation (2.42):
d = (WF - WE) / V (2.42)
where d - density
WF - weight of pycnometer with the sample
WE - weight of empty pycnometer
V - volume of the sample in pycnometer
It is important to note that density is very sensitive to temperature. Thus, it is

very important to thermostat the sample before any measurement is made.
2.5.2 Viscosity Determination
Viscosity is the second most important physical parameter for crude oil. It
characterizes not only one of the physical properties, but also the quality of most
crude oil products such as lubricating oils and lubricants.
The term viscosity is derived from the flow behavior of a liquid. It is a
measure of resistance to flow. Viscosity can also be defined as inner friction or
inner resistance of the sample against flow.
There are two types of viscosity:
- dynamic viscosity and
- kinematic viscosity.
The two types of viscosity are often used by crude oil chemists for various
purposes. The kinematic viscosity can be measured with the Ostwald viscometer.
The Ostwald viscometer is the most popular instrument used by crude oil chem-
ists for determination of kinematic viscosity. A schematic of the Ostwald vis-
cometer is presented in Figure 2.66.
160 Chapter 2
Fig. 2.66: Ostwald viscometer:

1 - viscometer
2 - sample level 1
3 - sample level 2
4 - capillary
5 - thermostat
The sample is introduced inside the viscometer for the analysis so that the
top limit of the sample is located exactly on sample level 1 (see Figure 2.66). After
the sample is well thermostatted in the thermostat 5 the analysis can start. The
sample is released for free motion through the capillary 4 for the analysis. The
analysis result is measured in terms of the time which the sample needs to flow
from sample level 1 to sample level 2. The viscosity result is evaluated from equa-
tion (2.43).
Tl = k • t (2.43)
where r| - kinematic viscosity

k - capillary coefficient
t - time which sample needs to flow from level 1 to level 2
The kinematic viscosity can easily be converted into dynamic viscosity by

equation (2.44).
v = r| • d (2.44)
where v - dynamic viscosity

d - sample density
Dynamic viscosity can be determined directly by using the rotation vis-

cometer. The scheme of such a viscometer is shown in Figure 2.67.
Fig. 2.67: Rotation viscometer:

2 - static cylinder
3 - rotating cylinder
4 - sample
The rotation viscometer consists of two coaxial cylinders, between which

the sample is introduced. The rotating cylinder is rotated with a constant velocity.
The static cylinder is immovable. The static cylinder is hung on a torsion wire,
which is turned, depending upon the flow resistance, at a more or less large angle.
This rotation angle can be read from a monitoring device. The rotation angle is a
measure of the viscosity of the liquid. The viscosity should be extracted or read
from calibration tables with regard to the measured rotation angle.
During the measurement of the viscosity by both methods, it is important to
note that viscosity is very sensitive to temperature, and thus it is important to
thermostat the viscometer before starting analysis.
2.5.3 Refractive Index Determination
Refractive index is an important physical property of crude oil and its prod-
ucts which is usually used for further evaluation of the characteristics of crude oil
and its products. Such characteristics include the n-d-M method described in an
earlier section of this chapter. Refractive index represents the ratio between two
angles, the angle of incidence and the angle of refraction. The angle of incidence
(aO is the angle of a light beam before hitting the sample, the angle of refraction
(0:2) is the angle of the light beam after hitting the sample. An example of refrac-
tion is shown in Figure 2.68.
162 Chapter 2
Fig. 2.68: Refraction

1 - beam of light
2 - angle of incidence
3 - atmosphere
4 - angle of the light beam after hitting the sample
5 - refracted beam
6 - sample
The refractive index is calculated by equation (2.45) with regard to the re-
fraction scheme shown on Figure 2.68.
nD = sin(aO / sin(a2) (2.45)
where nd - refractive index

OC] - angle of incidence
oc2 - angle of the light beam after hitting the sample
The refractive index is measured directly by refractometers. The most

popular refractometers used in the laboratories use the functioning principle shown
in Figure 2.69. This figure shows a combination of two different prisms. Bottom
prism has a rough surface to create scattered light striking the liquid-glass inter-
face. The incident beam relating to the critical angle. The refractive index of the
sample is determined by measurement of the refraction angle of the refracted
beam of light 1 (see Figure 2.69)
A few drops of the liquid sample are placed on the bottom prism. The re-
fractive index can be read directly from the built-in scale, looking into the refrac-
tometer.
Fig. 2.69: Functioning principle of the refractometer:

1 - refracted beam of light
2 - upper prism
3 - sample
4 - bottom prism
5 - incidence beam of light
Refractometry is the last analysis method discussed in this part of the book.
However, some more analysis methods can be found in chapter 8 of this book. The
reason to describe these analysis methods in another chapter is the high
importance attached to these methods for asphaltene chemistry, which is an
important part of crude oil chemistry.
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Part II
REGIONAL PETROLEUM INDUSTRY
OVERVIEW
It would be appropriate to say at this point that this chapter deals more
with crude oil economy than with crude oil chemistry. However, the aim of this
chapter is to show the importance of crude oil chemistry not only for crude oil
chemists, but also for all of mankind. Almost everything around us is derived
from crude oil. This includes plastic parts, car fuel, jet fuel, oils, and even as-
phalt on the road; these are all made from petroleum. It is hard to imagine what
modern life would look like without these items, which began their existence
from the oil well.
Petroleum is responsible not only for making our life more comfortable,
but also it has a great influence on international politics. It is well known that
crude oil is often called "black gold". This name emphasizes the importance of
petroleum vis-a-vis the world economy.
The foregoing discussion explains why this chapter deserves a place in
this book. It helps us to understand the importance of crude oil chemistry for the
people making decisions about the future of petroleum education, for example.
This chapter shows new impressive sides of this branch of study.
171
Petroleum Producing Countries:
OPEC and Non-OPEC
3.1 INTRODUCTION
The many applications of petroleum have been known from ancient times.
Initially, primitive ways were employed in petroleum operations. Examples in-
clude collecting petroleum from the ground surface and the processing of oil
sands. The development of the petroleum industry started when mechanical drill-
ing for oil wells for petroleum production was employed in 1859 in the USA.
Practically all petroleum extracted in the world now makes use of mechanical
drilling.
At the moment, there is a reserve of up to 140,000 million tons of economi-
cally exploitable petroleum referred to as proven reserves. About 3,400 million
tons of crude oil is processed annually in refineries to high-quality finished prod-
ucts. Petroleum has played a very important role in the economy of many coun-
tries.
In the two chapters (chapters 3 and 4) in part II of this book, the reader will
be taken on a trip from the west to the east involving some crude oil producing
countries. The influence of the crude oil industry and petroleum organizations
such as the Organization of Petroleum Exporting Countries (OPEC) is shown in
these chapters.
173
174 Chapters
3.1.1 Short Background on OPEC
Before the reader starts on the promised trip, a short history of the most
important organization for every crude oil producer is given. This organization is
OPEC.
All the countries that control the world petroleum market can be broadly
classified as the west cartel and the east cartel. The east organization is called
OPEC, acronym for Organization of Petroleum Exporting Countries. This organi-
zation controls up to 61 % of the world petroleum export. OPEC is a multinational
union of crude oil extracting countries. The aim of this organization is to coordi-
nate the oil policy on the world market as well as control petroleum deliveries.
This organization was founded in 1960 and now twelve states belong to OPEC:
Algeria, Gabon, Indonesia, Iran, Iraq, Qatar, Kuwait, Libya, Nigeria, Saudi Ara-
bia, the United Arab Emirates and Venezuela. Ecuador joined OPEC in 1973 and
withdrew its membership in 1992. The main headquarters of OPEC is now located
in Europe in Vienna, Austria.
The work of OPEC is controlled by half-yearly meetings attended by crude
oil ministers or finance ministers of OPEC member countries. Since 1988, there
has been the establishment of a ministerial supervisory committee. The aim of this
committee is to control and develop new guidelines for crude oil extraction strat-
egy. An economic commission checks the price strategy. Since 1994, a new organ
of the OPEC general secretariat leads various research projects, and is also respon-
sible for the legal and administrative questions inside the organization.
However, it can be said that the reason for the founding of OPEC was to
control the huge crude oil supply in comparison to the demand towards the end of
the 1950s. Oil prices increased as a result of this control of the difference between
supply and demand. Consequently, the international currency (money) paid by
international oil companies (for purchasing crude oil) to oil producing countries
increased. Thus, the Organization of Petroleum Exporting Countries appears to
have been founded to correct this payment imbalance. From 1973 to 1974, OPEC
obtained almost a quadruple increase for the international selling price for crude
oil at almost twelve US Dollars per barrel. A consequence of this price increase
was the first world oil crisis. In 1979 and 1980, OPEC members started a second
round of price increases, which raised oil prices to over 30 US Dollars per barrel,
which led to a rapid rise in inflation in industrial nations. And thus, the second
world oil crisis came into existence.
The following Table 3.1 compares crude oil extraction levels in OPEC
countries in 1999. From the Table, it can be seen that Saudi Arabia is the largest
crude oil producer among the OPEC countries. It must be emphasized that Saudi
Arabia also extracts more crude oil than any other country in the world.
OPEC and Non-OPEC Petroleum Producing Countries 175
Table 3.1: Crude oil extraction in OPEC countries (1999).
Country Oil extraction

[Million tons per
annum]
Nigeria 98.1
Kuwait 97.9
Indonesia 70.5
Libya 66.4
Qatar 35.5
Algeria 56.0
United Arab Emirates 109.6
Iraq 132.5
Venezuela 154.8
Iran 180.4
Saudi Arabia 413.4
3.2 NORTH AMERICA
3.2.1 United States [1-2]
The history of the petroleum industry in North America, in general, and the
United States, in particular, can be considered to date back to the year 1846 when
a Canadian archeologist, A. Hesner, developed a petroleum distillation process for
petroleum rich porous minerals. Kerosene was the main product in this process.
Fortunately, kerosene was the main fuel for lighting and was considered to be
better than light oil. As a result, this simple type of distillation process was widely
used. About thirty-four companies were already using the process by the end of
the 1850s. By this time also, the USA was already producing kerosene at the rate
of 8 million barrels per year.
In 1859, the former railway conductor E. Drake drilled the first oil well for
petroleum extraction. This was the first known oil well in the world that used
mechanical drilling. The method was so simple and effective that, shortly after it
was introduced, it was employed by many companies. The major reason was that
it could extract a large amount of petroleum in a less expensive manner.
By the 1860s, there was a rapid growth in the number of petroleum compa-
nies and oil refineries. The main product of these pioneer oil refineries was kero-
sene. In the little town of Cleveland, fifteen such refineries were in business. In
1865, the young John D. Rockefeller bought one such refinery. This was the be-
ginning of the Rockefeller family and the oil company known as Standard Oil.
In 1873, Standard Oil became the biggest oil enterprise in the USA. In the
1880s, Standard Oil began to expand outside of the USA. In 1885, a major part of
176 Chapters
the company business (70%) was outside of the USA. In 1895, this company tried
to share the world petroleum market with the Russian government, but Russia did
not accept this offer. After the strong economic crisis in Russia, and the First
World War as well as the Russian Revolution, the national economy of Russia
crumbled. At this time, Standard Oil was the world's biggest petroleum enterprise.
Practically, Standard Oil was a world monopoly. In 1911, the U.S. Supreme Court
ordered the break-up of the Standard Oil Trust, resulting in the spin-off of 34
companies. It was from this break-up of the world's biggest petroleum monopoly
that Exxon, Mobil, Texaco, SOCo (Amoco) and Soccal (Chevron) came into ex-
istence.
The next stage in the development of the petroleum industry in the USA
began after the First World War. At this time, high quality gasoline became the
main product of the processing of petroleum. This required the development of
new technologies for oil processing and complete reorganization of the structure
of refineries. The policy of the state was directed against monopolies and the gov-
ernment began to take steps to put petroleum business under state control. Federal
taxes for fuels and other petroleum products increased. In 1928, the biggest petro-
leum enterprises in the USA such as Exxon, Mobil, Chevron, Texaco, Gulf, the
British company British Petroleum, and British-Hollandaise Shell formed an in-
ternational organization called Seven Sisters. This organization played a very
important role in the development of petroleum extraction (used interchangeably
with production) in the Middle East regions and in transportation of this petroleum
to the United States.
The extensive development of the automobile industry in the 1930s helped
to sustain the level of petroleum processing and market in the years of the great
crisis. In 1933, the government, in conjunction with petroleum enterprises, tried to
stabilize the existing prices of fuels and petroleum products. It is important to note
that in the 1930s, the American petroleum companies, helped by the development
of many petroleum fields in the Arabian East, aided further development of the
Seven Sisters.
During the Second World War, the state control of the petroleum industry
was much stronger. The following operations were centralized and controlled by
the state: petroleum transfer from the Arabian East, petroleum products transfer in
the land, and fixing the price for fuels and petroleum products.
After the Second World War, the world saw five petroleum crises. However,
these had little influence on the American petroleum industry because of the good
relationship that existed between the government and the petroleum companies.
Because of this good relationship, the petroleum industry had the opportunity to
extract cheap oil from the Arabian East. This explains why prices for petroleum
products were constant in the time between 1947 and 1967. There was an increase
in petroleum import during this period because the petroleum imported from the
Arabian East was 15-20 times cheaper than domestic petroleum.
The period of cheap petroleum ended in the 1970s, at which time an organi-
zation known as Organization of the Petroleum Exporting Countries (OPEC) was
formed. Member countries were the countries of the Arabian East, Nigeria, Alge-
ria, Ecuador and Venezuela. All these countries stopped the selling of cheap pe-
troleum to the United States and the Seven Sisters. This was the start of the in-
crease in price for petroleum products in the USA and the beginning of the petro-
leum crisis. The export from the Arabian East was still at a very high level be-
cause, despite the relatively high prices of petroleum, the oil exported from OPEC
countries was cheaper than domestic petroleum.
The introduction of new ecological laws became the basis for the second
increase of petroleum prices. This required the development of new technologies
for the production of fuels with a higher quality as well as the reorganization of the
structure of petroleum refineries. The state price control played a positive role
during the period of price increase such that during the 1980s, the prices were
more or less stabilized. By 1986, petroleum prices were as low as 10 US$ per
barrel. In the 1990s, there was a greater stability in the price of petroleum in the
market. The price changed by only US$ 3-4 per barrel.
Nowadays, petroleum and natural gas are the biggest source of energy. To-
gether, they supply 65 percent of the energy used in the USA. Figure 3.1 shows
the breakdown of power sources as given by a U.S. Energy Agency.
About half of the oil consumed in the USA is produced in the United States.
The rest is imported.
The United States has 3,013 million tons of proven petroleum reserves.
At the end of the twentieth century, petroleum reserves had been declining
in the USA at an average of 2 percent per year. However, the fact that older re-
serves were added to these estimates and more negative revisions made the decline
much more severe in 1998. If drilling resumes, it is expected that the 2 percent
declining trend will be reestablished in the future. As the reserve base depletes
through production, the price of exploration rises through the increased cost of
deeper drilling.
At the present time, the following four areas account for 79 percent of U.S.
crude oil proven reserves:
Alaska 24%
Texas 23%
California 18%
Gulf of Mexico Federal Offshore 13%
Of these four areas, California increased its reserves in 1998, while Alaska,
the Gulf of Mexico, and Texas all had decreases in crude oil proven reserves.
The year 1999 saw a rapid recovery in oil prices, offsetting the weakness of
the previous year. The annual average price of petroleum rose by up to 39% in
1998.
178 Chapters
Nuclear Renewable
Coal
Gas
Fig. 3.1: The breakdown of power sources.
3.2.2 Canada [3]
Canada is another petroleum producer in North America. In comparison

with other petroleum producers, Canada is considered to be the biggest non-
conventional resource base (consisting of oil sands deposits in northern Alberta) in
the world.
These non-conventional resources can only be treated by secondary proc-
esses, which include thermal, catalytic cracking, and/or visbreaking. Thus, differ-
ent technologies and secondary production processes are used for the treatment of
non-conventional resources. Consequently, Canada has a reputation as a pioneer
country in non-conventional oil production. The Canadian industry has been very
successful at reducing the cost of developing these resources. The production from
oil sands is almost a major component in crude oil production in Canada.
Canada is the world's third largest producer of natural gas and eleventh
largest producer of crude oil. Canada produces much more petroleum and natural
gas than is consumed in the domestic market. Consequently, petroleum and natural
gas export plays a very important role in the Canadian economy. Another factor
that influenced the activity in the Canadian petroleum industry was the pipeline
expansion in the year 2000. This opened up new markets. A major fraction of
petroleum products are exported to markets in the United States.
3.3 RUSSIA [4-6]
In Russia, the first set of oil wells was drilled in Kuban in 1864. In 1866,
one of the wells produced a petroleum fountain with a volume of more than 1,300
barrels per day. Then, the extraction of petroleum was conducted by the main
monopolies that were dependent on foreign capital. There was not much mechani-
zation of the oil extraction process. Therefore, a lot more wells had to be produced
to maximize the income. In the beginning of the 20th century, Russia occupied
first place in the production of petroleum.
The main areas of oil extraction in the first years of the Soviet regime in
Russia were Baku and Northern Caucasus. However, the oil wells of these old
areas failed to satisfy the needs of the developing industry. Construction started in
Bashkiria and resulted in the creation of the large Volgo-Ural petroleum area. The
new oil wells in Central Asia in Kazakhstan were discovered for which the pro-
duction of petroleum reached approximately 210 million barrels per day. The
Second World War (1939 - 1945) brought serious damage to the areas of North-
ern Caucasus. This essentially reduced the volume of petroleum extraction. How-
ever, the period after the war brought a parallel restoration of the oil-extraction
complexes of Groznyj and Maikop, marking the development of the largest re-
serves in the Volgo-Ural petroleum area. And by 1960, the reserves had already
produced approximately 71% of the petroleum extracted in the country. Fifty
years after the Second World War, about 270 million barrels has been extracted. In
the 60th year, this value is expected to increase up to 990 million barrels. In 1974
on the other hand, the unique West-Siberian oil fields attained a leading position,
and even overtook the level of petroleum extraction in Tataria.
3.3.1 The Role of the Petroleum Industry for Russia
Before the political reorganization, the so-called "Perestroyka", petroleum

and gas were the backbone of the Soviet Union economy. The cheap power pro-
vided by oil and gas prevented the structural reorganization of the energy depend-
ent industry in USSR. Petroleum and gas also united the countries of the eastern
block. Foreign currency from the export of gas and oil was used to provide the
consumer market with imported goods.
Much has changed since then. The internal state structure has been radically
changed. The process of reorganization in the Russian administration has reached
an advanced stage. Meanwhile, oil and gas still remain the major source of foreign
currency for the country.
The oil and gas industry significantly strengthened the national economy
even during the years of reforms. After its initial disorder, the oil and gas industry
attained independence. As regards the Russian economy, the oil and gas industry
sector was damaged to a much smaller degree by the recession than the manufac-
turing and other industry sectors.
It is important to note that a majority of the industries in the processing
sector are unprofitable even though they consume power in excess of that pre-
scribed world wide during the fuel and energy crisis in 1970s. In the scenario of
manufacture decline, social problems and unemployment, the stable and export-
oriented oil and gas industry became the much-needed backbone for the economy
of Russia. Even now, the processing sector is still in deep crisis.
180 Chapter 3
Thus, the oil and gas sector is the forte of Russia. The oil industry of the
Russian Federation is closely connected to all sectors of the national economy and
has a huge importance for the Russian economy. The demand for petroleum and
gas is rather stable, though it is subject to crisis and decrease in price. Thus, in the
face of tax increase such as prescribed in Russia, this export-oriented operation
can be brought to liquidation. For these reasons, practically all advanced states of
the world and Russia, in particular, are interested in the successful development of
the Russian oil and gas industry.
3.3.2 Reforms in the Russian Oil Industry
As is well known, the more economically developed the state is, the more
advanced will its scientific and technological base be. For this state, most of the
imported goods will essentially be raw material. On the other hand, export goods
will comprise of expensive finished products and technological know how.
The construction of a similar system in Russia was the underlying basis for
Perestroyka. The structural reorganization of the Russian economy at the begin-
ning of the reforms were as follows: (1) to provide modern and high technological
economy, (2) to develop a political economy where ownership of property is pos-
sible, and (3) to make demonopolization and other socio-economic transforma-
tions. The economic reforms were also to provide liberalization of foreign trade
activities, as well as introduce modern energy-saving technologies. In other words,
the task was to restructure the national economy, in the shortest time, to a strong
industrial base that is founded on modern technologies. As such, the economy
would be competitive.
Unfortunately, the model of Russian economy got oriented towards the
export of raw materials initially during the reforms, contrary to original intentions.
This was so partly because the processing sector was basically noncompetitive and
was in a very difficult economic situation. Consequently, the former central uni-
form economic complex in Russia broke up into separate industrial and territorial-
industrial corporations (including a fuel and energy complex) during the reforms.
This exclusive old monopoly was very non-uniform by its territorial-sector struc-
ture. There was constant struggle for privileges and sources of state financing
between the enterprises and associations. Simultaneously, the new monopolies and
commercial groupings closely connected to external market were promptly formed
during the years of reforms in the country. These were the commercial structures
that had interest in the reformed Russian economy.
As was noted previously, the petroleum industry was stable even under
crisis conditions in Russia. However, problems existed in the oil industry as well.
These problems perhaps provided the challenges and opportunities for future de-
velopments. The petroleum and gas industry is represented in the gas sector by
Gazprom, and in the petroleum sector by such petroleum corporations as
LUKOIL, YUKOS, SIDANKO, ROSNEFT, etc. These companies were formed
during the structural reorganization of the oil and gas industries. This reorganiza-
tion had the following basic stages:
1. 1987-1990: The development of self-financing enterprises in the oil and gas
sectors, the expansion of economic independence for the enterprises, and be-
ing direct exporters of power sources to the world markets.
2. 1991-1994: The associations of the enterprises as vertical integrated struc-
tures, the beginning of privatization of holding petroleum companies, the
creation of an infrastructure for the shares market, coming into existence of
financial and industrial groups and consortia for participation in international
projects.
3. Since 1995: The concentration of economic authority in vertically integrated
companies, the transformation of companies from state controlled enterprises
into private companies by means of the mechanism of money auctions, reor-
ganization of the capital of the companies.
In the first stage (i.e., by the end of the 1980s), Russia introduced some elements
of market driven economy. A first step became the transition of the enterprises to
being self-financing. State ownership of the manufacturing sector was kept. How-
ever, in the long term, it was expected to transform into private or collective enter-
prises over the transitive period. The first stage of the structural reorganization of
the national economy could not eliminate crisis. Instead, it was aggravated. There
was a strategic miscalculation in the first stage of reform. The fact that privatiza-
tion could lead to a high degree of natural monopolization of the oil industry was
not considered. The splitting of the petroleum industry into separate enterprises,
which actually occurred after easing the state control, aggravated the crisis in the
oil industry.
In 1992, during the second stage of the accepted Russian program for priva-
tization, a mechanism for easing State control for the petroleum sector was worked
out. The essence was that the control package (the shares) of the enterprises re-
mained the property of the state for a fixed term. Privatization of the sector pro-
ceeded in two stages. At first, all the enterprises entering into the system known as
"Rosneftgas" and "Glavnefteprodukt" were transformed to open joint-stock com-
panies. After that, the creation of the basis for the joint-stock vertically integrated
holding companies began. The state enterprise, Rosneft, was created for commer-
cial management of the state shares of the enterprises that were not included in one
company on the basis of Rosneftgas. For the transport enterprises holding compa-
nies, "Transneft" and "Transnefteprodukt" were created. This distinctive feature of
the second stage of the oil and gas industry reforms led to the escalation of the
structural crisis. This was also promoted by the macro-economical preconditions.
With liberalization of the prices in the beginning of 1995, inflation was no longer
hidden, and the rates of inflation exceeded 30-40% per month. It affected the
strong growth performance of petroleum and gas export, and simultaneously there
was recession of internal consumption.
182 Chapters
The main characteristic of the third stage of the reforms in the oil and gas
industry in Russia was the new redistribution of property rights to the active enter-
prises and companies based mostly on political considerations. The second stage
of privatization of enterprises began after 1995. This was the key moment for the
realization of auctions pledged. The state gave the opportunity for commercial
banks to participate in crediting the federal programs by giving share packages
belonging to the state as pledges. The pledging auction represented the transition
of control share packages of the companies to banks with the prospect of their
repayment. By the end of 1996, the banks had received the right of repayment for
the shares. This created the prospect for transformation of all petroleum companies
into private enterprises.
Two opposing opinions have emerged as to further organizational develop-
ment of the gas industry. One of them proposed monopoly by the Russian power
since this would provide the stability needed by the gas industry even under to-
day's adverse conditions. The other prefers splitting into enterprises such as in
Gazprom and similar to the existing enterprises in the petroleum industry. The
former opinion is based on the thought that splitting the gas industry will weaken
its competitiveness in the world market.
3.3.3 Russian Petroleum and Gas in the World Market
Russia is not actively involved in formulating the world energy policy.

However, the slightest socio-economic and political instability in Moscow or
Tyumen is reflected in the petroleum price in the stock exchanges in New York or
in London.
Up till now, petroleum policy was defined by two cartels - west and east.
The first unites the six largest petroleum companies that extracts 40 percent of oil
(by volume) from countries that are not OPEC members. The cumulative volume
of sales for these companies in 1991 was almost 400 billion dollars. The eastern
cartel (OPEC) includes thirteen countries, which makes up 38 percent of world oil
production and 61 percent of world petroleum export. The oil production in Russia
makes up 10% of world petroleum production. Therefore, it is possible to say with
confidence that Russia occupies a strong position in the international petroleum
market. For example, OPEC declared before the crisis that the member states of
this organization could not fill any shortage of petroleum, should the world market
lose Russia.
It may not be possible for petroleum to be completely replaced by alterna-
tive power sources in the foreseeable future. According to forecasts, the world
demand will grow at the rate of 1.5 percent per year, and the supply will essen-
tially not increase, unless Iraq gets a new quota to increase the volume of petro-
leum for export. Before the energy crisis in 1973, the world's oil extraction was
practically doubled every ten years during the past 70 years. But now, only four
member countries of OPEC (which hold 66% of the world oil reserves) can in-
crease their volume of oil extraction. These are Saudi Arabia, Kuwait, Nigeria and
Iraq.
There was recently a very difficult situation in the world petroleum market.
The prices for petroleum had fallen to less than 10 dollars per barrel for the first
time in a long time. OPEC countries wanted to see an increase of even up to 30
dollars per barrel. With this in mind, it became necessary to reduce the export of
petroleum to the world market, even though each country did not want to do so at
the expense of its overall export.
The military actions of the USA and Great Britain in December 16-18 of
1998 on Iraq also had positive consequences on Russia. As a result of the aerial
bombardment, the Iraq factory for petroleum processing as well as ports for pe-
troleum export were destroyed. It is necessary to note that, although Iraq produces
only about 3% of the world's petroleum due to sanctions, this petroleum influ-
enced world petroleum prices. Iraqi petroleum is of very high quality but attracts a
very low price. As a result, prices increased sharply on the stock exchanges in
London and New York following the incident. Experts forecasted that the price
would reach 30 dollars per barrel. All this could have a positive effect for the
economy of Russia.
Irrespective of the situation regarding energy sources in the world market,
petroleum and gas always will play an important role in the home market because
they are the most valuable raw material for the petrochemical industry. More than
2000 kinds of products are made from this raw material. Russia is interested that
domestic petrochemical synthesis becomes an independent and powerful sector of
industrial manufacture, and also becomes competitive in the world market. It is
also interested that the country exports not only crude oil, but also much more
value-added products of petroleum processing. This will bring appreciable income
into the country.
3.3.4 Structure of the Petroleum Sector in Russia
The main problems of the petroleum sector in post Perestrojka is that of the
reduced proven oil fields and rising cost of development for the available oil
fields. This problem exists because of insufficient financing of geological pros-
pecting, which implies that exploration of new oil fields has been partially sus-
pended. According to expert forecasts, geological prospecting can potentially
increase production for the Russian Federation from 5 billion up to 7.5 billion
barrels per year (about 2 billion barrels was extracted in 1997). In 1992, Russia
occupied second place in the world for reconnoitered oil wells (after Saudi Arabia
on which territory a third of the world oil reserves is concentrated). The oil reserve
in Russia in 1995 was 140 billion barrels of petroleum.
It should be noted that the degree of conformability of foreseen oil fields is
very low and there are still a large share of oil wells with high costs of develop-
ment (of all the oil fields, only 55% have high efficiency).
184 Chapters
Even in Western Siberia where the most gain of reserves is expected, about
40% of this gain will not be efficient oil fields with extraction volume from new
oil wells less than 70 barrels per day. This is the limit of profitability for this re-
gion.
Therefore, the present condition of the petroleum industry in Russia is char-
acterized by volume reduction of industrial petroleum reserves, a decrease of both
quality and rates of processing, reduction in prospecting and operational drilling,
and an increase of quantity of idle oil wells. It is also characterized by the absence
of significantly large reserves; need to be involved in industrial operation of oil
wells which are located in difficult areas; increasing technical and technological
difficulties by the sector; insufficient attention to the requirements of social devel-
opment and ecology.
Experts have given reasons for the difficult economic situation in the Rus-
sian petroleum sector:
• Production in the biggest oil fields that are state funded and are the main
components of the resource base in Russia are substantially completed.
• New developed oil fields are worsened by oil conditions. No large or produc-
tive oil fields has recently been opened.
• The financing of exploration has been reduced. So, in Western Siberia, where
the degree of development for foreseen resources was about 35 percent, the
financing of geological works, which began in 1989, was reduced to 30 per-
cent. The volumes of prospecting drilling have decreased as well.
• There is not enough highly-efficient technology and equipment for production
and drilling. The main part of this production has deteriorated by more than
50 percent. Only 14 percent of machines and equipment reach world stan-
dards. With the disintegration of the USSR, the situation has worsened with
deliveries of drilling equipment from the countries of CIS.
• The low internal prices for petroleum do not provide self-financing for the oil-
extracting enterprises. This situation has persisted because after a series of in-
creases, there are declines in the prices for petroleum in the world and do-
mestic markets. As a result, there has been a serious deterioration of technical
and financial maintenance of the sector.
• The shortage of effective and ecological equipment creates pollution prob-
lems in the oil sector. Significant material and financial resources have been
spent on solving these problems. Unfortunately, these do not contribute di-
rectly to the increase in the production of petroleum.
• As the oil and gas market is controlled by the State private companies, there is
presently no central oil and gas agency to broker deals between domestic and
international organizations as well as private individuals.
• Debts of republics for the supplied petroleum.
The decline of the oil-extracting industry is caused by complex and inter-

connected reasons. The exit from the present situation is complicated by the global
nature of other problems. Therefore, if the economic crisis in the country persists
and the process of political reform in the former Soviet Union does not proceed
smoothly, the production of petroleum will be reduced.
In the petroleum sector as well as the gas industry, the problem of lack of
foreign investments is very serious. It is necessary to note that the flow of invest-
ments in Russia was never large during the years of reforms, in comparison with
China and other former socialist countries. Investment is necessary for the energy
sector of the economy, though this money and this amount of the joint projects is
obviously not sufficient to extricate the sector from crisis. The reasons for the
small cash flow are related to both economic and political situations in Russia as
well as the absence of a leader among the oil companies in the petroleum sector.
On the other hand, Russian companies have begun to carry out projects in
other countries (Prikaspiy, Kazakhstan, Iraq, etc.). In fact, these projects have
continued despite the last global crisis in Russia. This can only illustrate the power
of the oil sector.
There are other methods to increase petroleum processing and stabilize the
petroleum industry. Two methods can be facilitated by the state: these are the
increase of prices for petroleum in the domestic market and an improved taxation
system for oil-extracting enterprises. Enterprises have obligations as well. These
are in technical equipment, extraction of petroleum from oil wells with small pe-
troleum reserves (it is possible only with an increase in prices for petroleum in the
domestic and/or world markets), increase in the level of oil processing and sale of
produced petroleum and petroleum products.
The Tyumen area is the main oil-extracting region of Russia. Today almost
80 percent of extraction in this area is performed by six enterprises
(Yuganskneftegas, Surgutneftegas, Nizhnevartovsneftegas, Noyaborskneftegas,
Kogalymneftegas and Langepasneftegas). But in the near future, the absolute
volumes of production will be reduced. According to expert forecasts, reduction in
Nizhnevartovsk will be to 60%, and in Yugansk to 45%. Presently, both the Rus-
sian policy and economy are determined practically by complicated interactions
between various independent oil enterprises. There is no recognized leader among
them, and there is also presently no competition. Such a disintegration creates
many problems. Integration has been postponed until the future because of (i) the
large dynamics of the sector, (ii) the decrease of production for one enterprise
leads to the increase of production for another enterprise, and (iii) strong competi-
tion by LUKOIL, YUKOS and SIBNEFT for influence in the region between.
3.4 ARABIAN EAST [7-9]
Modern Arabian East includes thirteen Arabian countries and the state of
Israel. Despite its modest population, the Arabian East occupies a rather prominent
position in world culture, politics and economics. The Arabian East owes this
prominence to two factors: first, a unique geographical location and second, ex-
186 Chapters
treme riches via petroleum. The Arabian East holds the largest petroleum reserves
in the world. At least four countries of this sub-region (Saudi Arabia, Iraq, Kuwait
and United Arab Emirates) have, in the last few decades, constantly been in the
top ten of oil extractors in the world. The eastern regions of the Arabian Persian
Gulf constitute the basic crude oil "rich" territory. Opposite this area is the western
Mediterranean region that is essentially lacking in petroleum reserves. Extraordi-
narily high levels of petroleum production, coupled with a small native population
in the Persian Gulf is responsible for this level of affluence in these countries.
In the 1980s, the developed countries of the West developed complex meas-
ures to prevent a relapse of the increase in the prices of petroleum similar to the
level that occurred in 1973, as was stated earlier. The price of petroleum had be-
gun to reduce after the crisis. There was now a strong interest in alternative energy
sources. This was a clear indication to exporters of petroleum that the prominence
or value attached to petroleum can decline. Thus, even with the exploration of new
reserves that added to the very large reserves of petroleum in the region, the possi-
bility of alternative energy sources meant that the value of those reserves could
decline. First, Bahrain, that had the least reserves of petroleum among the coun-
tries of this region, had once seen the possibility of exhausting their petroleum
reserves. However, new reserves are being discovered all the time since the explo-
ration of new oil fields is a continuous process.
Petroleum exporters are usually interested in raw material, spare parts,
equipment, furnishings and especially of technologies delivered by transnational
corporations. The form of business cooperation between transnational corporations
on the one hand and the locals on the other hand is typically tuned towards a
mixed enterprise with more than 50% participation of local capital. As well, there
are also "non-joint"-stock forms of activity involving license agreements, training
of personnel, management and advertising, contracts on a "turn-key basis", and
engineering.
The developed countries that benefit from export of petroleum from the
Arabian East have definitely succeeded in their investments. The transnational
corporations and large international financial organizations (for example, the In-
ternational Monetary Fund) start from a simple investment of < 1 percent, to more
purposeful investments by proposing personal participation in management and
forcing acceptance of their decisions. The volume of foreign investments in Saudi
Arabia is estimated at hundreds of billions of dollars, and most of this ends up in
the USA. Kuwait owns a part of many British, Canadian, American, Western
European and Japanese oil companies, including British Petroleum, General Mo-
tors, IBM, Kodak, Total, Sony, etc. Besides Kuwait's three refineries, it also owns
three European refineries located in Denmark, Netherlands and Italy. It also owns
a thousand tank stations in Denmark, Sweden, Great Britain, Italy and Norway as
well as ten air-refueling stations in large Western European airports. Kuwait has
25 of its own oil tankers. Kuwait today owns a marketing network (involving the
full cycle from production until sale to the ultimate user) for a significant part of
produced petroleum. Foreign investments in Kuwait by the developed western
countries achieve profits of not less than 100 billion dollars. These profits from
foreign capital investments have become an essential source of foreign currency in
Kuwait.
3.4.1 Oman
Oman began oil extraction and export much later than the other countries of
this region. Therefore, although Oman is well endowed with petroleum reserves
(400 tons of petroleum per citizen), it remains a relatively not highly developed
country. Modern infrastructure is yet to fully take shape in Oman.
3.4.2 Iraq
The process of nationalization of the petroleum industry was completed in

1975. Today, Iraq provides approximately 3% of the world's petroleum supplies.
Analysts attribute the high petroleum activity and capacity to the availability of an
oil-extracting complex in Iraq. More than half the number of oil fields in the world
are concentrated in the Persian Gulf. A considerable fraction of this is located in
Iraq.
Iraq occupies second place (after Saudi Arabia) in the world in terms of
petroleum and gas reserves. It has a proven reserve of about 112.5 billion barrels.
However, in view of the UN sanctions, the rate of production of petroleum has
been low. For example, in the period from January - August 1998, the production
rate was approximately 2 million barrels per day. In the absence of UN sanctions,
Iraq projects that in the first year the level of production would be 3 million barrels
per day. After 3-5 years, the production rate would increase to 3.5 million barrels
per day, and to 6 million barrels per day in 10 years. If it uses the full pipeline
loading capacity, Iraq is capable of exporting 1.4-2A million barrels per day. This
will be made up of 0.8-1.6 million barrels per day over the pipeline at Circuc-
Jeheyn and 0.6-0.8 million barrels per day over port of Mine Al-Bacr).
Iraq nationalized the mineral industry in 1972 by putting the sector under the
control of the ministry responsible for the petroleum industry and the Iraq State
Petroleum Company. The Iraq nationalization was completed by confiscation of
the Iraqi petroleum participating company, co-owners of which were British Pe-
troleum, Total, Shell, Exxon, Mobil, and Partex. Before the Iran-Iraq war, Petro-
bras and Elf Aquitaine also operated in Iraq under contracts alongside with the
Iraqi Petroleum Company. While these companies were operating in Iraq, many of
the largest oil fields, such as the ones in Kircooc (1927), Rumeyla (1953), Buzur-
gan (1969), Abu Jirab (1971), Megun (1976) and Nahr Umar (1977) were opened.
188 Chapters
The main company now in Iraq is the Iraq State Petroleum Company. The
following companies are working independently but are still subordinates to the
State Petroleum Company:
The State Company for Oil Projects (SCOP) is responsible for work con-
nected to the development of upstream and downstream projects.
The Oil Exploration Company (OEC) is responsible for prospecting and geo-
physical works.
The State Organization for Oil Marketing (SOMO) is engaged in the trade of
petroleum and is responsible for connections with organization of the coun-
tries to which they export Iraqi oil.
The Iraqi Oil Tankers Company (IOTC) - transport tanker company.
Northern Oil Company (NOC).
Southern Oil Company (SOC).
The last two companies are engaged in extracting petroleum in the northern
and southern parts of Iraq, respectively.
Finally, it has to be noted that as a result of the use of modern technologies
(horizontal and multilateral drilling) for petroleum extraction from Iraq oil wells,
the estimated proven petroleum reserves in Iraq are sure to increase in the near
future. It is also necessary to emphasize that a major part of the research and de-
velopment work in Iraq is still in progress. There is the intention to research on the
deep oil wells on Jurassic and Triassic levels (mainly in the Western Desert). A
successful outcome can open up additional oil reserves. However, research in this
area has not been carried out up till now.
3.4.3 Iran
The proven petroleum reserve estimates in Iran are 90 billion barrels (not
less than 9% of all world reserves). In 1998, 3.6 million barrels of petroleum were
extracted daily from Iranian oil fields. Daily consumption of petroleum is 1.13
million barrels. Capacity of petroleum processing is 1.45 barrels per day. The
importers of Iranian oil are essentially Japan, South Korea, Great Britain, China,
Turkey, Thailand, India, Brazil and Taiwan. The petroleum and gas industry of
Iran is under the complete control of the state. The State Petroleum Company is
called National Iranian Oil Company NIOC. It conducts research on development
of both petroleum and gas wells. It is also engaged in providing transportation for
both the raw petroleum and its products. The National Iranian Gas Company
(NIGC) is engaged in extracting, processing, transporting and the export of gas,
whereas the National Petrochemical Company (NPC) is responsible for petro-
chemical manufacture in Iran. The most active foreign companies in Iran today are
Gazprom, Petronas, Shell and Total. The main oil fields in Iran are Gagaran, Ma-
run, Avaz, Bangistan, Aga Gari, Raga-i-Safid, Pars and Hakim. The main oil re-
fining factories are Abadan (capacity 477,000 barrels per day), Isfagan (251,000
barrels per day), Bandar Abas (220,400 barrels per day), Teheran (213,750 barrels
per day), Arak (142,500 barrels per day), Tebriz (106,400 barrels per day), Shiraz
(38,000 barrels per day), Kermanshah (28,500 barrels per day) and Lavan (20,000
barrels per day).
In August of 1996, the American Congress approved a law that was aimed
at imposing sanctions against Iran and Libya (so-called ILSA). The provisions of
the law sought to ban non-American companies investing not less than 40 million
dollars annually from performing the development of petroleum and gas wells in
Iran. In 1997, the investment limit was lowered to 20 million dollars. ILSA is not
the first sanction imposed by the USA against Iran. For example, in the beginning
of 1995, President Clinton signed two governmental orders, according to which
American companies and their subsidiaries are not permitted to finance the devel-
opment of any petroleum sector in Iran. One of the large-scale contracts cancelled
as a result of these orders was the contract between Iran and the American com-
pany Conoco for the development of blocks A and E of the Sirri oil field. The
project was estimated to be 550 millions dollars. French Total and Petronas were
quickly engaged to replace Conoco. In the middle of August of 1997, President
Clinton signed one more governmental order (Nr. 13059), which stipulated inter-
diction for any investment actions of American citizens in Iran. Despite ILSA, a
consortium comprising Total, Petronas and Gazprom has continued with the proj-
ect of developing gas wells called the Southern Pars (volume of investments was 2
billion dollars).
From a purely objective reasoning in May of 1998, the White House made it
clear that the ILSA sanctions were not applicable to oil and gas pipelines that were
only connecting through the territory of Iran. This move probably resulted from
the construction of major pipelines and gas pipelines from Kazakhstan, Azerbaijan
and Turkmenestan. It has to be noted that Iran occupies a strategic geopolitical
location for connection of petroleum transportation routes. This unique location
allows a considerable decrease in transportation price for transfer of raw material
to the world markets through connecting pipelines in Iran in comparison with
other routes (for example, through Turkey).
In December of 1998, the President of Iran declared that the main thrust of
government in the petroleum sector was the re-structuring and modernization of
the petroleum industry, and the opening up of new oil fields. In January of 1999,
the parliament of Iran ordered the Ministry of Petroleum of Iran to report monthly
concerning work that was carried out. In turn, the National Iranian Petroleum
Company (NIOC) concentrated efforts on prospecting work. Accordingly, NIOC's
plan was to drill 61 prospecting oil wells in the sea and on land by 2000.
By the year 2000, Iran was able to offer about 20 projects in gas and oil
sector to investors. These included measures for development of sea deposits and
for finishing the modernization of a number of refineries (for example, on an is-
land Lavan). In March of 1998, Bow Valley Energy (Canada) and British Premier
Oil signed a contract for 270 millions dollars for providing development of a sea
oil field called Balal valued at an estimated 80 millions barrels of petroleum. But
190 Chapters
at the end of 1998, Bow Valley Energy left the project, with the explanation of
financial problems resulting from the Asian crisis. In February of 1999, the gov-
ernment of Iran gave the rights for the development of the sea oil field at Dorud
and gas field near Harg Islands to a French company Elf Aquitaine and an Italian
enterprise ENI. In the opinion of the Iranian party, the prospecting of Dorunda (the
project is estimated to be half a billion dollars) will increase their proven petro-
leum reserves to 700 million barrels and an increase in the daily production of
petroleum from 90 to 220 thousand barrels.
In January of 1999, British Petroleum and Amoco began negotiation with
the Iranian government about the development of Avaz oil field. The same oil
field also attracted the French enterprise, Total. At the same time the Norwegian
company Saga Petroleum initiated negotiations with the Iranian government con-
cerning development of Dehl Uran and Cheshmen-Kosh oil fields. Saga Petroleum
has signed an agreement with NIOC for 2.7 millions dollars for seismic data in a
number of prospective places, including the block of Dara and the sea oil well
Handidgan. In December of 1998, Gazprom and NIOC - Naftgaran Engineering
Services Co. created a joint venture aimed at carrying out prospecting and drilling
work in Iran.
3.4.4 Qatar
The main foreign trade partners for Qatar are Japan, the USA, Great Britain,
Germany, France and Italy. Oil export accounts for 80% of total export.
The proven petroleum reserve estimate for Qatar is 3.7 billions barrels.
More than 650,000 barrels of petroleum is extracted in Qatar daily. The country
exports more than 600,000 barrels of petroleum per day. Approximately 70% of
petroleum in Qatar is exported to Japan and less than 10% to other countries of
Southeast Asia. The capacity for oil processing in Qatar is 57.5 thousand barrels of
petroleum per day. The petroleum sector of Qatar is under the total control of the
state. The state petroleum company of Qatar - Qatar General Petroleum Corpora-
tion (QGPC) - is engaged in prospecting work and the production of petroleum
products. The National Oil Distribution Company (NODCO) carries out the proc-
essing of petroleum whereas Qatar Petrochemical Company (QAPCO) is engaged
in petrochemical manufacture. Qatar Fertilizer Company (QAFCO) produces
fertilizers. On the other hand, Qatar Liquefied Gas Company (Qatargas) and Ras
Laffan LNG Company supervise manufacture and marketing of liquefied natural
gas (LNG).
The "overland" oil field of Qatar is in Duhan. About 2.2 billion barrels of
petroleum is concentrated there. It should be remembered that the proven petro-
leum reserve of Qatar is about 3.7 billion barrels. More than 1.5 billion barrels of
petroleum are concentrated in six shelf oil fields (Bui Hanan, Meydan Mahzam, Id
Al-Shargi, Al-Shahin, Al-Rayan and Al-Halig). Practically all extracted petroleum
from Qatar is exported to the countries of Southeast Asia.
One more significant oil field - Al-Holig - is located near the sea border
between Qatar and Iran. The work on this field began in March of 1997 (it has to
be noted that the French company Elf Aquitaine planned to begin the work in
1991). In March of 1998, this French Company extracted petroleum at the rate of
up to 30 thousand barrels per day from this field. Contract "production sharing"
signed between Elf Aquinaine and Qatar was made for 25 years. Elf Aquitaine has
55% of individual share while 45% share belongs to Italian Agip. The industrial
reserves of petroleum in Al-Haliga are estimated at 70-80 millions barrels. Nowa-
days, Al-Shahin is considered to be one of the most productive oil fields in Qatar.
Approximately 100 thousand barrels of petroleum per day are extracted from this
field. In 2000, the Danish company was going to finish a project to increase the
level of production to 150 thousand barrels per day.
3.4.5 Kuwait
The history of the petroleum industry in Kuwait can be considered to have

started in 1934. At this time, sheyh Ahmad Al-Gdaber Al-Salah allocated a place
for business collaboration between Anglo-Persian Oil (now British Petroleum) and
Gulf Oil Corporation. Drilling began in 1936 and in 1938, the Burgan oil field was
opened. But its development only began after the Second World War, and export
started from 1946. In I960, the Kuwait national company was established. The
share of the state was 60% at first, and became 100% since 1975. In 1980, Kuwait
Petroleum Corporation (KPC) was established. Included as sectors were the Ku-
wait national company and many others. Kuwait has been a member of OPEC
since its creation in 1960. At the time of the Iraq-Kuwait war in August of 1990,
the production of petroleum in the country was approximately 100 million tons,
from which 10 million tons were extracted from oil wells in shared zone taking
place under joint administration of Saudi Arabia and Kuwait. Production in the
territory of the country has been conducted on 12 basic deposits.
A major portion of the oil production is exported to more than 30 countries.
The main importer of Kuwaiti petroleum is Japan. In Kuwait, there are four oil
refineries with a total capacity of 40 million tons per year. In 1989, 38.6 million
tons of petroleum were produced, from which six million tons were used inside
the country. The rest was exported.
During the Iraq-Kuwait war, 800 or more than half of the oil wells in Ku-
wait and the shared Zone were destroyed. One-third of the petroleum extracted in
the period preceding the war was burned during the war. It is estimated that by the
time the last fires on oil wells were extinguished petroleum worth approximately
40 billion dollars was lost. After restoration of the oil wells, there was significant
reduction of pressure in the oil wells. As a result, secondary and tertiary methods
of oil extraction were required for production. The consequence has been a four-
fold increase in the cost of extraction (four dollars per ton before the war). As a
192 Chapters
result, the capacity for oil processing has decreased to 6.5 million tons per year
(more than six times lower).
The proven petroleum reserve estimate in Kuwait is 96.85 billion barrels.
This accounts for 10% of world reserves. Natural gas wells are 1500 billion cubic
meters. The annual volume of natural gas extraction is 7.8 billion cubic meters.
The oil-extracting capacity is 2.35 million barrels per day. In 1998, Kuwait ex-
tracted 101 million barrels of petroleum from its wells. It was expected that there
would be the potential to bring the extraction to 2.5 million barrels per day at the
end of 2000 and up to three million barrels per day by 2005. Two thirds of the
extracted petroleum is exported, 20% is exported to the USA, 50% to Southeast
Asian and Japan.
The oil and gas industry of Kuwait is subordinated to Kuwait Petroleum
Corporation (KPC). Its structure includes five companies. (1) Kuwait Oil Corpo-
ration (KOC) looks at both the production and export of petroleum and gas. (2)
Kuwait National Petroleum Company looks after oil processing and manufacture
of liquified natural gas, as well as their marketing and export. (3) Petrochemical
Industries Company (PIC) is engaged in the manufacture and export of petro-
chemical products. (4) Kuwait Oil Tankers (KOTC) engages in the transportation
of petroleum, petroleum products and liquefied gas. (5) Kuwait Foreign Petroleum
Exploration Company looks at both the extraction of petroleum and gas abroad. In
1998, the Supreme Council of Kuwait accepted the decisions to reorganize the
KPC, as well as privatize the PIC and KOTC.
The activity of foreign oil companies is limited by the agreement concerning
technical support. KPC has signed agreements with Chevron, British Petroleum,
Shell, Exxon and Total. Generally, there are 150 foreign firms, mostly from the
USA and England, involved in the petroleum business. About 15 billion dollars of
investments is required in order to realize the "ten years program".
Western oil companies insist on production sharing for capital investments
and "know-how" in the development of oil wells. The Supreme Council of petro-
leum accepted cooperation with foreign firms on the conditions of production
sharing, but progress in this direction was suspended because of strong opposition
from the National Assembly. As a compromise, the oil ministry developed a
model of cooperation with foreign companies with agreements only for technical
service. According to the arrangement, the foreign company will be completely
responsible for an oil well, including the investment, its development, as well as
applying the required technology and equipment. All petroleum remains the prop-
erty of Kuwait, but the foreign company, besides indemnification for operational
expenses and deductions for the capital investments, receives a certain percentage
from the sale of additional volume of raw material extracted with the help of their
know-how. This model of attracting investors to the local market has been referred
to as the Kuwaiti project.
In the first stage of the project, the model will be used for the development
of five northern and two western oil wells. As a result of the application of ad-
vanced western technologies, it is expected that by 2005, the extraction of petro-
leum will increase as given below. From 400,000 to 900,000 barrels per day in the
northern oil wells, 225,000 to 515,000 barrels per day in the Raudatein oil wells,
95,000 to 250,000 barrels per day in Sabrie, 3,000 to 30,000 barrels per day in
Bahrahe, and 78,000 to 110,000 barrels per day in Ratge and Abdali. Western oil
wells should give an extraction volume of 270,000 barrels per day. The Kuwaiti
project also includes the construction of a new export terminal on the island of
Bubiyan.
Readiness to cooperate in the Kuwaiti project was expressed by Mobil,
British Petroleum, Amoco, Shell, Chevron, Texaco, Conoco, Philips, Arco, Elf,
Total and Lasmo. In view of the large number of potential partners, Kuwait will
not give the whole field to only one foreign company, but to a foreign enterprise to
form a consortium of two or more firms.
One of the strategic directions of Kuwait petroleum policy is the creation of
infrastructure for oil processing and marketing of petroleum products abroad. This
is achieved by purchasing shares by foreign oil companies that will allow an ef-
fective control of the complete cycle of extraction, processing, and marketing of
petroleum and petroleum products. This is expected to increase the capacity of oil
refineries abroad to 700 thousand barrels per day, for those in Europe up to 300
thousand barrels per day, and in Asia up to 400 thousand barrels per day. The
overall capacity of oil refineries owned by Kuwait in Denmark, Netherlands and
Italy is 230 thousand barrels per day. Kuwait supervises 6.5 thousand gas stations
in Western Europe. By the signing of an agreement with Swedish companies,
Kuwait supervises 26% of the oil market in this country. The agreements for the
creation of joint refineries with China, Pakistan and Thailand with capacity of 300
thousand barrels per day have already been signed.
Nationalization of the petroleum sectors by the largest producers in OPEC
such as in Iraq, Venezuela, Saudi Arabia and Kuwait resulted in the reduction of
investments by Kuwait in these countries. The extra funds freed up were spent for
the development of new sources of raw material in other regions of the world.
According to a Middle East Economic Survey, 350 billion dollars was spent to
increase the volume of petroleum extraction in nontraditional regions in 1980-
1995.
The application of modern technologies for prospecting, developing and
operating petroleum wells has essentially reduced financial expenses for these
needs (approximately 40%). This scenario has also resulted in the increase of
petroleum export and a decrease in the price of crude oil. The planned increase in
the volume of petroleum extraction will be twelve million barrels per day in 2005,
from which the part for OPEC is nine million barrels per day, and the part for
other countries is about three million barrels per day. After 2005 it is predicted that
there will be recession of oil manufacture in the so-called independent exporters
States.
194 Chapters
3.4.6 United Arab Emirates
The proven petroleum reserve estimate of the United Arabian Emirates is

approximately 98 billion barrels (slightly less than 10% of world oil reserves). The
biggest part of oil wells is concentrated in Emirate Abu Dabi. The extraction of
petroleum in United Arab Emirates exceeds 2.3 million barrels per day. Nowa-
days, approximately 2.2 million barrels of petroleum is exported. The main im-
porters of petroleum from the United Arab Emirates are Japan (more than 60% of
general export) and other countries of Southeast Asia (not less than 20%). The
capacity for oil processing in the United Arab Emirates is approximately 287
thousand barrels per day.
The petroleum sector in each Emirate is controlled by the government. The
State Petroleum Company of United Arab Emirates is known as the Abu Dhabi
National Oil Company (ADNOC). This includes three oil and gas operational
companies, five service companies, two transport companies (sea transportation),
etc. The main wells are in Abu Dabi-Asab, Beb, Bu Hasa and Al-Zakum.
3.4.7 Saudi Arabia
The major portion of exports from Saudi Arabia is petroleum and petroleum
products. The income from petroleum export is about 24 billion dollars (90% of
the general income). It should be noted especially that, despite competition from
Mexico, Venezuela and Canada, Saudi Arabia remains the main exporter of pe-
troleum to the USA and Japan.
The proven oil reserve estimate for Saudi Arabia is 261.5 billion barrels
(almost a quarter of the proven oil reserves in the world). The daily extraction of
petroleum in Saudi Arabia exceeds 8 million barrels. Oil refining capacity is 1.6
million barrels per day. The petroleum industry in the country was nationalized in
the 1970s. The petroleum sector is operated by the Supreme Petroleum Council
and the state companies of Saudi Arabian Oil Co. (Saudi Aramco) and Petro-
chemical Saudi Basic Industries Corporation (SABIC). The main oil fields are in
Gavar, Safaniya, Nazhd, Berry, Manifa, Zuluf, Shaybah, Abu Saafa, Hursaniya
and Abgeyg. The main foreign companies operating in Saudi Arabia are the Ara-
bian Oil Company from Japan (AOC), Mobil, Shell and Texaco. However, the
Arabian Oil Company has not been operating in Saudi Arabia since the beginning
of 2000.
In Saudi Arabia there is approximately a total of 77 oil and gas fields. How-
ever, the main oil fields of the country are concentrated in eight areas. One of them
is Gavar, the biggest overland Oil field with reserves estimated at 70 billion bar-
rels of petroleum. Another is Safania, the largest shelf oil field in the world, that
has reserves estimated at 19 billion barrels of petroleum.
The Japanese company AOC operates on two shelf oil wells, Hafgy and
Hut, and extracts about 300 thousand barrels per day. American Texaco developed
three oil wells on the ground, Vafra, Southern Favaris and Southern Um Gudayr,
and extracts more than 200 thousand barrels per day. Texaco has signed a contract
for its operation to last till 2010, and the American company plans to considerably
increase the volume of production. In September of 1998, the Minister of Oil and
Natural Resources of Saudi Arabia met with heads of a number of American oil
companies (Chevron, Mobil, Texaco, Arco, Conoco, Phillips Petroleum). As a
result of these negotiations, officials of Saudi Arabia have asked the companies to
present their bids for possible joint projects in the gas and petrochemical sectors.
International Petroleum Companies
4.1 BRITISH PETROLEUM [9]
British Petroleum is one of the biggest companies in Britain and one of the
world's largest oil and petrochemicals groups. At the beginning of its history it was
known as the Anglo-Persian Oil Company.
The history of the British Petroleum or the Anglo-Persian Oil Company
began with the work of William Knox D'Arcy shortly after the turn of the twenti-
eth century (1901). William Knox D'Arcy obtained a concession from the Shah of
Persia to explore the oil resources of the country, excluding the five northern
provinces that bordered Russia. Having been granted the concession, D'Arcy em-
ployed an engineer, George Reynolds, to undertake the task of exploring for oil in
Persia.
Meanwhile, the costs mounted, stretching D'Arcy's resources to the point
where he sought outside financial assistance. This came in 1905 from the Burmah
Oil Company, which provided new funds for his venture.
More exploration in Persia followed without success until eventually, in
May of 1908, Reynolds and his associates struck oil in commercial quantities at
Masjid-i-Suleiman in southwest Persia. It was the first commercial oil discovery in
the Middle East. This signaled the emergence of that region as an oil producing
area.
After the discovery had been made, the Anglo-Persian Oil Company was
formed in 1909 to develop the oilfield and exploit the concession. At the time of
Anglo-Persian's formation, 97% of its ordinary shares was owned by the Burmah
Oil Company. The rest were owned by Lord Strathcona, the company's first
chairman.
Although D'Arcy was appointed a director and remained on the board until
his death in 1917, he was not to play a major part in the new company's business.
His role as the initial risk-taking investor was past and the daunting task of devel-
197
198 Chapter 4
oping the oil discovery into a commercial enterprise shifted to others, amongst
whom one particular person stands out: Charles Greenway. Greenway was one of
Anglo-Persian's founder-directors, becoming managing director in 1910 and
chairman, after Strathcona, in 1914.
Greenway, anxious to avoid falling under the domination of Royal Dutch-
Shell, also turned to another potential source of revenue and capital: the British
government. The basis of an agreement to their mutual advantage lay in Green-
way's desire to find new capital and an outlet for Anglo-Persian's fuel oil; and, on
the government's part, in the desire by the Admiralty to obtain secure supplies of
fuel oil, which had advantages over coal as a fuel, for the fleet of the Royal Navy.
After long negotiations, agreement was reached in 1914 shortly before the
outbreak of the First World War. Anglo-Persian was contracted to supply the
Admiralty with fuel oil and the government injected two million pounds of new
capital into the company, receiving in return a majority shareholding and the right
to appoint two directors to Anglo-Persian's board.
Although the government undertook not to interfere in Anglo-Persian's
normal commercial operations, its shareholding introduced an unusual political
dimension to the company's affairs. In later years, the government shareholding
was reduced and, apart from a tiny residual holding, ended in 1987.
Further expansion followed in the decade following the First World War.
New marketing methods were introduced, with curbside pumps replacing two-
gallon tins for the distribution of motor spirit (gasoline). Anglo-Persian also mar-
keted its products in Iran and Iraq; it established an international chain of marine
bunkering stations, and in 1926 began to market aviation spirit. New refineries,
much smaller than the plant at Abadan, also came on stream at Landarcy in South
Wales in 1921 and at Grangemouth in Scotland in 1924. Moreover, the company's
majority-owned French associate had a refinery at Courchelettes, near Douai. On
the other side of the world, in Australia, a new refinery at Laverton, near Mel-
bourne, was commissioned in 1924.
Exploration was carried out not only in the Middle East, but also in other
areas, such as Canada, South America, Africa, Papua New Guinea and Europe.
By the time Greenway retired as chairman in March 1927, he had realized
his main strategic goal of establishing Anglo-Persian as one of the world's largest
oil companies, with a substantial presence in all phases of the industry. In 1935,
the company was renamed the Anglo-Iranian Oil Company.
After the Second World War, Europe had to be reconstructed. This de-
manded a high amount of oil that enabled Anglo-Iranian to expand its business
greatly. The company's sales, profits, capital expenditure and employment all rose
to record levels in the late 1940s. By this time, the refinery at Abadan was the
largest in the world.
While the company was expanding its operations in the late 1940s, it was
also engaged in negotiations with the Iranian government concerning the terms of
its oil concession. Long and complex negotiations failed to produce an agreement,
and in 1951 the Iranian government passed legislation nationalizing the company's
International Petroleum Companies 199
assets in Iran. It was then Britain's largest single overseas investment. The nation-
alization precipitated a major international crisis in which the British government
became deeply involved. The company's operations in Iran were brought to a halt.
Only after three years of intensive negotiations was the crisis resolved by the
formation of a consortium of oil companies, which, by agreement with the Iranian
government, re-started the Iranian oil industry in 1954. Anglo-Iranian was re-
named The British Petroleum Company in 1954 and held a 40% share in the con-
sortium.
At first, it was noted that the company focused its business in the Middle
East, first of all in Persia (Iran). From the late 1960s the center of company inter-
ests shifted westwards, towards the USA and Britain itself.
Although all of these events were important for the company, it was hydro-
carbons under the North Sea and under the permafrost of Alaska that were to play
the key role in transforming British Petroleum into the company it is today. Ear-
lier, in 1959, the Dutch had discovered a giant gas field on the edge of the North
Sea at Groningen. This discovery encouraged others to begin searching for hydro-
carbons offshore. British Petroleum had their first success in British waters when,
in 1965, it found the West Sole gas field, which it brought on stream two years
later. The search for oil spread further north, and in 1970 British Petroleum dis-
covered the Forties field, the first major oil and gas commercial discovery in the
UK sector.
At this time in Alaska, USA, British Petroleum was rewarded for ten years'
exploration effort when, in 1969, it announced a major oil discovery at Prudhoe
Bay on the North Slope. When it became clear that through its large share in Prud-
hoe Bay, British Petroleum acquired the rights to part of the biggest oilfield in the
USA, the company decided that its Alaskan oil could best be handled by a well-
established US refining and marketing company. It signed an agreement with the
Standard Oil Company of Ohio in August of 1969. This company, the original
John D. Rockefeller Standard Oil, was the market leader in Ohio and was strongly
represented in neighboring states.
Under the agreement, which became effective from January 1, 1970, Stan-
dard took over British Petroleum leases at Prudhoe Bay and some East Coast
downstream assets that British Petroleum had acquired in 1968. In return, British
Petroleum acquired 25% of Standard Oil equity, a stake that would rise to a ma-
jority holding in 1978 when the Standard Oil share of Alaskan production passed
600,000 barrels a day.
The 1970s saw the great petroleum crisis that was to have serious effects on
the world's economy. British Petroleum lost direct access to most of its supplies of
OPEC oil as the OPEC countries took control of production and prices.
In 1973, the price explosion had a dramatic effect on the demand and the
sales of British Petroleum. By 1978, sales were a little higher, but then came the
Iranian revolution and another major rise in the price of oil. In 1979, BP suffered
further blows when its assets in Nigeria were nationalized and its supplies from
Kuwait cut back. By 1980, its sales dropped again.
200 Chapter 4
The company was rescued, thanks to high investments outside of the Middle
East. Since the early 1980s, British Petroleum has developed many more oil and
gas fields in the North Sea. Among these have been, in the UK sector, Magnus, the
Village gas fields at Miller and Bruce and, in Norwegian waters, Ula and Gyda. In
Alaska, the construction of the Trans-Alaska Pipeline System enabled the Prudhoe
Bay field to come on stream in 1977. In 1981, the Kuparuk field also started pro-
duction, and towards the end of 1987, the world's first continuous commercial
production was recorded from an offshore area in the Arctic when the Endicott
field was commissioned.
In 1989, the company launched a campaign to introduce a stronger corporate
identity, featuring a restylcd British Petroleum shield and an emphasis on the color
green. In a complementary program that was to prove highly successful, British
Petroleum started to re-image its global network of service stations in a new de-
sign and livery.
At the same time, British Petroleum explorers, in the quest to find new
sources of oil and gas, began to focus their skills more and more on regions of the
world that for political or technical reasons remained relatively unexplored. The
regions included Colombia, the Republics of the former Soviet Union, and the
deep water areas of the Gulf of Mexico.
The process of integration following this major transactional phase was very
well advanced in the year 2000 and British Petroleum acquired a new base from
which to take the next step forward. The combination of British Petroleum,
Amoco, ARCO and Burmah Castrol provides the area with the skills and the peo-
ple necessary to deliver a distinctive rate of performance growth on a sustainable
basis.
British Petroleum at the beginning of the twentieth century is an interna-
tional company, having operations in over 70 countries. Its key businesses are oil
and gas exploration and production; the refining, marketing and supply of petro-
leum products; and the manufacturing and marketing of chemicals.
4.2 CASTROL [10]
The history of Castrol can be considered to have begun in the twentieth

century, when Charles Cheers Wakefield founded the specialty lubricant company.
This company played a key role in the development of the transport industry.
Many of developments in the area of lubricants can be credited to Castrol. In
1909, the motor oil based on castor oil appeared on the market. Twenty-four years
later, the company became the first company in the world to use additives in motor
oil (organic compounds of chrome).
In 1949, the Deutsche Castrol GmbH company introduced motor oils with
anti-corrosive and anti-oxidative additives to the market. Three years later, the
company developed an absolutely new type of motor oil with low viscosity for
sport cars. This was the reason why Castrol was the chosen oil for many of the
sport events where world speed and endurance records, on land, sea and air, were
broken. The land speed record alone has been broken 21 times by cars using Cas-
trol lubricants.
In 1975, the company became the first in the world to introduce a new oil,
SAE 15W-40, to the market. One year later, Castrol developed an oil using a hun-
dred percent synthetic oil as base.
In 1986, Castrol developed the first oils with low phosphor content to pro-
tect catalysts. And within nine years, Castrol created a synthetic oil with the low-
est viscosity.
At the beginning of the twentieth century, the products of Castrol helped
machines and instruments to achieve greater reliability, endurance and cost effec-
tiveness. The new technologies developed by Castrol have resulted in technologi-
cal achievements that make Castrol lubricants the cost-effective choice across a
wide range of applications.
4.3 EXXONMOBIL [11]
The history of the ExxonMobil corporation began when Exxon and Mobil
companies were, at the beginning the 20th century, components of one company
(Standard Oil, see the first section of chapter 3). At the end of the century, they
came together as a single organization. For most of the years in between, they
blazed separate trails as independent, competing enterprises. Each company placed
a singular imprint on the energy industry and on a dynamic era of world history.
Both Exxon and Mobil have their roots in the late 19th century with the
Standard Oil Trust. Standard Oil Company of New Jersey and Standard Oil Com-
pany of New York were the chief predecessor companies of Exxon and Mobil.
For both companies, the remainder of the 19th century was a time of expan-
sion beyond America's shores. The large kerosene market enabled overseas ship-
ments of products in large quantities. Affiliates and sales offices of both compa-
nies spread across Europe and Asia. Standard Oil's MEI FOO kerosene lamps
introduced illumination across China and opened a vast new market.
After the dissolution of Standard Oil Trust, the American kerosene output
was eclipsed for the first time by a formerly discarded byproduct - gasoline. The
growing automotive market ultimately inspired the product trademark Mobiloil,
registered by Socony in 1920. Jersey Standard and Socony separately faced rising
competition. Both companies were not fully integrated. Over the next twenty
years, each expanded across the U.S. and abroad.
Large acquisitions and mergers helped Jersey Standard acquire a 50 percent
interest in Humble Oil and Refining Company, a Texas oil producer. Socony pur-
chased a 45 percent interest in Magnolia Petroleum Company, a major refiner,
marketer and pipeline transporter. In 1931, Socony merged with Vacuum Oil Co.,
an industry pioneer dating back to 1866 and a growing Standard Oil spin-off in its
own right.
202 Chapter 4
In the Asia-Pacific, Jersey Standard had oil production and refineries in

Indonesia, but no marketing network. Socony-Vacuum had Asian marketing out-
lets supplied remotely from California. In 1933, Jersey Standard and Socony-
Vacuum merged their interests in the Asian region. Standard-Vacuum Oil operated
in 50 countries, from East Africa to New Zealand, before it dissolved in 1962.
The intensive expansion of the companies was slowed down by the Second
World War. Each company improved the refining output to supply the war effort.
This was the main motivation for the new technologies developed, such as Jersey
Standard's groundbreaking process for increasing the fuel octane number and
Socony-Vacuum's synthetic lubricants. Both companies suffered wartime casual-
ties. Many refineries and other facilities in Europe and Asia were destroyed.
Over the next few years after the war, ExxonMobil's predecessor companies
started to process refinery by-products into many basic petrochemical and numer-
ous derivatives. Since the end of the Second World War, the two companies each
already had advanced technologies and expanded business in more than 100
countries.
Mobil Chemical Company was formed in 1960. In 2000, the principal prod-
ucts included all the basic aromatics and olefins for the petrochemical industry,
ethylene glycol and polyethylene. The company produced synthetic lubricating
oils, additives, propylene packaging films and catalysts. Manufacturing facilities
were located in 10 countries.
Exxon Chemical Company became a worldwide organization in 1965 and in
2000 was a major producer and marketer of olefins, aromatics, polyethylene and
polypropylene along with specialty lines such as elastomers, plasticizers, solvents,
process fluids, oxo alcohols and adhesive resins. The two chemical companies
combined their operations within ExxonMobil Chemical.
In 1955, Socony-Vacuum became Socony Mobil Oil Company and, in
1966, Mobil Oil Corporation. Ten years later, a newly incorporated Mobil Corpo-
ration embraced Mobil Oil as a wholly owned subsidiary. Jersey Standard changed
its name to Exxon Corporation in 1972 and established Exxon as an uncontested
trademark throughout the United States. In other parts of the world, Exxon and its
affiliated companies continued to use its long-time Esso trademark and affiliate
name.
During the oil crisis in the 1970s, Exxon and Mobil escalated exploration
and development of oil wells outside of the Middle East: in the North Sea, the
Gulf of Mexico, Africa and Asia. By the early 1980s, oil was in surplus, and prices
fell. In the mean time, Exxon and Mobil continued to operate at a relatively low
price. Each company continued to advance new technologies, introduce marketing
innovations and extend its reach into emerging, high-growth markets. The two
companies became more efficient, reduced costs and increased shareholder value.
In 1998, Exxon and Mobil signed the historic document (for both compa-
nies): a definitive agreement to merge and form a new company called ExxonMo-
bil Corporation. After shareholder and regulatory approvals, the merger was com-
pleted in November 30th, 1999.
The modern world marketing of the ExxonMobil products proceeds under

the symbol of the tiger. This tiger was spotted in England in the mid-1930s, when
it was the Esso symbol. This tiger was stopped in its tracks by the Second World
War. The Exxon brand tiger returned in 1953 when competitive gasoline market-
ing resumed. In England and elsewhere in Europe, the powerful cat helped dispel
memories of the low-quality fuels available during the war years.
In 1959, as tiger advertisements waned in Europe, the tiger came to life in
Chicago, USA, where an advertising copywriter sat at his typewriter thinking up
symbols of power for a local Esso campaign. At the same time, a famous spot
slogan (which still exists now) appeared: "Put a Tiger in Your Tank". At first, this
tiger was the friendly cartoon character. After the Arab oil embargo in 1973, the
world began to focus on the importance of energy conservation. Esso marketers
realized this serious issue deserved a more serious symbol than a cartoon. In 1975,
Esso marketers in Britain introduced the first television advertisement featuring a
real tiger to depict strength and reassurance.
The modern ExxonMobil Corporation conducts business in more than 200
countries around the world, whether it is exploration and production of oil and gas,
manufacturing and marketing of fuels, lubes and chemicals, electric power gen-
eration or coal and minerals operations.
The upstream business of the corporation is organized into five global com-
panies:
• Exploration
• Development
• Production
• Gas Marketing
• Research
The ExxonMobil corporation is the world's largest non-government pro-

ducer and reserves holder for petroleum products.
The proven reserves of the corporation stand at 21 billion oil-equivalent
barrels, about 13 years of production at current levels. The non-proven portion of
the resource base is approximately 48 billion oil-equivalent barrels.
ExxonMobil Exploration company has activities in 48 countries around the
world and undeveloped acreage holdings in excess of 120 million acres. In 1998,
the companies added resources of more than 1.7 billion oil-equivalent barrels.
ExxonMobil Development Company's works are geographically and tech-
nically diverse, ranging from heavy oil in Venezuela to deep-water development in
the Gulf of Mexico, West Africa (e.g. Nigeria) and Indonesia to liquefied natural
gas in Qatar. The portfolio includes both company-operated projects and major
projects operated by others.
The ExxonMobil Production Company is responsible for one of the largest
industrial portfolios of worldwide producing oil and gas operations. ExxonMobil
204 Chapter 4
produces 4-4.5 million oil-equivalent barrels of oil and gas per day from 24 coun-
tries.
The ExxonMobil Gas Marketing Company is the world largest non-
governmental marketer of gas. In 1998, ExxonMobil sold gas and liquefied natural
gas in 25 countries. The organization maintains gas-marketing offices in 19 coun-
tries.
The ExxonMobil Research Company provides the successful technical
expertise and large work experience of both companies that has historically con-
tributed to Exxon and Mobil's successes. The Upstream Research Company fa-
cilitates efficient and effective technology development and transfer to ExxonMo-
bil upstream companies. Exxon and Mobil have historically shared a strong com-
mitment to upstream technology research and have pioneered many key technolo-
gies in use today. Continued development of breakthrough and proprietary tech-
nologies will allow ExxonMobil to access and develop new resources at a lower
cost.
ExxonMobil downstream business includes refining, retail marketing, lubri-
cant basestock production and sales, finished lubricants, petroleum specialty prod-
ucts and downstream technology. The global downstream business is divided into
four companies:
• Refining and Supply
• Fuels Marketing
• Lubricants and Petroleum Specialties
• Research and Engineering
The ExxonMobil Refining and Supply Company operations include supply,

marine and pipeline transportation and refining and fuels terminaling. The com-
pany has operations in North, Central and South America; the Caribbean; Europe;
the Middle East and the Asia Pacific region.
The ExxonMobil Fuels Marketing Company provides the marketing and
sales of fuel products to retail customers, industrial and wholesale customers and
aviation and marine customers. The Exxon Mobil Corporation brings together
three world known brands Exxon, Esso and Mobil.
ExxonMobil Lubricants and Petroleum Specialties Company is organized
along eight discrete business lines: Passenger Vehicle Lubricants, Commercial
Vehicle Lubricants, Industrial Lubricants, Marine Lubricants, Aviation Lubricants,
Basestocks, Petroleum Specialties (wax, process oils and so on), and Asphalt for
roads and roofing.
ExxonMobil Research and Engineering Company provides the research,
development and use of the process, product, and engineering technology to sup-
port downstream and selected upstream and chemical segments of ExxonMobil
worldwide businesses.
4.4 NESTE/FORTUM [12]
Neste company was created in 1948 to secure the oil supply in Finland. In
that year, the company owned the first oil tanker and started oil import.
Even before 1966, Neste started crude oil refining operations in Naantali and
Porvoo. The annual capacity of both refineries was about fourteen million tons. At
that time, these two refineries were the.most advanced oil refineries in Europe.
Four years later, the company began petrochemicals and plastics production. This
led to that company becoming the largest company in Finland to play an important
role in balancing the former Finland-Soviet trade.
By 1980, Neste was already in the international oil and chemical market.
Ten years later, the business of the company expanded to the North Sea and the
Middle East. Neste service stations appeared in the Baltic Sea region states. The
petrochemicals joint venture with the Russian company - Gazprom - was created.
In 1995, Neste's shares appeared on the Helsinki Stock Exchange. Three
years later, a new company, Fortum, was founded and Neste became its subsidi-
ary. In the same year, the share of Fortum appeared on the Helsinki Stock Ex-
change.
Fortum manufactures petroleum products for use in traffic, heating, industry,
agriculture and energy generation. Additionally, Fortum manufactures methyl
tertiary-butyl ether (MTBE) in Finland, Portugal, Canada and Saudi Arabia and
tertiary-amyl methyl ether (TAME) at its Porvoo refinery. MTBE and TAME are
essential components in reformulated gasoline. Fortum is the leading producer of
reformulated fuels in northern Europe.
The company supplies only reformulated gasoline and diesel fuels to the
market. Reformulated gasoline is improved with regard to octane number by using
oxygenates. City Diesel made by Fortum is sulfur-free. Neste and later Fortum
was the first company in Europe to start the manufacture and marketing of refor-
mulated gasoline. The range of gasolines comprises two unleaded grades: Futura
95 ER and Futura 98 ER for vehicles fitted with catalytic converters.
Futura CityDiesel is a very high quality, sulfur-free diesel fuel (or fuel with
sulfur content less than 0.005 wt%). Futura CityDiesel has a minimum cetane
number of 53. Another kind of diesel fuel manufactured by Fortum is conventional
diesel with a low sulfur content.
Fortum is well known on the market with its high quality oils that use
polyalphaolefins (PAO) and extra high viscosity index (EHVI) oils as base oils.
PAO are synthetic oils of very high quality that are used for oils manufacture for
the transport, food and cosmetic industries. Neste was one of four companies in
the world that manufactured PAO oils. EHVI oils are manufactured using the
hydro-isomerization process. The quality of this oil is very close to the quality of
PAO and much higher than the quality of the normal mineral oils.
The well known high quality motor oils of Neste, and later Fortum, are the
Neste City Pro oils. All these oils are based on synthetic base oils and they exhibit
a very high quality in a wide temperature range. Neste Torbo oils are the high
206 Chapter 4
quality oils for diesel motors working with low sulfur diesel fuel. Neste Hydraulic
oils are high quality hydraulic oils working in a wide temperature range. The
Neste Biohydraul is the synthetic bio-degradable oil for working in the natural
environment.
4.5 SHELL [13]
The history of this oil company (one of the biggest) began in 1833, in espe-
cially unusual circumstances for an oil concern, when Englishman Marcus Samuel
opened a little shop in London, selling antiques, curios and sea shells to Victorian
enthusiasts. Shells were wildly popular then for decoration, and it did not take long
before the trading of shells turned into a thriving general import/export business.
The history of Shell as a real oil enterprise began in early 1890, when Mar-
cus Samuel Junior made a visit to Batum on the Black Sea from where Russian oil
from Baku was imported. The businessman was very impressed by the scale of
operations. He saw a large market for kerosene in the Far East where it was used
for lamps and cooking. Unfortunately, American Standard Oil Trust had a monop-
oly on the business. So, Marcus had to find a way to undercut prices. Quite sepa-
rately, the Dutch company, Royal Dutch Petroleum Company, was formed to
develop an oilfield in Pangkalan Brandan in Sumatra. Established in the Hague, it
enjoyed the support of King William III of the Netherlands.
The solution was found in the Suez Canal. In 1892, Marcus Samuel com-
missioned the first special oil-tanker, SS Murex, launched at Hartlepool, which
delivered 4,000 tonnes of Russian kerosene to Singapore and Bangkok.
Marcus Samuel and Company and the Royal Dutch Company competed
with each other and with the US giant Standard Oil, and by 1897 Samuel's oil
business had become so extensive that he formed a separate company to operate it.
Taking the name from the original business, the new company was registered as
the Shell Transport and Trading Company.
In 1901, Shell Transport had become the first oil company to draw its sup-
plies from all around the world, with owned or contracted production from Bor-
neo, Russia, Romania and Texas. Its markets were also very widespread in the
world, with its products kerosene for lighting and heating, lubricants and fuel oil.
In 1903, the Shell Transport and Trading Company and Royal Dutch
merged together into the enterprise called Asiatic Petroleum Company. The part-
nership between these two enterprises worked so well that four years later, in
1907, it was extended to operations world-wide, with the creation of the Royal
Dutch/Shell Group of Companies. The two parent companies retained their sepa-
rate businesses and own the Group, with more than 1,700 active companies, in the
proportion of 60% to Royal Dutch Petroleum and 40% to Shell Transport and
Trading Company.
Shell UK was created when Shell-Mex and British Petroleum, which had
combined forces during the Great Depression of the 1930s, decided to break up.
Shell-Mex Limited had been the distribution organization of the Shell and Eagle
Groups, the latter being a Mexican company in which Shell took an interest in
1919.
During the Second World War, all oil companies in Great Britain set aside
their usual competition, working together under the guidance of one of Shell
Transport's senior directors, Andrew Agnew, and providing unbranded "Pool"
products. This arrangement continued into peacetime. When more normal condi-
tions had been restored, Shell was determined to re-establish its pre-war market.
The world marketing for Shell proceeds under the logo of the pecten, or
scallop shell. This sign is derived from the time when Marcus Samuel and his
brother Sam Samuel founded The Shell Transport and Trading Company in Lon-
don on the 18th of October 1897. They named the new venture after their late
father's most profitable trade - decorative sea shells. The new company's first trade
mark, registered on the 10th of October 1900, was a picture of the mussel. In 1961
the pecten was evolving into a pure emblem. It became so in 1971 and the word
SHELL vanished from its body - a silent, but strong sign of Shell.
The many developments of Shell scientists and researchers are remarkable.
In the 1950s, Shell scientists studied the introduction of the first generation of
detergent additives.
In the 1960s, a second generation of Shell detergents was introduced leading
to a better performance by engines, greater fuel economy and lower emissions. In
1984, a new state of the art detergent and an entirely new concept in fuel technol-
ogy - the spark aider - was developed. This helped cars become more driveable,
especially when cold.
Shell launched its advanced fuels range, the first range of fuels all contain-
ing detergent additives, in 1988. The launch followed more than 25 million miles
of road tests - one of the most thorough.
A Shell engine test showed Shell Advanced fuels were 375 times cleaner
than standard market fuel and the competitors had to respond by adding detergent
to their gasoline.
Additive technology continued improving. In 1994, Shell launched an even
better detergent package, enabling drivers to gain an average of nine extra miles to
a tankfull of gasoline, faster acceleration and still lower emissions.
Shell continued its development of new fuels in 1995 with the introduction
of Shell Advanced Low Lead 4 Star and the first low sulfur diesel to be manufac-
tured in the UK. These two new fuels continued to give drivers more ways of
reducing the impact of their vehicles on atmospheric quality.
Since 1999, the Shell businesses in the UK became a part of the Royal
Dutch/Shell Group of companies.
The main types of product offered to the market under the sign of Shell are:
• Shell Premium Unleaded and Shell Super Unleaded gasoline - improved
gasoline.
• Shell Lead Replacement gasoline, the new improved mark of gasoline has
been on the market since the 1s' of January, 2000.
208 Chapter 4
• Shell Pura Diesel is a market leading ultra low sulfur diesel which, in the year
2000, has already met the known year 2005 emissions standards.
• The range of motor oils providing superior performance in passenger car
engines. The range includes fully synthetic, semi-synthetic and mineral oils
for different types of engines, age and operation.
• Oil formulated for heavy diesel use and tailored to exceed both industrial
specifications and equipment manufacturers' requirements.
• The range of high temperature and high performance greases for lubrication
of automotive wheel bearings.
• Automatic transmission fluids suitable for automotive hydraulic, power
steering and some manual transmission applications.
• Fuel efficient gear oils which deliver ultimate performance.
• Synthetic air compressor oils which give outstanding performance in rotary
and reciprocating compressors.
• Oils that are specially formulated to give excellent performance in rotary and
reciprocating compressors.
• The range of conventional and high performance, milky soluble cutting fluids
that ensure high cooling rates, good lubrication and excellent anti corrosion
properties.
• Low smoking, low misting range of neat oils suitable for all neat and metal-
working applications giving excellent tool life and component finish.
• Corrosion protectors for machine components from one week to two years.
• High performance industrial gear oils for use in all helical, bevel and spur
gear boxes.
• High quality lubricant for bearing and circulation systems.
• The high performance multipurpose greases suitable for use in high tempera-
tures and in the presence of moisture.
• Lithium base greases designed to give high performance in industrial bear-
ings.
• The high technology grease that enables optimum performance for grease
lubrication in industrial bearings, giving extended regreasing intervals and
improved equipment life.
• High performance anti-wear hydraulic oils that are universally acknowledged
as the market leader in the field of industrial hydraulic and fluid power lubri-
cation.
4.6 TOTAL/FINA/ELF [14,15]
The first part of this corporate company, PetroFina, was founded in the year
1920. Within four years, PetroFina was already a well known company that had its
own distributor, PurFina, for sales in Holland and Belgium. In 1924, the Compag-
nie Francaise des Petroles, one of the ancestors of Total, was formed. In 1927, this
company discovered the first oil field near Kirkuk in Iraq. Two years later, the
shares of this company appeared on the Paris Bourse.
In the meantime, the new company - Compagnie Francaise de Raffinange-
together with Compagnie Francaise des Petroles and in conjunction with the
French state and several private French companies got involved in the French
petroleum business.
In 1931, Compagnie Navale des Peroles was formed from Compagnie
Francaise des Petroles. Two years later, a company, Compagnie Francaise de
Raffinage, was formed. This company was responsible for petroleum processing.
This company had already owned its own petroleum refinery only within two
years of formation.
It was only in 1945 that the successors of the third part, Total Fina Elf com-
panies, was born. These were the French companies Regie Autonome des Petroles
(RAP), the Societe Nationale des Petroles d'Aquitaine (SNPA) and the Bureau de
Recherches de Petrole (BRP). The actual start of the formation for these compa-
nies can be considered to be the year 1939, when the exploration of the oil field at
Saint-Marcet in Aquitaine yielded some success.
In 1947, the first marketing subsidiary of the petroleum enterprises, the
ancestors of Total, was created. This company was named Compagnie Francaise
De Distribution des Petroles en Afrioque (CFDPA).
The Societe Industrielle Beige des Petroles (Belgian Industrial Petroleum
Company) - SIBP - was founded in Antwerp in 1949 as a result of the industrial
integration through the control of the refining process after the Second World War
and began production in 1951. In the same time, PetroFina undertook exploration
and production in Mexico, Canada, Angola, and Egypt. It was during these years
that the company started its world-wide growth. In 1954, PetroFina started its
petrochemical production with its first plastic manufacturing.
In 1954, the parent company of Total Petroleum participated in the Iranian
Oil Consortium. In the same year, the first trade mark - TOTAL - was created and
the first marketing company for Total products was thus founded.
Two years later, the Hassi-Messaoud oil field and Hassi R'Mel gas field in
the Algerian Sahara were discovered, and within three years Compagnie Francaise
des Petroles began the commercial production and operation on oil wells in these
fields.
In 1964, the Compagnie Francaise des Petroles started exploration opera-
tions in the North Sea and four years later started its involvement in Indonesia.
In 1965, the historic decision for the future of Elf Company was accepted.
RAP and BRP merged to form Enterprise de Recherches et d'Activites Petrolieres
(ERAP). ERAP was the real foundation stone for the future Elf Aquitaine group,
which comprised a chain of specialties from the oil well to the pump. It was not
until this year that the ancestors of this company discovered oil fields all over the
world. The company was assured oil production and treatment. It was therefore
decided to add refining and marketing as essential supplements. The Union Ge-
210 Chapter 4
nerale des Petroles (UGP) was formed, and then the Union Industrielle des Pe-
troles (UIP).
Since 1967, all the products of the Elf ancestor companies have come to the
market with only one short name: ELF.
In 1970, the petroleum company which is well known nowadays as Total
Petroleum was founded. This foundation was actually the renaming of an already
existing company: the French Petroleum Company of Canada. Within three years,
the share of this company had already appeared on the London Stock Exchange,
and within one year Total Indonesia started commercial production in East Ka-
limantan.
After three years, Total Petroleum began the commercial production from
the Frigg gas field in the North Sea. In the same year, the historical document, the
agreement of the merger of the Compagnie Auxiliare de Navigation and the Com-
pagnie Navale des Petroles to form the Total Compagnie Francaise de Navigation,
was signed.
In 1972, PetroFina bought back all their shares in Societe Industrielle Beige
des Petroles. The company focused on its refining activities. Fina Raffinaderij
Antwerpen became the center of an integrated petroleum and petrochemical net-
work.
In 1980, agreement was signed for the start of exploration and production in
China. In 1981, work started in the refinery at Victoria in Cameroon that was built
and operated with technical assistance from Total.
In 1983, there existed the new merger of Minatome and Total Energie de-
velopment to form Total Compagnie Miniere. Two years later, the Compagnie
Francoise des Petroleum was renamed Total CFP.
In 1987, Total owned the hydrocarbon assets held by TIPCO in the United
States, as well as those of FRANCAREP ITALIA. In the same year, Total owned
the petroleum refinery at Denver in the United States.
In 1988, the products of Fina chemical production were sold around Europe
and in the USA.
Three years later, Total started the discovery of the oil field at Cusiana in
Colombia and the gas field at Peciko in Indonesia. In the same year, the company
name - Total - was adopted as the official trade mark and the international com-
pany name. In the same year Total shares appeared on the New York Stock Ex-
change and the direct share holding of the French government in Total was re-
duced from 31.7 to 5.4%.
Five years later, the shares of Elf Aquitaine appeared on the New York
Stock Exchange. As of the end of the twentieth century, Elf Aquitaine had three
strong company sectors: hydrocarbons, chemicals and health.
In 1995, Total was selected to lead the Yemen gas liquefaction project. One
year later, a further 4% of Total capital was divested by the French government;
that reduced government stake to 0.97%.
In the twenty-first century, TotalFinaElf has combined the strengths of Total

group, PetroFina and Elf Aquitaine, and has thus become the fourth largest oil and
gas company in the world.
The Mitteldeutsche Erdoel Rafenerie Middle German Petroleum Refinery
(MIDER) was built and operated by Elf in 1995. This refinery is especially inter-
esting, because of the application of cutting age technologies and processes in the
refinery. Some details concerning this refinery are given below.
The refinery has been designed for an operating life of approximately 30
years. At the end of the twentieth century, MIDER was the most modern petro-
leum refinery in Europe. This was built based on the old Leuna Refinery and pro-
jected to use Russian oil first of all. New construction included the product pipe-
line Leuna-Harimannsdorf/Bohlen and the rail- and road-loading facilities as well
as parts of the effluent treating plant. On the supply side, a refinery owned power
station was built by STEAG (power plant operator) whereas Linde built the hy-
drogen plant.
The first and therefore unique distillation process developed by Elf together
with Technip in the 1980s operates at the MIDER refinery.
Energy consumption of the rectification process is reduced via integrated
atmospheric and vacuum rectification as well as optimal utilization and operation
of heat flows. MIDER claims to save some 50,000 tons of fuel oil per annum
compared with a traditional distillation process. The process is characterized by
the use of five instead of the usual two distillation columns. The process develop-
ment was based on the objective of avoiding unnecessary overheating of the light
components. Additionally, it avoids degrading the thermal levels associated with
the drawing off of heavy fractions.
The processing of Russian crude in the above mentioned unit results in a
vacuum residue with boiling point of over 585°C. Progressive distillation yields
the following fractions:
• Light gasoline (IBP-80°C)
• Naphtha as feedstock for the petrochemical industry (80-95°C)
• Heavy naphtha (96-160°C)
• Kerosene (160-225°C)
• Light and heavy gas oil, vacuum gas oil (225-400°C)
• Medium, and heavy VGO as catalytic cracking feed (400-585°C)
• Vacuum residue for bitumen production and feed for visbreaker
Maurice Promager, manager of R&D of Elf Antar France, quotes the fuel
consumption of the progressive distillation as being 1.25% fuel oil equivalent
(FOE) for the Soviet Export Blend and 1.15% FOE for the Arabian heavy oil. This
compares with 1.7% to 2.0% for the Arabian light oil by conventional processing.
The selection of process units and individual processes was determined by
projected product specifications, required range of products and the overriding
necessity to minimize residue yield.
212 Chapter 4
In the partial oxidation for the production of methanol (POX/methanol)

complex, a major portion of the visbreaker residue (approximately 670,000 tons
per annum) is converted to gas. Part of the syngas produced in the POX is used to
cover the hydrogen demand of the refinery. Therefore, a plant producing high
purity hydrogen has been installed and is operated by Linde. Another part of the
syngas is added to the refinery fuel gas system for consumption in the process
furnaces, which are exclusively gas fired.
Downstream of progressive distillation, light distillates are processed in an
alkylation unit (sulfuric acid catalysts), a hydro-treater for naphtha, and a continu-
ous catalytic reformer (CCR). The alkylation unit is fed essentially with olefins
from catalytic cracking. The middle distillates are fed to two identical gas oil hy-
drofmers with integrated hydrogen sulfide removal for vacuum flash gas and a
dual train (each 60% capacity) sulfur unit utilizing Sulfreen to achieve a guaran-
teed 99.5% conversion.
Vacuum distillate undergoes hydrogenation in the VGO hydrogenation unit
before being fed to the catalytic cracking (FCC), whilst vacuum residue passes to
the visbreaker for further conversion. FCC residue is used as a fuel component in
the refinery's own power station, and it supplies the refinery, in return, with steam
and electrical power. It includes three oil- and one gas-fired boilers and is de-
signed for 110 MW output.
There are several levels of automation in the refineries. These embrace not
only the vital process control system, but also the laboratory information man-
agement system (LIMS) and the general company data processing. These are
distinguishing features of the refinery systems concept. In this way, the central
databank incorporates relevant updated production data, information from LIMS
and other refinery internal data systems to serve the overall management needs.
The process control system includes almost all refinery plants, covering not
only the process plants but also tankage, pipeline supervision and effluent treat-
ment. The POX/methanol complex and the loading facilities are, however not
included in the system. The dispatch computer has been tailored to the details and
requirements of the loading operation. The POX/methanol complex is equipped
with its own system that is linked with the refinery control room for the purpose of
data exchange. Similarly, the refinery power station exchanges data with the refin-
ery control room in order to match the dynamics of supply and demand.
There are a total of five panel operators who manage the central refinery
control room. Outside personnel carry out solely supervisory tasks.
Panel operators handle a total of 40,000 individual data points visualized in
four control groups containing four display units in each case, and an extra group
containing five display units. Foxboro supplied the control system. The number of
units attended to by each individual panel operator is obviously related to the total
number of control loops involved. At the same time, consideration also had to be
given to the physical boundaries of the individual units to facilitate effective com-
munication with outside operators.
The safety system of the refinery is called "AES" and has been applied to
units with high danger potential in addition to the usual shut down system. The
AES system was developed originally for use in steam crackers and ethylene
plants, and is initiated using both simultaneously pressing and turning a switch.
AES offers the process operator three stages of action. In the first stage, the
unit is put into a safe stationary condition, essentially by cutting off or, if need be,
rerouting of feed/product streams together with heat and steam inputs to ensure
that no additional risks can be brought into the unit. Under this condition, it would
be possible to re-stream the unit with little effort. Initiation of stage two would
effect isolation of the unit and relief to flare at a predefined pressure level. With
this, the relevant section of the unit would be completely sealed off from neigh-
boring sections. Finally, by initiating stage three the whole unit would undergo
sealing off and relief.
Furthermore, the AES system can be programmed to any relevant time
functions on a sequential shut-down. Such a system appears at a first glance not to
be too complicated, but when one realizes that all the units are connected with
each other, then shutting down one unit in an emergency situation could be seen as
a significant disturbance to the integrated production. Therefore, in all cases where
immediate action is needed, neighboring units have to become involved and are
put into an appropriate safe condition.
The refinery is primarily supplied with Russian crude oil via pipelines.
However, this crude oil can also be supplied via the Baltic ports of Rostock and
Danzig. For this purpose the MVL (Schwedt pipeline) is available together with
the raw material pipeline Rostock-Bohlen (RRB), which belongs to the Dow
Chemical Company, and is used for supplying its olefin group (BSL) in Bohlen
with ethylene cracker feedstock in a roundabout way via Leuna. The refinery tank
farm, consisting of a total of 63 tanks, has a crude oil storage capacity of roughly
300,000 m3. In addition, 490,000 m3 capacity is available for intermediate prod-
ucts and 265,000 m3 for finished products. LPG tankage totals 11 tanks with a
capacity of 24,000 m3.
Finished products are distributed by rail, road and pipelines. Rail and pipe-
line distribution each account for roughly 4 million tons per year. Road transport
accounts for a total of 3 million tons per year of products for customers within a
150 km radius of the refinery. The Central German Product Pipeline (MIPRO) has
a design capacity of 3.2 million tons per year and is used for supplying the Hart-
mannsdorf depot near Chemnitz.
With an annual production of over four million tons of diesel fuel and do-
mestic heating oil in addition to two million tons of motor gasoline, the refinery is
in a position to almost fulfill local demand.
MIDER will process Russian export blend crude oil almost exclusively.
Arabian heavy crude oil will form the exception in the summer months, whilst
producing bitumen. Segregated vacuum residues from Arabian heavy oils and
Russian export blend crude oil will be blended to meet local bitumen specifica-
tions and demands.
214 Chapter 4
There are abundant connections between the new refinery and other petro-
chemical sites. Up to 700,000 tons per year of naphtha (LDF) will be charged to
the feedstock pipeline Rostock-Bohlen for processing in Bohlen. Refinery pro-
duced methanol, amongst other things, goes to two customers in Leuna, namely
Atochem for their formaldehyde based glue production and UCB for the manu-
facture of amines and formamides.
The refinery yields include 50% middle distillates, 23% gasoline, 7% LDF,
and 2% LPG. Most of the C3 LPG (70%) is propylene, which is mainly used for
cumol synthesis via the caprolactum process, operated by Caproleuna in Leuna.
Regarding product quality, the gasoline will be produced with a benzene
content < 1%, sulfur content < 0.01% and aromatics content of 35%. Diesel fuel
will have a sulfur content of < 0.05% with a lower capability of < 0.025%, and a
cetane index of 52.
4.7 LUKOil [16]
OAO LUKOil is the leader of Russia's fuel and energy complex. LUKOil is
the first Russian integrated oil company operating in all the petroleum processing
spheres from petroleum extracting to marketing of petroleum products. LUKOil
was formed in 1991 in the form of a business concern, based on the three biggest
oil and gas producing enterprises in Western Siberia - Langepasneftegaz,
Uraineftegaz and Kogalymneftegaz. The first letters of these names were com-
bined to form LUKOil. Subsequently, LUKOil absorbed other oil-producing, oil-
refining, sales, petrochemical, transportation and other oil business enterprises.
In the year 2000, the LUKOil concern was expected to expand its operations
in 40 regions of Russia and 25 countries outside of Russia. This company owns
one of the biggest proven petroleum reserves in the world that is owned by a pri-
vate oil company. LUKOil proven reserves in 2000 exceed two billion tonnes.
This company takes first place among Russian companies in terms of the volume
of oil produced.
In 1999, the company produced 75.6 million tonnes of oil and 4.7 billion
cubic metres of gas. A large proportion of the oil is extracted by its basic oil-
producing subsidiary, OOO LUKOIL-Western Siberia, which includes:
• LUKOil-Langepasneftegaz
• LUKOil-Uraineftegaz
• LUKOil-Kogalymneftegaz
• LUKOil-Pokachevneft
In the western part of Russia, oil production is carried out by the main oil-
and gas-producing subsidiaries of the company:
• OOO LUKOil -Astrakhanmorneft
• OOO LUKOil- Kaliningradmorneft
• OOO LUKOil- Nizhevolzhskneft

• OOO LUKOil-Permneft
• ZAO LUKOil-Perm
• OAO KomiTEK
In 1999, the oil production in European Russia that was carried out by LU-
KOil amounted to 24 million tonnes. In the same year, OAO LUKOil acquired the
oil company KomiTEK, the result being a substantial increase in the company's
raw material base: proven oil reserves increased by 400 million tonnes and those
of gas by 47 billion cubic meters.
The ultimate assessment of the reserves based on the results of tests of deep
prospecting wells is expected at the end of the year 2000.
LUKOil is the first Russian petroleum enterprise to start the manufacture of
high quality half-synthetic and fully synthetic oils. The products of this company
are used not only on the domestic market, but also on the European and American
markets.
The quality of LUKOil oils has been certified and recommended by the
German companies Mercedes, BMW and VW.
4.8 YUKOS [17]
YUKOS was formed on the 15th of April 1993 according to the government
decree No. 354. The acronym YUKOS was chosen as the name for the company,
with its letters taken from the names of its original two primary operating units:
• Yuganskneftegas - one of Russia's largest oil production units, located in the
Tyumen region
• Kuibishevnefteorgsintes - a major petrochemical holding located in the Sam-
ara region
In that year, YUKOS comprised one production entity, Yuganskneftegas;

three refineries, Kuibishev, Novokuibishevsk and Syzran; and eight petroleum
product suppliers located in the Russian regions of Samara, Penza, Voronezh,
Oryol, Bryansk, Tambov, Lipetsk and Ulyanovsk.
Two years later, the company owned a second production entity, Samara-
neftegas, along with a number of product marketing and research and development
organizations.
As a result of the financially difficult transition period, the Russian govern-
ment decided to sell YUKOS'S state-owned shares to private investors. Through a
series of tenders and auctions held in 1995-1996, YUKOS became the first fully
privatized Russian oil company. The major purchaser was a group of private in-
vestors led by YUKOS Chairman Mr. Mikhail Khodorkovsky.
216 Chapter 4
Under Mr. Khodorkovsky's leadership, YUKOS completely repaid its debts

(accumulated while it was a government-owned company) to the Russian federal
and regional governments. In the first year following its privatization, YUKOS
received 1 billion US$ in loans and investments primarily due to the efforts of the
company's new modern management team.
In 1997, YUKOS acquired a controlling stake in the Eastern Oil Company
(Russian acronym VNK), thus adding to its existing assets a third production en-
tity. The configuration and profiles of the VNK enterprises complemented those
already under YUKOS control and allowed the company to expand both in terms
of operational capacity and eastern geographical reach. At the same time, YUKOS
initiated systematic efforts to integrate VNK and its subsidiaries into its corporate,
financial and operational structures.
In 1998, YUKOS signed an agreement establishing a strategic alliance with
Schlumberger, one of the world's largest oilfield service companies. Under the
agreement, YUKOS outsources a significant part of its oilfield service operations
to Schlumberger. This has enabled YUKOS to fundamentally restructure many of
its own service enterprises. Moreover, the cost of the oil well being served has
been reduced by 22 percent, yielding a significant reduction in overall production
costs.
In 1999, a production enhancement network was established, a reservoir
enhancement network was developed, and a technology network set up to opti-
mize equipment utilization. About 800 wells were treated during the year, and a
total of 1,500 well candidates were identified.
In the twenty-first century, YUKOS has become the second largest oil com-
pany in terms of oil production and reserves in Russia.
The company products include all the ranges of fuels and oils made in the
petroleum industry. The products are sold on the domestic and international mar-
kets.
4.9 TNK [18]
Tyumenskya Neftyanaya Kompaniya (Tyumen Oil Company) or TNK was

formed as an open joint-stock company in 1995 and is known as the most stable
petroleum company in Russia.
Until 1997, the company and its subsidiaries operated as an autonomous
production and financial division resulting in a decline of overall production and
lack of financial control. In July 1997, Novy Holding acquired a forty percent
stake in TNK through an investment tender. Novy Holding spent more than
US$600 million to regain control of the shares and to acquire additional shares in
the subsidiaries. By February 1998, Novy Holding together with Novy Petroleum
increased their joint stake in TNK's charter capital to 50.1 percent. The new share-
holders launched a large-scale restructuring program to create an efficient and
responsive vertically integrated production and management structure.
In 1998, the restructuring of INK began with the first step taken by Novy
Holding to replace the management of TNK with individuals educated in the west,
having extensive experience with international oil giants and possessing compre-
hensive knowledge of the Russian oil industry.
In October of 2000, Tyumen Oil Company received the American Society
for Competitiveness's (ASC) annual award for leadership in developing globally
competitive practices in an emerging economy.
The products of the company include:
• Gasoline with octane numbers of 92, 95, 98; all kinds of gasoline made by
TNK are unleaded; the company has started the production of reformulated
gasoline
• Diesel fuel with a sulfur content of 0.2%, and an ecological diesel with a
sulfur content of 0.05%
• Domestic fuel
• Residual fuels
• Industrial oils
• Motor oils
• Additives for motor oils
• Catalysts for the Petroleum treatment processes, such as reforming and hydro-
treating
Bibliography
U.S. Crude Oil, Natural Gas, and Natural Gas Liquids Reserves.
1998 Annual Report, December 1999, Energy Information Administration
Office of Oil and Gas, U.S. Department of Energy.
Internet Publication: BP Amoco, Chicago, IL. BP Amoco in Alaska:

Badami Factsheet. http://www.bpamoco.com.
P. Seidel. Schweres Erdol - ein alternativer Rohstoff zur Erzeugung von

Treibstoffen. Expert Verlag, Renningen-Malmsheim, 1994.
E. N. Kokotchikova. Macroeconomicheskoe znachenie neftegazovogo

kompleksa v economike Rossii. GANG, 1996.
N. A. Kruglov. Vchera, segodnya, zavtra neftyanoj i gazovoj

promyshlennosti. INGIRGI, 1995.
Internet: homepage of BP Company, http://www.bp.com/default.asp.

218 Chapter 4
7 V. A. Dinkov. Neftyanaya promyshlennost vchera, segodnya, zavtra. Mos-

cow, VNIIOENG, 1988.
8 Nezavisimoe neftyanoe obozrenie. Moscow, VNIIOENG, Nr. 1, 1993.
9 V. L. Berezin. Neft i gaz zapodnoy Sibiri, Moscow, 1990.
10 Internet: homepage of Castrol Company, http://www.castrol.com.
11 Internet: homepage of ExxonMobil Company.

http://www.mobil.com/index_flat.html.
12 Internet: homepage of Neste/Fortum Company, http://www.neste.com/.
13 Internet: homepage of Shell Company, http://www.shell.com/.
14 Internet: homepage of Total / Fina / Elf Company.

http://www.totalfinaelf.com/fr/html/index.htm.
15 Stand der Technik bei Raffinerien im Hinblick auf die IPPC-Richtlinie.

Bericht IB-610, Umweltbundesamtes.
16 Internet: homepage of LUKOil Company, http://www.lukoil.ru/.
17 Internet: homepage of Yukos Company, http://www.yukos.ru/.
18 Internet: homepage of TNK Company, http://www.tnk.ru/.

Part III
MAIN PROCESSES IN THE
PETROLEUM REFINING INDUSTRY
OVERVIEW
Every modern refinery is uniquely designed to process a given crude petro-

leum into selected products. It is therefore necessary to know the chemistry of the
crude to be processed into selected products in order to make an appropriate de-
sign of the refinery processes to use. The process designer needs to produce a
design to meet the business objectives of the refinery by selecting from an array of
basic processing units. In general, these units together perform three functions:
• separating the many types of hydrocarbons present in crude oils into fractions
of more closely related properties,
• chemically converting the separated hydrocarbons into more desirable prod-
ucts, and
• purifying the products by removing unwanted elements and compounds.
The following processes are employed in almost every modern refinery to

perform these three functions:
petroleum rectification,
vacuum rectification,
hydroprocessing,
gas processing plant,
sulfur recovery unit (SRU),
reforming (platforming),
isomerization and hydroisomerization,
alkylation,
polymerization,
catalytic cracking,
hydrocracking,
219
220 Part III
• thermal cracking,
• visbreaking,
• residue conversion processes,
• blending.
These processes can be classified as primary or secondary processes. In this book,

primary processes are used to describe processes in which crude petro-
leum/products undergo only physical treatment. On the other hand, secondary
processes describe processes in which petroleum/products undergo chemical trans-
formations.
Furthermore, additional processes are required in order to provide the pe-
troleum processing units with steam, electric power and cooling water that are
needed for these units to function. In modern refinery complexes, the energy con-
sumption is low (lower than 5% of the crude oil throughput). Water consumption
is low as well (below 1 m3 per ton of crude oil).
Crude Oil Distillation
5.1 PETROLEUM AND GAS PREPARATION
As a rule, the initial stage of petroleum extraction from oil wells occurs
under the natural layer pressure practically without contamination with water.
With time, however, the water layer gets produced together with the petroleum
layer. About two-thirds of all petroleum is extracted in high humidity conditions.
Water layers can differ considerably by their chemical and bacteriological con-
tents. During the extraction of this mixture of petroleum with water layer, an
emulsion is formed. Emulsions can be considered to be a physical mixture of two
immiscible liquids, one of which is distributed in another phase as droplets of
various sizes. The water present in petroleum results in an increase in the trans-
portation price because of an increase in both volume and viscosity of the resulting
liquid to be transported.
The presence of corrosive mineral salts in solution in the water leads to fast
deterioration of petroleum pumps and oil refining equipment. The presence of up
to 0.1% of water in petroleum leads to intensive foam formation in the rectifica-
tion tower of oil refineries. This results in an alteration of the technological
scheme for oil processing. Besides, it also affects the condensation equipment.
The light fractions of petroleum (gases from methane to butane) are valuable
raw materials for the chemical industry from which products such as solvents,
liquid motor fuel, alcohol, synthetic rubber, fertilizers, artificial fiber and other
products of organic synthesis are made. Therefore, it is necessary to reduce the
loss of light fractions during petroleum processing. Thus, all hydrocarbons deriv-
able from petroleum need to be preserved for subsequent processing.
Modern petrochemical complexes manufacture various high-quality oils and
fuels as well as new types of chemical products. The quality of these products
depends on the quality of the initial raw material, i.e. crude petroleum. In the past,
the technological processing scheme of older oil refineries could be used to proc-
ess crude petroleum with mineral salts contents of 100—500 mg/L. Petroleum
with a lower salt content is required in modern refineries. Thus, frequently before
221
222 Chapter 5
oil processing, it is necessary to completely remove salt from the petroleum by

desalting.
The presence of different types of salt impurities in petroleum affects pipe-
lines and oil pumps. This complicates the petroleum-processing scheme because
the solids form scales in coolers/refrigerators and furnaces. This leads to a reduc-
tion in the heat transfer coefficient of the scaled surface. Solid impurities also
promote emulsion formation.
The presence of mineral salts in the form of crystals in petroleum and in
solution in water leads to extensive corrosion of metallic parts of equipment and
pipelines. It also leads to an increase in emulsion stability, thereby adding to the
complication in the petroleum-processing scheme. The quantity of mineral salts
dissolved in water divided by its volume is called General Mineralization.
Under favorable conditions, a part of magnesium chloride (MgCla) and
calcium chloride (CaCl2) present in the water layer can be hydrolyzed with the
formation of hydrochloric acid. Also, hydrogen sulfide is formed during petroleum
processing as a result of decomposition of sulfur compounds. This increases the
intensity of corrosion of metals in the presence of water. Hydrogen chloride in
water solution also corrodes metal parts. Corrosion is especially intensified in the
presence of hydrogen sulfide and hydrochloric acid in water. The requirement for
petroleum quality is, in some cases, very stringent: the contents of salts should not
be more than 40 mg/L in the presence of water, whose content should only be up
to 0.1%.
These requirements and other reasons make the preparation of petroleum
before processing very necessary. Petroleum preparation includes drying (removal
of water or dewatering) and desalting of petroleum, and complete or partial re-
moval of dissolved gas.
5.1.1 Formation of Petroleum Emulsions and Their Basic Properties
In order to select the proper drying process, it is necessary to know both the
mechanism of formation and properties of petroleum emulsions.
Usually, no emulsions are formed within the petroleum layer. Emulsion
formation begins during the movement of petroleum to the mouth of the oil well
and intensifies during further transport of petroleum in pipes (i.e. emulsions are
predominant where there is the potential for continuous mixing of petroleum and
water). The intensity of emulsion formation in an oil well depends on the method
of petroleum extraction. This, in turn, is defined by the character of the oil wells,
time of its operation and physical-chemical properties of the petroleum.
When petroleum is extracted from oil wells using the natural layer pressure
(which is typical in the initial period of oil well operation), there is usually a very
high rate of extraction of the oil from the oil well. The intensity of petroleum
mixing with water in elevating pipes of the oil well increases due to dispersion of
Crude Oil Distillation 223
the solved gases at decreasing pressure. This leads to emulsion formation at the
early stages of movement of the petroleum-water mixture.
During deep pumping extraction of petroleum, emulsion formation occurs in
the valves, in the pump cylinders and in the elevating pipes during the reciprocat-
ing movement of pump bars.
In the compressor oil well, the base of the emulsion formation is the same as
at extraction using natural layer pressure. Air sometimes mixes with the gas in an
oil well and oxidizes a part of the heavy hydrocarbons to form asphaltenes-
resinous materials. These adversely influence emulsion formation negatively.
Thus, the presence of salts of organic acids as well as asphaltenes-resinous materi-
als leads to emulsion formation. This type of emulsion has a very high stability.
It is important to distinguish two phases in emulsions - the discontinuous
and continuous phases. The continuous phase is the liquid in which very small
droplets of another liquid are dispersed. The discontinuous phase is the liquid that
is dispersed in the form of fine droplets in the continuous phase.
Two types of emulsions are distinguishable - "oil in water" and "water in
oil". The type of emulsion formed basically depends on the volume ratio of the
two phases. The continuous phase is the liquid with the greater volume. In practice
the most frequently known emulsion is the water in oil emulsion.
The presence of emulsifiers (materials that promote emulsion formation)
influences the ability to form an emulsion between petroleum and water. Emulsifi-
ers act by lowering the interfacial tension between the phases and creating a strong
adsorbed layer around the surface of the internal phase. Emulsifiers that are solu-
ble in water (hydrophilic) promote the creation of oil in water emulsion. Alkaline
soaps, starch and so on are such hydrophilic emulsifiers. Hydrophobic emulsifiers
(i.e. soluble in petroleum) promote the formation of water in oil emulsions. Hy-
drophobic emulsifiers include resins dispersed in particle form within soot, clay
and other substances. Petroleum emulsions can be characterized using properties
such as viscosity, dispersion, density, electrical properties and stability. The vis-
cosity of petroleum emulsion changes within wide ranges and depends on the
viscosity of petroleum, temperature, and amounts of petroleum and water.
Petroleum emulsions that are disperse systems have unusual properties
under certain conditions, i.e. they are Newtonian liquids. Thus, petroleum emul-
sions like all Newtonian liquids can be characterized by an effective viscosity.
Dispersion of the emulsion is the degree of distribution of the droplets of the
discontinuous phase in the continuous phase. Dispersion is characterized by the
diameter of the droplets d, and by D = 1/d (- specific surface area) calculated by
dividing the total surface area of the particles by their total volume.
The sizes of droplets can change depending on the physical-chemical prop-
erties of petroleum and water as well as the conditions of emulsion formation.
Sizes range from 0.1 micron up to several tens of mm. Disperse systems which
consist of droplets of the same size (single diameter) are referred to as mono-
disperse. On the other hand, systems that consist of droplets of different sizes are
called poly-disperse systems. Petroleum emulsions are poly-dispersed systems.
224 Chapter 5
The critical droplet size that can exist in the flow at a given thermodynamic
mode is determined by the velocity of movement of the mixture of water and
petroleum, interfacial tension between the phases and pulsation of flow.
In the turbulent flow regime, caused by non-uniformity of pulsation and
variable cross section of pipeline, the existence of droplets of various diameters is
possible. Fine droplets that move in the section of pipeline of lower velocity gradi-
ents and smaller pulsation tend towards agglomeration, whereas those that move
in the zones of high velocity gradients and large pulsation tend towards splitting.
The presence of additional factors (such as heating, addition of emulsifier, etc.)
under certain hydrodynamic conditions can lead to the separation of the emulsion
phases in the pipelines.
A higher degree of emulsion stability depends on the structure of the com-
pounds that constitute the protective layer formed on the surface of the droplet.
The emulsifier adsorbs on the surface of the droplet and covers it with a preserving
layer thereby stabilizing the droplet. This layer prevents droplets from merging
with each other (i.e. promotes emulsion formation and stability).
The chemical nature of water in the petroleum layer has an influence on the
stability of petroleum emulsions. All the water layers contain chemically different
materials. However, they can all be divided into two basic groups: the first group
is hard water containing calcium chloride, magnesium chloride, etc.; the second
group is alkaline water. The presence of increased amounts of acid in the water
layer leads to the formation of more stable emulsions. Adding alkali to the emul-
sion can reduce the amount of acid in the water layer.
5.1.2 Separation of Water-Oil Emulsions
The process sequence of breaking petroleum emulsions follows the con-

secutive steps: agglomeration and flocculation of droplets, destruction of the pro-
tecting layers, coagulation of the droplets of the disperse water up to a size suffi-
cient to further merge by the influence of gravity, and then falling down to the
bottom of the separator.
If the droplets have sufficient energy for the destruction of the protecting
layers to occur, then the droplets will merge.
A number of technological methods are applied for petroleum drying. The
choice of method for petroleum drying and performance scheme employed sub-
stantially depends on the amount and condition of water present.
Water contained in crude petroleum appears in free form, i.e. non-dispersed
form, in some cases. Such water can be removed from petroleum directly by co-
agulation.
More often however, water in crude petroleum is present in its dispersed
form, emulsion of water in oil. There are two versions of this emulsion: mechani-
cal non-stabilized and stabilized by interfacial-active substances. This distinction
for emulsions is essential for petroleum drying. Water from non-stabilized emul-
sions can be easily separated by the usual settling method or by settling with mod-
erate heating. More complex processes, such as intensive heating, chemical proc-
essing, electrical processing, and combinations of these methods are required for
separation of water from stabilized emulsions.
For designing the schemes for drying of petroleum under industrial condi-
tions, it is necessary to determine for the petroleum to be dried the water content in
the petroleum, type and quantity of impurities in water, and also the conditions in
which water is present.
The processes of drying and desalting are very similar. In desalting, how-
ever, the water is removed from the petroleum together with the dissolved mineral
salts. If it is desired, more complete desalting is achieved by introducing additional
fresh water to the petroleum to dissolve the mineral salts and subsequent drying.
Settling, centrifugation and filtration are mechanical methods for petroleum
drying.
Settling is applied if unstable emulsions are processed. Here, the droplets are
stratified due to the difference in the densities of the materials in the phases.
The droplets' settling speed for designing separators is calculated using the
formulas:
«,*= dPiZfiLRe" (5.1)

55.5 pk
for 2 < Re < 500:
(5.2)
for Re > 500:

where: Re - Reynolds number {(dcopd)/(i)
(J. - viscosity of medium
CD - settling speed
Pa - density of the discontinuous phase
Pk - density of the continuous phase
d - diameter of the droplet or particle
g - acceleration due to gravity (9.8 m/s2)
These equations imply that the major factors that influence the efficiency of
emulsion separation are:
226 Chapter 5
• Densities of the phases in the emulsion (essentially, the difference in density

of the phases is responsible for gravitational separation);
• The viscosity of the emulsion phases, especially the viscosity of the continu-
ous phase (this is a very significant factor and affects efficiency of petroleum
drying by affecting transport of droplets or particles through the medium);
• Diameter of droplets or particles of the discontinuous phase (this factor is
very important because the settling speeds of the droplets or particles grow
proportionately to the square of their diameters);
• The acceleration of the droplets or particles is due to their presence in the
natural gravitational field. The value of the acceleration is approximately 9.8
m/s";
• The area available for settling.
These factors can therefore be used in design to improve the efficiency of

emulsion separation. The favorable ways to apply these factors are as follows:
• Increase of temperature of the emulsion. This reduces the viscosity of the
emulsion phases, and reduces the interfacial tension between the phases (the
thermal methods of petroleum drying are based on this principle);
• Increase of droplet sizes of the discontinuous phases via various methods such
as using chemicals and applying an electrical field (the chemical and electri-
cal methods of petroleum drying are based on this principle);
• Increase of the settling speed of the droplets by replacing the natural gravita-
tional force by the more powerful centrifugal force. Centrifugal force influ-
ences water and mechanical impurities in that their densities are higher than
the density of petroleum. The method of centrifugation is not very productive
but is complicated, and therefore has not found wide application in the oil in-
dustry;
• Increase of the useful settling area without increase of the general area of
separator. The use of parallel plates in horizontal separators and separated
disks in separators is based on this principle.
The efficiency of emulsion separation is reduced in the case where the den-
sity between the dispersed droplets or particles and the continuous phase is very
small. Also, stabilized emulsions cannot be separated by mechanical methods. A
significant proportion of "water in oil" emulsions is in this category.
Adverse hydraulic conditions of settling such as turbulence, convective
flows, mixing, etc. represent negative influences on emulsion separation. Signifi-
cant improvement of separation efficiency for petroleum emulsions is achieved by
the use of gravitational settling in combination with thermal, chemical and electri-
cal methods.
5.1.3 Mechanical Petroleum Drying
The most basic method in mechanical petroleum drying is gravitational

settling. There are two types of settling modes: periodic (i.e. batch) and continu-
ous. These are carried out in batch and continuous separators, respectively.
Cylindrical separating tanks (settling tanks), similar to petroleum storage
tanks, are usually employed as batch separators. Crude petroleum intended for
drying is pumped into the tank through the distribution pipeline. After filling the
tank, the content is allowed to stay for a predetermined period known as settling
time. The water then settles to the bottom section while petroleum floats on the top
section of the tank. The settling is carried out under a mild petroleum treatment
condition. Petroleum and water are taken out separately from the tank at the end of
the petroleum drying process. A positive result is achieved from the tank only if
the petroleum obtained is free of water.
In the case continuous separation, two types of separators can be distin-
guished: horizontal and vertical continuous separators. Horizontal separators are
subdivided into longitudinal and radial. Longitudinal horizontal separators can be
rectangular or round depending on the geometry of the cross section.
In gravitational continuous separators, the settling is carried out by the con-
tinuous flow of liquid through the separator. The separator is designed to achieve a
desired degree of settling in a predetermined holding or settling time.
5.1.4 Thermal Petroleum Drying
One of the modern ways of drying petroleum is thermal drying or thermal

processing. In this case, the petroleum for drying is heated up before the settling
step. Heating destabilizes the "water in petroleum" emulsion and promotes the
merger of fine droplets of water into larger droplets. Usually, protection layers
consisting of asphaltene-resinous substances and paraffins are formed on the
emulsion surface of water droplets. At normal temperatures, these layers create a
very stable structure that prevents the merging of droplets. By increasing the tem-
perature, the viscosity of the materials that form the protective layer is considera-
bly decreased. This leads to a reduction of the stability of the disperse structure,
thereby facilitating the merging of the water droplets. Besides, the viscosity of
petroleum is lowered as a result of heating. This promotes the acceleration of the
water separating from petroleum by settling. Thermal methods alone are applied
rarely in industry but they are used in combination with settling. In modern meth-
ods, thermal processing is usually used as a component of a more complex set of
methods of petroleum drying, for example, in combination with treatment with
chemical additives and settling (thermo-chemical drying), as well as in combina-
tion with electrical processing, etc.
228 Chapter 5
The heating of petroleum intended for drying is carried out in special heat-
ing sets (heaters). A large variety of such heaters have been developed. The heat-
ers are installed in a technological scheme of petroleum drying after the section
that deals with the separation of gases from petroleum, but before introducing the
petroleum into the separator.
5.1.5 Chemical Methods of Petroleum Drying
The chemical drying methods are widely employed in the modern petroleum
industry for petroleum drying. The fundamental principle of such methods is the
destruction of the "water in petroleum" emulsions by using chemical additives.
Many types of such additives have already been developed in the industry. The
efficiency of chemical petroleum drying depends substantially on the type of ad-
ditive used. The choice of an effective additive, in turn, depends on the type of
emulsion that is to be destabilized. In each case, the choice of additive is made
after the petroleum is analyzed in special laboratories.
Like in other combined petroleum drying methods, chemical drying is fol-
lowed with settling of the emulsion under the influence of gravity. Heating of the
petroleum is employed in some drying systems in combination with the use of
additives. The additive is added and blended with the emulsion. This creates the
conditions for removing the water from petroleum by settling. It is possible to
apply both periodic and continuous emulsion separation, but nowadays preference
is given to the continuous process. There are three locations where the chemical
drying of petroleum could be implemented:
1. Drying and separation carried out inside the petroleum oil well;
2. Drying and separation carried out in the collector's pipeline;
3. Petroleum drying carried out directly in separation tanks where additives are
added to the tank that is filled with petroleum.
The first two methods have many advantages and are more effective than
the third method.
Filtration that is based on the selective adsorption of different substances is
employed for the separation of unstable emulsions. The material of the filter layer
can be dry sand; glass; aspen, maple, poplar and other types of non-resinous wood;
and metal particles. Glass fiber, which is usually well moistened with water and
not with petroleum is used quite often. Petroleum drying by filtration is applied
very seldom because of low productivity as well as the need to change the filter
material frequently.
5.1.6 Thermal Chemical Petroleum Drying
The stability of the protective layers is reduced or completely destroyed by

thermal chemical methods. This method accelerates the process of petroleum
emulsion separation. For more than 80% of petroleum processed, the thermal
chemical method is used. This method has become widely used due to the oppor-
tunity it presents to treat petroleum with varying water contents without changing
the technological processing scheme, as well as the ability to change the additives
depending on the emulsion properties without replacing any of the devices used in
a standard technological scheme. However, the thermal chemical method has a
number of drawbacks. These include high additive prices and high heat consump-
tion.
Desalting and drying processes are usually conducted in the industry at
temperatures ranging from 50 to!00°C. If a higher temperature is to be used, then
the process must be carried out at a high pressure because of the need to keep the
emulsion in the liquid phase. For this purpose, it is necessary to use separators
with thicker walls. This leads to an increase in the price for the hardware.
The reduction of the protective influence of the interfacial layers on the
water droplets is essentially affected by the presence of additives. All additives can
be divided into:
• electrolyte
• non-electrolyte
• colloidal additives
Some organic and mineral acids (sulfuric, hydrochloric and acetic acids),
alkali and salts (table salt, chloride ion, etc.) can be used as electrolytes. The elec-
trolytes can form the insoluble products which reduce stability of the protection
layer or promote their destruction. Electrolytes as additives are applied extremely
rarely because of their high price and, particularly, their corrosive properties as it
affects the separators. The non-electrolytes are organic substances which are capa-
ble of dissolving the protective film on the water droplets and reducing the viscos-
ity of petroleum. This leads to the acceleration of the water droplets. This type of
additive can be gasoline, acetone, alcohol, benzene, phenol, etc. Non-electrolytes
are not used in industry because of their high price.
Colloidal additives are interfacial active substances which can destroy emul-
sions or weaken the protective film and can transform the native water in oil emul-
sion into the opposite type (oil in water); i.e. it can promote emulsion inversion.
Most effective additives are formed by reaction of ethylene oxide with or-
ganic substances; they are widely applied in the industry. Using the ethylene ox-
ide/organic substance ratio involved in the reaction to produce the additive can
control the efficiency of this additive group. The additive solubility in water in-
creases with the lengthening of the ethylene oxide chain. If it is necessary, it is
possible to make these additives with hydrophobic properties by reactions with
230 Chapter 5
propylene oxide, i.e. there is the opportunity to create various additives with dif-
ferent properties.
The additives should dissolve well in one of the emulsion phases (in water
or petroleum), i.e. they should be hydrophilic or hydrophobia, in order to be able
to destroy the protective film of the water droplets. Also, they should be inert to
metals, should not worsen the quality of petroleum, should be cheap, and should
be of universal applicability with respect to use for various emulsions.
The sooner the additive is added to the emulsion of water in petroleum, the
easier the separation. For separation, however, just adding the additive to petro-
leum is not sufficient. It is necessary to ensure the best possible contact between
the additive and the water droplets. Intensive mixing and emulsion heating can
achieve this.
Electrical desalting and drying of petroleum is especially widely applied in
the industry, but less often in the oil wells. The opportunity created by the applica-
tion of the electrical method in combination with many other methods can be
attributed to one main advantage of this method.
It is known that the separation of petroleum using an electrical field with
variable frequency is more effective than the separation with a constant electrical
field.
Viscosity and density of the emulsion, dispersion, water content, electrical
properties as well as the stability of the protective films considerably influence the
efficiency of electrical separation. However, the main factor is the intensity of the
electrical field. The electrical separators are operated at the current industrial fre-
quency (50 Hz for Europe and 60 Hz for North America), rarely by constant cur-
rent. The voltage on the electrodes in the separators ranges from 10,000 to 45,000
V.
The electrical separators can be spherical and cylindrical in geometry, and
can be installed in horizontal or vertical orientation.
5.1.7 Stabilization of Petroleum
The extracted petroleum can contain dissolved gases (nitrogen, oxygen,

hydrogen sulfide, carbonic acid, argon and others) and light hydrocarbons in vari-
ous quantities. During petroleum transportation from the oil wells to the oil refin-
ery the gases are lost from the oil because of insufficient hermetic sealing of the
pipelines and storage tanks. This leads to significant losses of the light petroleum
fractions. During evaporation of light fractions such as methane, ethane and pro-
pane, the relatively heavier hydrocarbons (butane, pentane, etc.) can be evaporated
as well. It is known that the more often petroleum contacts with the atmosphere
and the longer these contacts are, the higher the loss of the light fractions.
To prevent the loss of petroleum, it is necessary to achieve complete her-
metic sealing during petroleum transportation by all methods. However, the exis-
tence currently of non-perfect hermetic pipelines does not allow this.
Hence, it is necessary to remove the gases and light fractions from petro-
leum at the oil wells and to direct them for further processing. This consequently
lowers the evaporation ability of petroleum.
It is also possible to prevent the loss of the light fractions of petroleum by
application of rational systems of petroleum extraction, gas treatment, and petro-
leum stabilization before its subsequent transport and storage. It is necessary to
understand that stabilization of petroleum in this case is the extraction of light
hydrocarbons (which under normal conditions are gases) for further processing in
the petrochemical industry.
Thus, separation is used in this case as the main method for petroleum stabi-
lization at the oil wells. Separators of the widest applicability are of gravitational
and centrifugal designs.
In gravitational separators, separation of droplets and firm suspensions from
a gas flow occurs by the influence of gravity. A high degree of gas and liquid
separation can only be achieved at a very slow flow speed. The optimum speed as
established in practice is 0.1 m/s at a pressure of 6 MPa. The proportion of petro-
leum suspension separation from the gas at this flow speed is 75—85%.
In centrifugal separators, separation of the gas from petroleum occurs by the
influence of a centrifugal force.
5.1.8 Technological Schemes for Petroleum Preparation
The extraction and preparation of petroleum and gas, which begin at the
opening of the oil wells and end at the preparation units, follow a uniform tech-
nological system. There are many technological schemes of petroleum prepara-
tion. However, they are usually considered together with the petroleum extraction
systems at the oil wells.
5.1.9 Pressure Extraction System
The pressure extraction system (see Fig. 5.1) is operated as follows. The
quantity of petroleum from each oil well (produced with the natural layer pressure)
is serially measured using an automatic group measurement unit. Then, the petro-
leum from various oil wells in the field is transported to the local separation sta-
tion. The quantity of the petroleum from the oil wells is measured after the pre-
liminary gas separation with the centrifugal separator. After that, the petroleum
and gas are directed to a local separation unit, where gas is separated from the
petroleum by the first stage separator at the pressure 4—5 bar and then directed to
the gas processing station. Petroleum with layer water and solved gases will be
pumped to the central processing station, where the second step of separation
232 Chapter 5
begins by the end of the separators. The gas from the second step of separation is
directed to the gas processing station using a set of compressors.
This pressure extraction system is completely hermetically sealed. Therefore
it excludes loss of gas and light petroleum fractions. The pressure extraction sys-
tem allows for petroleum preparation at a central processing station for oils from
several oil wells located in an area up to a 100-km radius. However, long distances
for petroleum transport can lead to the creation of stable emulsions. With high
humidity of the petroleum, this can lead to an increase in operations and transport
costs. Nevertheless, it is one of the promising systems of petroleum extraction that
is widely applied.
There are many technological schemes for petroleum preparation. However,
technical and economic considerations determine which scheme is used and the
location of installation. It is known that the lowest capital investment and opera-
tional costs for petroleum preparation are for installations in locations of the great-
est petroleum concentration (collector stations, commodity parks, and head of-
fices).
*nL»|cs | r-«i
^GPS
Fig. 5.1: Pressure extracting systems:

I - bypasses, 2 - separators, 3 - measurement devices, 4 - collectors, 5 - first
stage separators, 6 - pumps, 7 - second stage separator, 8 - third stage separator,
9 - reservoirs, CS - Compressor station, GPS - Gas Processing Station.
The optimal technological scheme for petroleum preparation is obtained

with a scheme that allows petroleum to be processed to the allowable contents of
water and salts, and with the necessary depth of stabilization at the lowest costs, in
the shortest possible process time.
In the modern petroleum industry, complex petroleum preparation is carried
out in areas close to the oil wells. Therefore, complex installations for petroleum
preparation at the petroleum wells also integrate the processes of drying, desalting
and stabilization.
Figure 5.2 shows the basic technological scheme of the installation for the
thermal chemical petroleum preparation.
Petroleum from the oil well is directed to the combined separation installa-
tion 2, in which hot water from settling tank 6 containing additives is directed to
mixer 1. This begins the partial separation of gas, petroleum and water. The sepa-
rated water is directed to petroleum traps 20, whereas the separated gas moves to
the gas processing station. The petroleum from separator 2 together with the re-
maining water is pumped by pump 3 through heat exchanger 4 and vapor heater 5.
Fig. 5.2: Technological scheme of the complex for thermal chemical petroleum prepara-
tion
1. Mixer, 2. Separator, 3. Pump, 4. Heat exchanger, 5. Vapor heater, 6-7. Settling
tanks, 8. Dryer, 9. Vacuum separator, 10. Refrigerator, 11. Hydro-centrifugal
separator, 12. Pump, 13. Water line, 14. Oven, 15. Vapor heater, 16. Oxygen tank,
17. Pump, 18. Compressor, 19. Separator, 20. Oil traps, 21. Pump, 22. Vessels, 23.
Pump, 24. Separators, 25. Vessel, 26. Tank, 27. Pump, 28. Compressor.
Then the heated petroleum is moved to settling tank 6 for the final separation of
petroleum from water. The separated water is carried away from the petroleum
with a major fraction of the mineral salts. For better desalting, the petroleum from
settling tank 6 is directed for mixing with hot fresh water pumped by pump 17
after pre-heating in the vapor heater 15 and removing the oxygen in tank 16. After
mixing fresh water with the petroleum, the emulsion is directed to settling tank 7,
where the required salt concentration is achieved. After desalting and separation of
water, the petroleum is directed, if required, from settling tank 7 to additional
desalting and drying in electrical dryer 8. If the water and salts contents are within
234 Chapter 5
the allowable limits after electrical dryer 8, the petroleum is moved directly to
vacuum separator 9. Vacuum compressors 12 transport the gases from separator 9,
from which after refrigerator 10 and hydro-centrifugal separator 11, a major frac-
tion of light hydrocarbons is separated. The condensed product from separator 11
is directed to gas and gasoline collectors. Additives are introduced into the petro-
leum before heat exchanger 4. This influences the interfacial property of the pro-
tective films between the two phases in the emulsion.
This system allows the cleaning of waste water and its subsequent direction
by pumps for the flooding of the oil layer.
5.2 DESALTING
Even with the preparation of petroleum at the oil wells, the crude oil often
contains water, inorganic salts, suspended solids, and water-soluble trace metal
compounds. As a first step in the refining process (to reduce corrosion, plugging,
and fouling of equipment and to prevent the poisoning catalysts in the processing
units), these contaminants must be removed by processes of desalting and dehy-
dration or drying.
The methods of desalting and dehydration are based on the same funda-
mental principles as those for petroleum preparation at the oil wells. The two most
typical methods of crude oil desalting: chemical and electrostatic separation, use
hot water as the extraction agent. In chemical desalting, water and chemical sur-
factant (demulsifiers) are added to the crude, heated so that salts and other impuri-
ties dissolve in the water or attach themselves to it, and then held in a tank where
they settle out. Electrical desalting is the application of high-voltage electrostatic
charges to concentrate suspended water globules at the bottom of the settling tank.
Surfactants are added only when the petroleum has a large amount of suspended
solids. Both methods of desalting are continuous. A third and less-common proc-
ess involves filtering heated crude using diatomaceous earth.
The feedstock crude oil is heated to between 110 and 160°C to reduce vis-
cosity and surface tension for easier mixing and separation of the water. The tem-
perature is limited by the vapor pressure of the petroleum. In both methods, other
chemicals may be added. Ammonia is often used to reduce corrosion. Caustic or
acid may be added to adjust the pH of the water wash.
Wastewater and contaminants are discharged from the bottom of the settling
tank to the wastewater treatment facility. The desalted crude is continuously drawn
from the top of the settling tanks and sent to the petroleum rectification unit. All
the apparatus for petroleum desalting and drying can be classified in two big
groups:
• spherical desalter
• cylindrical desalter, which can be sub-classified into:
horizontal
vertical
During electrical desalting, electricity is used to increase the rate of move-

ment the water droplets with the solved salts as well as to accelerate the merging
of small droplets to form bigger ones. These cause the separation of the droplets
from the petroleum emulsion.
In modern refineries, the sections for petroleum desalting and drying are
combined with atmospheric and vacuum rectification.
5.3 ATMOSPHERIC RECTIFICATION
The petroleum prepared at the oil well comes to the petroleum refinery and
the first process at modern refineries (excluding the refineries working only with
non-conventional feed) is atmospheric rectification. The first refinery, which was
opened in 1861, produced only kerosene and this was possible by using simple
atmospheric distillation alone. The by-products of this refinery included tar and
naphtha. For the next thirty years, kerosene still remained the main product that
consumers wanted. Two significant events changed this situation:
• invention of electric light decreased the demand for kerosene,
• invention of the internal combustion engine created a demand for diesel fuel
and gasoline.
Distillation is the process involving the conversion of a liquid into vapor that
is subsequently condensed back to a liquid. It is exemplified when steam*from a
kettle becomes deposited as droplets of distilled water on a cold surface. A simple
example of a distillation unit is shown in Figure 3.3.
Distillation is used to separate volatile products from non-volatile sub-
stances. The early experimentalists also employed distillation. Aristotle (384-322
BC) mentioned that pure water was made by evaporation of seawater.
Most methods of distillation used by industry are variations of simple dis-
tillation. The basic operation of the industrial process requires the use of the same
principal installations as the above mentioned example of simple distillation: a still
(flask and gas burner) in which a liquid is heated and partly vaporized, a condenser
to cool the vapor, and a receiver to collect the distillate. In the still is charged a
mixture of substances with different boiling points. The lowest boiling products
distill first, followed by others in order of increasing boiling temperatures. In
comparison to our example shown in Figure 5.3, larger equipment made of metal
or ceramic is employed for industrial applications.
In the petroleum industry, the method of fractional distillation, differential
distillation, or rectification is utilized for the primary separation of crude oil into
fractions with regard to their boiling temperatures, because simple distillation is
not efficient for separating liquids whose boiling points lie close to one another.
236 Chapter 5
non-volatile
volatile
material
product
Fig. 5.3: A simple distillation unit.
In this operation, the vapors from distillation are repeatedly condensed and re-
vaporized in the next evaporator. Figure 5.4 shows the principle of differential
distillation or rectification. This installation works on the basis of the reverse or
counter-current flow principle. For a steady state functioning of the rectification
unit, it is important that there is equilibrium in every evaporator. This means that
for the example shown, the following equations have to be obeyed:
• Yo = x,
• YH = XK
Instead of the example shown, rectification towers are used for rectification
in the petroleum industry. Rectification towers can be classified as follows:
On the basis of the area of application:
• atmospheric towers
• vacuum towers
On the basis of the type of tower internals:
• Tray towers
• Trickle or packed towers
ii
n v ; YII
volatile
product
feed
non-volatile
substances
Fig. 5.4: Differential distillation, rectification.

nv - stream of vapor product
ri] - stream of liquid product
y - concentration of the light component in vapor
x - concentration of the light component in liquid
On the basis of the type of function:

• simple towers
• complicated towers
One example of the simple tray tower is shown in Figure 5.5. From Figure
5.5, it is clearly seen that for the effective functioning of all types of rectification
towers, it is especially important to return back to the tower part of the head con-
densed vapor and bottom product. The objective is to achieve the closest possible
contact between the rising vapor and the descending liquid so as to allow only the
most volatile material to rise in the form of vapor to the receiver, while returning
the less volatile material as liquid towards the still.
238 Chapter 5
A comparison of the towers shown in Figures 5.5 and 5.6 illustrates the
difference between simple and complicated towers. The main difference between
these two types of rectification towers is that in a complicated tower, many vola-
tile products or side products are obtained. The addition of small towers called
strippers are used to improve the purity of the side products. The function of the
stripper is the same as for the big rectification towers.
volatile
product
bottom
product
Fig. 5.5: The simple tray tower.

volatile
product 1
volatile
product 2
volatile
feed 1 product 3
feed 2 volatile
product 4
bottom
product
Fig. 5.6: Complicated rectification tower.
The schematic that illustrates the function of the tower tray is shown in
Figure 5.7. It is shown that the tray tower has the same function as shown in Fig-
ure 5.4. The only difference is that in the actual rectification tower, the trays also
play the role of the evaporators. The vapor goes through the liquid on the trays and
there is material transfer in the bubble regime. The liquid coming from the top tray
(phlegm) carries the material exchanged between the liquid and vapor phases in
the tower.
Sieve trays consist of punched metal sheets with holes of diameters of 4-13
mm with a division of the holes of 2.5 to 4 times dho|e (see Fig. 5.8). The proper-
240 Chapter 5
tion of liquid on the tower trays ranges from 0.05 to 0.2 times the feed. Although
there are many types of trays, only three are used in the petroleum industry. These
are:
• sieve trays
• bubble cap trays
• valve trays
The liquid does not flow through the holes, but is held by the pressure loss during
vapor flow through the tray holes. This determines that there is limited range of
feed load.
vapor liquid
Fig. 5.7: The principle of the tray tower function.
In valve trays, the holes in the tray are bigger. Also, the valves are mobile
and cannot be completely closed. These valves ensure that the flow of the liquid
through the tray holes is impossible even with varying feed loads. The hole di-
ameter of this type of tray ranges from 20 to 30 mm, valve diameter from 40 to 50
mm and division of the tray holes 1.5 to 3 times dva|ve. Figure 5.9 shows an exam-
ple of the valve in the valve tray.
dhole = 4 - 13 mm
LJL dhole '

I
( 2 . 5 - 4)
!•**!
Fig. 5.8: Sieve tray.
The bubble cap trays have the largest range of feed load possible. However,
it is also the most expensive. By immersing the bell edges into the liquid (this
being necessary for bubble formation), the pressure loss can be characterized by
the static proportion for the bell tray. During very low gas load, all the bells are no
longer functioning, so that the liquid does not have sufficient contact with the
vapor phase. This leads to a decrease in the tray efficiency. An example of the bell
for the bubble cap tray is shown in Figure 5.10.
Fig. 5.9: Valve in the valve tray.
liquid liquid
vapor
Fig. 5.10: The bell of the bubble cap tray.

242 Chapter 5
Packed or trickle towers have similar disadvantages as tray towers. Packing

materials are used in the packed tower instead of trays as in the tray tower. An
example of the trickle or packed tower is shown in Figure 5.11.
volatile
product
feed
bottom
product
Fig. 5.11: The packed or trickle tower.
In comparison with tray towers, the packed or trickle towers have the fol-
lowing advantages:
• low pressure loss
• low installation cost
• more homogenate mixture of the vapor and liquid phases
• better material exchange between the vapor and the liquid phases
There are many types of packings for packed towers. However, the most
frequently used are as shown below:
The main property of the packing for rectification towers is the specific
surface area, which determines the efficiency of the packing. The larger the spe-
cific surface area, the more effectively the packing operates.
For both types of towers, it is important to determine the number of theoreti-
cal trays required to perform fractionation to specified compositions of fractions.
For packed or trickle towers, the theoretical tray is replaced with the height
equivalent of the packed layer equivalent to one theoretical tray.
There are a few methods to evaluate the number theoretical trays. Tray to
tray calculations is one the most popular methods.
Raschig-ring
Pall-ring
Intalox-saddle
Bed-saddle
An illustration of this method is given below for a mixture containing four

components. Components 1 and 2 have to be present in the volatile product,
whereas components 3 and 4 have to be present in the bottom product. Therefore,
the separation cut is between components 2 and 3. Moreover, components 2 and 3
have different boiling temperatures and are present in different amounts in the two
products. They are called "key components (key - K)". Component 2 is the lighter
or volatile component (LK - light key) whereas component 3 is the heavier or
bottom component (HK - heavy key).
244 Chapter 5
In the rectification tower, four equations are available from material bal-
ances (overall and component material balances) for the separation of the four
components. If the feed or input amount and its composition are known, then one
has two unknown streams H (head product) and B (bottom product) and three
unknown concentrations in each stream. Thus, generally there are eight unknown
values for a four component mixture. Only two of these unknown values are to be
determined. Thus the material balance of the rectification tower can be evaluated
to obtain the top and bottom product rates. The vapor stream in the stripping sec-
tion can be determined as the vapor stream ascending from the tower bottom. This
stream can be taken as constant throughout the stripping section of the tower. This
vapor stream plus the fraction of feed that is vapor will yield both the head product
stream as well as the reflux stream that will be returned to the tower. The reflux
ratio can be determined based on the minimum reflux. There is a method for the
evaluation of the minimum reflux. This method will be shown in a later section.
The next step for the calculation of the number of theoretical trays is to
make a material balance around the tower bottom (it can also be started from the
tower top). The concentrations of the components in the ascending vapor stream
are calculated from equilibrium equation (Dalton Raoult laws) for the existing
mixture composition in the tower bottom (5.3).
(5.3)
where y , - the concentration of component i in the vapor

Xj - the concentration of component /' in the liquid
Psi- saturated vapor pressure of component i
p - pressure in the rectification tower
For hydrocarbons, these equilibrium relations are often represented by y, = K,x,

where K, = PS,/P = K-factor for component i. K-factors are functions of both pres-
sure and temperature but assumed to be independent of composition. Also, for a
multi-component mixture, a relative volatility (otj) can be defined for each compo-
nent with one of the components, say 3, as a basis such that a, = K/Kj. Charts for
K-factors for various components are available in Handbooks.
For a four component mixture, the above equilibrium relations will yield
three independent equations thereby providing the three extra equations required
to determine all the eight unknowns. The equilibrium equations together with the
material balance equations are applied to each plate to calculate the vapor and
liquid compositions for each plate as follows.
The liquid flow from the first tray at the tower bottom results from balances
(5 .4, Fig. 5. 12):
(5.4)
The boiling temperature of liquid L] is calculated on a trial and error basis. This
must be lower than the temperature of the tower bottom. This boiling temperature
is calculated on the basis that at a specific pressure this temperature must satisfy
the relation Ey, = 1.0. For a mixture of components 1,2,3 and 4 with component 3
as the basis, Zy, = LK,x/ = KjIcx/X; = Z(Ps/P)x, = 1.0. The trial starts with a guess
of a temperature. Then the values of af are calculated from the values of K, (read
from a chart) at this temperature. The value of K3 is calculated as Kj = 1.0/Ece,x,.
Then the temperature corresponding to the calculated value of K? is compared to
the assumed temperature. If the values are different, the calculated temperature is
used for the next iteration. After the final temperature is known (i.e. convergence
is reached), the vapor composition is calculated from equation 5.1 or its equiva-
lents.
1. tray
\ bottom
bottom heating
Fig. 5.12: Tower bottom.
The calculation of the temperature difference between the bottom and the
first tray makes use of heat balance at the tower bottom.
The next step is the calculation of the liquid composition in tray 2 using
material balance equations and the vapor composition for the first tray of the down
part of the tower. During this calculation, it is important to remember that the
composition of the liquid phase on the first tray is the same as the vapor composi-
tion in the tower bottom. This is because the liquid on the first tray is the product
of the condensation of the vapor produced at the bottom of the tower. The material
balance is shown in equation (5.5):
246 Chapter 5
L, + V, = Vs + L, (5.5)
The balance element for the equation (5.5) is shown in Figure 5.13.
These tray-by-tray calculations are continued until we reach the input or
feed tray where the calculated composition of the input is similar to the actual feed
composition.
The calculation of the upper section of the rectification tower proceeds in
the same way as the bottom section. In this case, the calculation could be started
from the top tray and proceeds towards the feed tray.
The disadvantage of this method is the need for iteration. Thus, the calcula-
tions are cumbersome and time-consuming if hand calculators are used. Nowadays
all calculations of theoretical number of trays are carried out by use of the com-
puter and many software packages for such calculations are available in the mar-
ket. Two approaches can be used for distillation calculations:
n-th tray
I
1 vnn-l
_
Fig. 5.13: Material Balance element of the rectification tower.
One is if the product compositions are known, then tray-by-tray calculations are
used to determine the number of trays needed to obtain those product composi-
tions. The other is if the number of trays is given (such as in an existing unit), then
calculations are made to determine the compositions of products that could be
obtained from such a unit.
If the distillation unit provides for side products and/or multiple feed loca-
tions, then the tray to tray calculations will use material balances for each tray that
account for these additional streams. Furthermore, it is important to note that frac-
tion cuts for crude oil fractionation are based more on boiling temperature ranges
rather than on composition.
The next important parameter required for rectification, as mentioned above,

is the minimum reflux. The minimum reflux is the value of reflux for which the
number of theoretical trays is infinite. In technical terms, a rectification tower that
has the number of trays over a hundred can be taken as having infinite number of
trays.
The McCabe-Thiele diagram is used (Fig. 5.14) for the calculation of the
minimum reflux.
The x-axis in this diagram shows the composition of the liquid phase in
equilibrium with the composition of the vapor phase (y-axis). The straight lines B2
and H2 are balance lines. These lines show the balance between two trays (the
composition of the vapor on the n - 1 tray equals the liquid composition on the nth
tray). The two points 3 and 2 are called pinch-points; on these points, the compo-
sitions of the liquid and vapor do not change any more from tray to tray. That
means that an infinite number of trays is required for rectification of such a mix-
ture with this reflux value.
Fig. 5.14: McCabe-Thiele diagram.
The following four operations need to be carried out to calculate the mini-
mum reflux:
1. assume a minimum reflux,
2. carry out the evaluation from tray to tray from B and H,
3. add a small amount of the lightest component to the mixture at the "pinch-
point" 3, and evaluate from tray to tray until the head of the tower,
248 Chapter 5
4. repeat as in point 3 for "pinch-point" 2. If the results of the third and fourth
points are equal, then the assumed value was correct. If not, then repeat all the
operations from the first until fourth point.
Rectification units in the petroleum industry are used to separate the crude
oil into fractions for subsequent processing in secondary processes such as cata-
lytic reforming, cracking, alkylation, or coking. In turn, each of these complex
secondary-processing units incorporates a fractional distillation tower to separate
its own reaction products.
Modern petroleum rectification units operate continuously over long periods
of time. For rectification, petroleum is drawn from storage tanks at ambient tem-
perature and pumped at a constant rate through a series of heat exchangers in order
to reach a temperature of approximately 120°C. The preheated petroleum passes
though an oven (see position O, Fig. 5.15). At this position it is heated to a tem-
perature between 315 and 400°C, depending on the type of petroleum and the
quality of the end products desired. A mixture of vapor and nonvaporized oil
passes from the oven into the rectification tower. The size of an industrial rectifi-
cation tower is about 45 meters tall with 20 to 40 fractionating trays. The most
common trays used in the petroleum industry are sieve or valve trays. Petroleum
vapor rises up through the trays to the top of the tower. It is condensed to a liquid
in a water- or air-cooled condenser at the top of the tower. A small amount of gas
remains uncondensed (see position 2, Fig. 5.15) and is piped into the refinery fuel-
gas system. A pressure control valve on the fuel-gas line maintains rectification
tower pressure at the desired value, usually near atmospheric pressure. Part of the
condensed liquid, reflux, is pumped back into the top of the column and descends
from tray to tray, contacting rising vapors as they pass through the slots in the
trays. The liquid progressively absorbs heavier constituents from the vapor and, in
turn, releases lighter constituents to the vapor phase.
The intermediate products, or side-streams (see positions 4, 5, Fig. 5.15) are
drawn at several points from the tower dependent on the fractions desired. Usually
these fractions are gasoline and diesel fractions. Dependent on the production type
in the refineries, jet fraction can be drawn as well. In addition, modern petroleum
rectification units employ intermediate reflux streams (Fig. 5.6).
T_
Tl
•>• 5
Fig. 5.15: The simple atmospheric rectification:

O - Oven
Tl - Rectification tower
E - Separator
1. Petroleum, 2. Light product, 3. Gasoline, 4. Kerosene, 5. Diesel, 6. Bottom product
Typical boiling ranges for various streams are as follows: light straight-run
naphtha (head), 20-95°C; heavy naphtha (side-stream), 90-165°C; crude kerosene
or jet (side-stream), 150-245°C; light gas oil or diesel (side-stream), 215-315°C.
Non-vaporized oil entering the tower flows downward over the trays (below the
feed tray) called stripping trays (Fig. 5.6). These act to remove any light constitu-
ents remaining in the liquid. In any case, steam is injected into the bottom of the
tower in order to reduce the partial pressure of the hydrocarbons; this plays a
similar role as a vacuum during vacuum rectification (see section 5.5). The residue
that is obtained from the bottom of the tower is suitable for blending into residual
fuels. Alternatively, it may be further distilled under vacuum conditions to yield
250 Chapter 5
quantities of distilled oils for manufacture into lubricating oils or for use as feed-
stock in gas oil cracking processes.
In the modern petroleum industry, a more complicated scheme of the rectifi-
cation unit, the so called "two-step rectification", is used. An illustration of this
type of rectification unit is shown in Figure 5.16.
The main difference between the simple rectification and two-step rectifica-
tion is the presence of the second rectification tower (T2) in the two-step unit. In
the latter case, the feed passes to the first rectification tower at a temperature of
approximately 200-240°C. Because of the low temperature used, the volatile
product from the first tower only forms part of the gasoline fraction. The bottom
product from Tl (Fig. 3.16) passes to the oven for heating until it reaches a feed
Tl T2
O-l
0-2
P-l
Fig. 5.16: 'Two-step" rectification unit:

O-l and O-2-Oven
Tl and T2 - Rectification tower
El and E2 - Separator
I. Petroleum, 2. Light product, 3. Gasoline, 4. Kerosene, 5. Diesel, 6. Bottom product
temperature of approximately 300-340°C. Further rectification of the petroleum

proceeds in the same way as in simple rectification. As compared with the two-
step rectification scheme, the main disadvantage of the simple rectification scheme
is that if very light (over 15% of gasoline) fractions or incompletely dry petroleum
passes to the simple rectification unit, it can cause an increased pressure in the heat
exchangers and the tower. This can lead to a decreased efficiency of the rectifica-
tion unit or, in the worse case, can lead to breaking of heating units.
In both rectification methods, a bottom product is produced that will be
separated into fractions in the vacuum distillation unit.
5.2.4 Vacuum Rectification
The principles and main units for vacuum rectification resemble those for
atmospheric rectification. The major exceptions are that larger-diameter towers are
used to maintain comparable vapor velocities at reduced operating pressures. A
vacuum of 50 to 100 mm of Hg absolute is produced by a vacuum pump or steam
ejector. The capacity of modern vacuum rectification units is about 3.5 million
tons per annum.
The primary advantage of vacuum rectification is that it allows the distilling
of heavier materials at lower temperatures than would be required at atmospheric
pressure, thus avoiding thermal cracking of the components. The input tempera-
ture of the atmospheric residue in the vacuum tower usually does not exceed
425°C. The residue from atmospheric rectification is preheated against distillates
and vacuum residue before heating up in the fired heater. From the heater outlet
the stream is fed to the vacuum tower. The high specific volume of vapor at low
pressure demands large tower diameters, particularly in the upper part. The lower
part of the tower (below the feed inlet) is used as a stripping section using steam to
reduce the partial pressure of hydrocarbons in the vapor phase.
An example of the one-step vacuum rectification is shown in Figure 5.17. In
Figure 5.17, the feed (atmospheric residue) passes through oven Ol to the vacuum
tower Tl. In this tower, the feed is typically separated into the following fractions:
vacuum residue 8, middle oil distillate 4, and light oil distillate 3. The middle oil
fraction is fractionated in tower T2 into fraction with narrower boiling temperature
ranges. Steam 2 is used to reduce the partial pressure of the oil fraction which,
finally, helps in the separation of the light fractions from the oil.
The one-step vacuum rectification unit does not allow for production of oil
fractions with desired market quality. This is why one-step vacuum rectification
units can be found nowadays only in small refineries. The scheme that allows for
the production of oil fractions with a higher quality is the two-step vacuum rectifi-
cation. An illustration of the two-step vacuum rectification plant is shown in Fig-
ure 5.18.
252 Chapter 5
T2
Tl
O2
Ol
Fig. 5.17: One-step vacuum rectification:

O-l and O-2-Oven
1. Residue from the rectification under the atmosphere pressure, 2. Light oil, 3-6. Distillate,
7-9. Vacuum residue
In the two-step rectification unit, the feed 1 in the first tower is distilled to
obtain the following fractions: light oil 2, middle oil 3, and partly distilled vacuum
residue 6. The vacuum residue from the first tower passes through oven Ol to
rectification tower T2, where it is fractionated to narrower fractions. In compari-
son with the one-step scheme, the two-step scheme requires more energy for pro-
duction, but the quality of the oil fractions is much higher.
The residue remaining after vacuum rectification is called "Goudron". This
may be used for blending to produce road asphalt or residual fuel oil, or it may be
used as a feedstock for thermal cracking or coking units. Vacuum rectification
units are an essential part of the many processing units required for the production
of lubricants.
In modern refineries, atmospheric and vacuum rectification processes are
rarely carried out in separate units. Usually, combined atmospheric-vacuum recti-
fication units are used for these processes. An illustration of a scheme for this
combined unit used in refineries in Russia is shown in Figure 5.19.
Petroleum 1 for rectification is fed from storage tanks at ambient tempera-
ture through a series of heat exchangers in order to attain the temperature of ap-
proximately 120°C (see Fig. 5.19). A controlled amount of fresh water is intro-
duced, and the mixture is pumped into an electrical desalting and drying unit
(EDDU), where it passes through an electrical field and a salt water phase is sepa-
rated. If the salt is not removed at this stage, it will be deposited later on the tubes
of the ovens or heat exchangers. This can cause plugging and corrosion.
Fig. 5.18: Two-step vacuum rectification:

O-l-Oven
1. Residue from the rectification under the atmosphere pressure, 2.Light distillates, 3-5.
Vacuum distillate, 6-7. Vacuum residue
The desalted crude oil passes through additional heat exchangers to the first at-
mospheric tower Tl. Light gasoline 2 is separated at the top of this tower from a
mixture of anti-corrosive additives added to the raw petroleum because of its high
sulfur content. The sulfur compounds can be very corrosive to the metallic tower
walls and this can lead to destruction of the units. Anti-corrosive additives slow
down corrosion of the rectification units. The bottom product from rectification
tower 1 passes to oven O2. There, it is heated to a temperature of approximately
350°C. A mixture of vapor and petroleum liquid passes from oven O2 into rectifi-
cation tower T2. The volatile product obtained in T2 is gasoline fraction. This
fraction passes to the next rectification tower T3, where it is fractionated into
fractions of light hydrocarbons, gases 3, and residue. The residue from T3 passes
to the section for secondary gasoline distillation (SSGD), where the gasoline frac-
tion is fractionated into narrower fractions (4-7) used for the production of fuels
and petrochemicals. The side-streams from rectification tower T2 consist of the
following fuel fractions: 8 - kerosene fraction with boiling range of 180-230°C, 9
- light diesel fraction (230-280°C), and 10 - heavy diesel fraction (280-350°C).
Rectification tower T2 employs intermediate reflux streams, which come from the
stripping section of three towers. Stream 15 is fed to the stripping sections of the
three towers as well as tower T2 in order to reduce the partial pressure of the light
products during rectification.
Petroleum from T2 that is not vaporized passes to oven O4, where it is
heated to a temperature of approximately 425°C (the input temperature in vacuum
tower T4). After this, the heated atmospheric residue passes to the vacuum tower
254 Chapter 5
Fig. 5.19: Combined atmospheric vacuum rectification unit:

T4 where it is fractionated into: oil fraction 11, gases, cracking products and the
rest of heavy diesel fraction 14, and vacuum residue or goudron 12.
It is seen that in the illustration (Fig. 5.19), a two-step atmospheric rectifica-
tion unit is combined with a one-step vacuum rectification unit. In modern refin-
eries, however, the combined rectification unit consists of a two-step atmospheric
unit and a two-step vacuum rectification unit. At the MIDER refinery in Germany
(the most modern refinery in Europe), a combination of a three-step atmospheric
and a one-step vacuum rectification unit is used. A scheme for this unit is shown
in Figure 5.20.
The unit shown in Figure 5.20 saves about 50,000 tons of fuel oil per year,
compared with a one-step rectification process with the same capacity. The proc-
ess development was based on the objective of avoiding unnecessary overheating
of light components. Additionally, it avoids the thermal degrading associated with
drawing off of heavy cuts. To this end, crude oil is pre-fractionated in the tower
operating with best conditions of 125°C and 2 bar, and then in a second stage at
131°C and 1 bar. The pre-distilled petroleum is then fractionated in the main atmo-
goudron
416°C
Fig. 5.20: Combined rectification unit:

T1-T5 - Rectification towers
Fig. 5.19 Legend:

O-1-O-4 -Oven
T1-T4 - Rectification tower
EDDU - Electrical desalting and drying unit
SSGD - Section for secondary gasoline distillation
1. Petroleum, 2. Gases, 3. Light gasoline, 4-7. Narrow fractions, 8. Kerosene, 9. Light
diesel, 10. Heavy diesel, 11. Oil fraction, 12. Vacuum residue, 13. Fraction 180-230°C, 14.
Heavy diesel, 15. Water - steam
256 Chapter 5
spheric tower at 1 bar and 357°C. The bottom product (atmospheric residue) is
subsequently heated to 416°C and passed to the vacuum column.
Processing of petroleum under the above-specified conditions results in a
vacuum residue of 585°C cut point. The combined rectification yields the fol-
lowing cuts:
• Straight-run gasoline (boiling begins 80°C)
• Naphtha as feedstock for the petrochemical industry (80-95°C)
• Heavy naphtha (96-160°C)
• Kerosene (160-225°C)
• Light and heavy gas oil and vacuum gas oil (225-400°C)
• Medium and heavy vacuum fraction as cat cracker feed (400-585°C)
• Vacuum residue for bitumen production and feed for visbreaker.
5.5 Heat Exchangers and Separators
The distillation tower is the most important equipment used in rectification units.
The different types of rectification towers and schemes have been described al-
ready in the preceding sections. In addition to towers, there are also other major
items of equipment used in the rectification unit. These are essentially units used
for heat transfer. Heat exchangers play a very important role not only in rectifica-
tion units, but also in petroleum processing as a whole. All the heat exchangers
used in the petroleum industry can be classified as follows:
• air-coolers
• tube-bundle or shell and tube heat exchanger
• finned heat exchanger
• U-tube heat exchanger
• double-pipe heat exchanger
The first four types of heat exchangers are especially popular in the petro-
leum industry. The double-pipe heat exchanger is only used for heating high vis-
cosity materials such as vacuum residue or bitumen. Figure 5.21 shows an exam-
ple of the horizontal tube-bundle heat exchanger.
The example of the heat exchanger shown in Figure 5.21 is used in the low
temperature range because of thermal expansion of the tubes. The U-tube heat
exchanger and finned heat exchanger were developed for operating at higher tem-
peratures. The last has the largest temperature interval of operation. Figures 5.22
and 5.23 show examples of these two types of heat exchangers, respectively.
From Figures 5.22 and 5.23, it is seen that there is room to accommodate the
thermal expansion of the tubes. In the case of the finned heat exchanger, the tubes
can expand in an expandable shell, whereas in the case of the U-tube heat ex-
changer, expansion room is provided because of the existence of free fixed tubes
in a firm shell.
The heat exchangers can be installed both vertically and horizontally. The
heaters for the rectification-tower bottom-product reflux are special units of inter-
est. There are four types of heat exchanger schemes. These are shown in Figure
5.24.
T
Fig. 5.21: Horizontal tube-bundle (shell and tube) heat exchanger.
A
~TT~ r\
Fig. 5.22: Finned heat exchanger.

258 Chapter 5
Fig. 5.23: U-tube heat exchanger.

T
a)
Fig. 5.24: Examples of the bottom product reflux:

a) Natural reflux with vertical heater
b) Natural reflux with horizontal heater
c) Forced reflux with vertical heater
d) Forced reflux with horizontal heater
The schemes with natural reflux are operated based on the principle of natu-
ral convection (i.e. circulation based on density difference between cold and
heated fluid streams) to create a thermo-siphon. The hotter stream has the lower
density. In natural reflux, the heated feed passes to the top of the heat exchanger
and then to the bottom of tower by itself while the colder stream drains from the
tower bottom to the heater. Forced reflux is based on using pumps for the circula-
tion.
The last major items of equipment in rectification units are the separators.
Separators are also used in many other technological schemes in the petroleum
industry where there is the need to separate materials based on density difference.
Usually, separators are vessels and can be classified as:
• horizontal
• vertical
• spherical
Processing of Light and Heavy
Distillates
INTRODUCTION
In foregoing sections, we presented only the primary processes for petro-

leum treatment. It is important to note that all these processes are called "primary
processes" because the petroleum only undergoes physical treatment. This means
that chemical changes to the feed do not occur. All the processes we will describe
in the sections of this chapter are referred to as "secondary processes". This is
intended to indicate that chemical changes of the feed occur during these treat-
ments.
6.1 THERMAL CRACKING
With the advent of the mass production of large numbers of gasoline-

powered vehicles, the demand for gasoline has grown dramatically. On the other
hand, distillation processes produce only a specific amount of gasoline from a
given quantity of crude oil of specific characteristics. In 1913, the thermal crack-
ing process was developed. In this process, heavy fuels containing large molecules
are broken into smaller ones to produce additional gasoline and distillate fuels by
application of both pressure and intense heat.
Thermal cracking is a radical chain process. The chain process contains
three main stages: chain start, chain growth and chain termination.
In the "chain start", cracking of the hydrocarbons in the heavy feed proceeds
at the weakest bonds of the hydrocarbons. Also, cracking of C-C bonds proceeds
first, because the energy requirement for C-C bond breakage in hydrocarbons is
always lower than that for C-H bond scission. In a long chain, the weakest C-C
bond (C-C bond with the lowest energy requirement for breakage) is at the center
of the molecule. Furthermore, the difference in energy of the C-C bond at different
261
262 Chapter 6
locations in a molecule is lower at a higher temperature than at lower tempera-

tures. This means that at moderate temperature (about 400-450°C), cracking of the
hydrocarbon chains proceeds symmetrically. At a higher temperature, cracking
can proceed almost with the same probability at every C-C bond in the hydrocar-
bon molecule.
It should be noted that paraffins and olefins are formed during paraffin
cracking (see (6.1)).
(6.1)
The olefins formed during thermal cracking are characterized by the fact
that the bond in the (^-position (the second bond from the double bond) is weaker
than the C-C bond in the paraffin chain. The energy of the bond in the paraffin
chain is approximately 320 kJ/mol, whereas the energy of the bond in the p-
position is 259 kJ/mol and the energy of the C-C bond in the a-position is 371
kJ/mol. This means that the olefins formed during cracking can be cracked more
extensively than the initial paraffins.
The side chains of aromatic rings can be cracked very extensively. The
energy of the bond in the (i-position for these compounds is 273 kJ/mol.
The next step after "chain start" is "chain growth". The same reactions as
occurred during "chain start" also occur in this stage of thermal cracking. How-
ever, the most important reaction of "chain growth" is the reaction for formation
of light stable molecules (HR), from the radical (-R) formed during chain start as
well as from the heavier radical from the feed molecule (6.2).
•R + CH3-CHrCHrCH2-CH3 -> HR + -CHrCHrCHrCHrCHj (6.2)
Different radicals have different reactivity for thermal cracking. In the fol-
lowing example, the radicals are presented in order of their reaction abilities:
R-H2C- > (R)2-C > (R)3-C-
Reaction (6.2) is one of the possible reactions of "chain growth". Another

reaction that can also occur in this stage is the cracking of radicals at the (3-bond
(6.3).
•CH2-CH2-CH2-CHrCH3 -> -CH2-H2C + •CH2-CH2-CH3

1 (6.3)
CH2=CH2
Processing of Light and Heavy Distillates 263
Another reaction type that occurs during the "chain growth" step of thermal
cracking is the addition reaction involving a radical and a double bond (6.4).
•CH3 + CH2=CH-CH3 -> CH3-CH2-CH-CH3 (6.4)
Chain termination is the last stage of every chain reaction. There are two
types of reactions that typically occur in thermal cracking chain termination. One
type is radical recombination (6.5).
•CH2-CH3 + -CH2-CH2-CH3 -» CH3-CH2-CH2-CH2-CH3 (6.5)
The second type is radical disproportionation (6.6).
•CH2-CH3 + -CH2-CH2-CH3 -» CH3-CH3 + CH2=CH-CH3 (6.6)
The greatest problem during thermal cracking arises from reactions involv-
ing aromatic feed. Aromatic compounds in the feed have a very high tendency to
undergo polycondensation reactions that lead to coke formation. Coke formation
decreases the yields of the desired gasoline and diesel fractions. One example of a
polycondensation reaction is shown in reaction (6.7).
-3H2
(6.7)
Reaction (6.7) is an illustration that molecules of some products from ther-

mal cracking reactions can sometimes be larger than the feed molecules.
It is not only the mechanism that is important in the processing of light and
heavy distillates. The kinetics of the chemical process is also important. Chemical
kinetics deals with the velocity of material conversion by the chemical reactions.
The smallest step of a chemical reaction is called an elementary reaction.
The reaction equation for an elementary reaction j with N components can be
presented as in equation (6.8).
264 Chapter 6
N N
i ' *' J ' R N l

*'-'' P
where v( - stoichiometric coefficients

XI,J,R- reactant i in reaction j
XJJP- product i in reaction j
Depending on the sum of the stoichiometric coefficients of the reactants

involved in the elementary reaction, one refers to such a reaction as being mono-
molecular, bimolecular, termolecular, etc. The concentration change caused by
one elementary reaction can be described by equation (6.9).
d[X L j ]/d[t]=v i j.r i j (6.9)
where ry - reaction velocity of reaction j
Reaction velocity is proportional to the concentration of the reactants raised

to the power of the reaction order. Reaction order is equal to the stoichiometric
coefficient for an elementary reaction. It has been shown in the foregoing discus-
sion that thermal cracking is a very complicated process involving reversible and
irreversible reactions. In this case, the reaction velocities for the elementary reac-
tions of the cracking process can be described by equation (6.10).
N v. . N
M
,p) (6.10)
Where kj - reaction velocity coefficient for the forward reaction

k_j - reaction velocity coefficient for the reverse reaction
The ratio of kj to k_j is called equilibrium constant. This constant depends on

the thermodynamic properties of the system and can be calculated by equation
(6.11).
(6.11)
where Kj - equilibrium constant for reaction j
The equilibrium constant calculated in this manner shows the maximum

possible degree of conversion of the feed into products. However, as was men-
tioned earlier, the equilibrium constant can be calculated based on the thermody-
namic conditions of the system. This can be done by using equation (6.12)
K P j = exp(-AG/RT) (6.12)
where Kpj - equilibrium constant for reaction j, at temperature T and pres-

sure P
AGj - Gibbs energy difference for reaction j, at temperature T and
pressure P
R - gas constant (8.317 J/mol)
T - reaction temperature (K)
The reactions that proceed with changes in volume and pressure are very
important. Thermal cracking proceeds at high temperatures, and many products of
this process are gaseous. This means that there is a volume increase during the
reaction. This dependence can be described by equation (6.13).
AG = AG 0 +19.13-log(P-T) (6.13)
where AG - Gibbs energy difference for reaction j, at temperature T and

pressure P
AGj - Gibbs energy difference for reaction j, at temperature T and by
standard pressure
P - pressure in the reaction zone
T - reaction temperature
It is obvious from equations (6.12) and (6.13) that the higher the pressure is,
the smaller is the equilibrium constant. This is valid for reactions such as thermal
cracking, which proceed with a volume increase. It means that a higher pressure
leads to an acceleration of polycondensation, alkylation, hydrogenation and other
reactions that proceed with a volume decrease.
The thermodynamic possibility of a reaction can be estimated by the value
of the Gibbs energy difference. Gibbs energy is the part of the internal energy of
the substance, which can be converted into work. This means that a reaction can
go spontaneously only in the case where the difference between the Gibbs energy
of products and reactants is negative. This implies that part of the Gibbs energy
has been converted into the work needed for making the reaction go.
Gibbs energy contains two values: enthalpy and entropy. Generally, this
energy can be presented as in equation (6.14).
G = H-T-S (6.14)
where G - Gibbs energy at temperature T

H - enthalpy at temperature T
S - entropy at temperature T
266 Chapter 6
T - temperature
The next equation (6.15), which is a derivation from equation (6.14), is used
for the calculation of the difference of the Gibbs energy. This equation is known as
Gibbs-Helmholtz equation.
AG = A H - T - A S (6.15)
where AG - difference in Gibbs energy at temperature T

AH - difference in enthalpy at temperature T
AS - difference in entropy at temperature T
T - temperature
The difference in enthalpy in this equation represents the total energy

change that takes place between the system and its environment. The multiplica-
tion of temperature and the term involving the difference in entropy represents the
energy used to take care of the intermolecular activity. This is wasted energy and
has to be subtracted from the total energy. An analogy can be drawn here between
a mechanical engine and a chemical reaction. When a mechanical engine performs
useful work, not all of the energy output of the engine goes towards work. Some
of the energy output is wasted to overcome friction of the moving parts. The en-
ergy to overcome friction is wasted energy and must be subtracted from the total
energy output in order to obtain useful energy that is capable of performing a task
or work. Similarly, the difference in Gibbs energy represents useful energy of a
chemical reaction.
The difference in the Gibbs energy for many reactions can be calculated
based on empirical tables that are available in references 7-10 at the end of part III
of this book.
However, most of the calculations of Gibbs energy are based on the rule that
Gibbs energy has a linear dependence on temperature. Usually, this dependence is
as presented in equation (6.16).
AG = A + B - T (6.16)
where A and B - coefficients specific for the chemical reaction

T - temperature
More about thermodynamic evaluations can be found in references 11 and

12 at the end of part III of this book.
Thermodynamics can only show how much of the reactants can be con-
verted into the product. Usually, thermal cracking reactions are relatively slow
reactions. This is why thermodynamic evaluation alone is often not enough to
guide the industrial thermal cracking process since this would suggest carrying out
the reactions at a low temperature to obtain a high conversion. Reactions at a low
temperature can be quite slow and impossible to carry out at industrial scale. Thus,
often it becomes necessary to increase the temperature of the process in order to
increase the velocity of the reaction, despite that this may not lead to the maximum
possible degree of conversion of the reactants. It is well known that increase of the
temperature by 10°C leads to an increase in the reaction velocity of 2-4 times.
This dependence can be described by the Arrhenius equation (6.17).
k = ko • exp(-EA/RT) (6.17)
where k - reaction velocity constant

ko -frequencyfactor
EA - activation energy
Activation energy in equation (6.17) shows the minimal energy level which
molecules must have to be able to react. The physical significance of this value
can be explained based on Boltzmann law, which is presented in equation (6.18).
NE = N-exp(-E/RT) (6.18)
where NE - number of molecules with energy higher than E

N - total number of molecules
E - energy
The Arrhenius equation can be developed based on the Boltzmann's law.

The physical significance can be better explained based on a comparison of equa-
tion (6.17) and (6.18). For example, the frequency factor can be compared with the
number of particles which are available in the reaction zone and can potentially
react to form the product. Reaction velocity constant can be compared with the
number of molecules that has energy higher than the activation energy.
The graphical presentation of Boltzmann's law can show the temperature
influence on reaction velocity. This is presented in Figure 6.1. The diagram of the
distribution of the kinetic energy on the molecules (Figure 6.1) shows that more
molecules with a high energy level are available at the higher temperature. If one
assumes that only the collisions of molecules with a certain energy (i.e. activation
energy) can lead to reaction, then the number of these molecules increases with a
temperature increase, and thus the increase in the reaction velocity. This implies
that only the molecules with energy higher than the activation energy for the reac-
tion can react to form reaction products. The effect of the reaction rate increase
with increasing temperature is due to the increase in the number of molecules with
sufficiently high energy.
268 Chapter 6
Every real chemical reaction leads to formation of product over many steps.
It also leads to formation of compounds that exist only for a short time as well.
This was shown in reaction (6.2). This chemical reaction can be represented by an
overall general equation (6.19).
Frequency
Energy
Fig. 6.1: Graphical presentation of Boltzmann's law:

T] first temperature, T2 second temperature, T, < T2, EA activation energy
A + B-» A-B-» P (6-19)
where A and B - reactants

A---B - transition complex
P - products
The transition complex in equation (6.19) is derived from the collision the-
ory. The main idea in this theory is that two molecules form a transition complex
by collision, which can exist only for a short time. Then, the activation energy is
the difference in the energy levels of the reactants and the transition complex. This
is presented in Figure 6.2.
From Figure 6.2, it is obvious that the formation of a transition complex is
possible only if a higher energy than the activation energy is released by the colli-
sion of two molecules. This implies that the kinetic energy of the movement of
molecule, as well as the rotational energy and vibrational energy of the reactants
must be higher than the activation energy to enable the formation of the transition
complex.
From equation (6.17) and Figure 6.1, it is obvious that temperature has a
large influence on every type of reaction. Desired reactions during thermal crack-
ing are reactions that lead to breakage of hydrocarbons. These types of reactions
are referred to as monomolecular reactions. This means that only one molecule of
reactant is needed to react to the product. The reaction velocity of such a reaction
can hardly be influenced by pressure. On the other hand, bi-molecular reactions
can be greatly influenced by pressure. These include polycondensation, alkylation,
hydration, and recombination. Most polymolecular reactions are undesired in
thermal cracking. However, most modern thermal cracking plants operate at high
pressures. The reason to carry out the industrial process under pressure is to pre-
vent further cracking of the light cracking products to gas. It should be noted that
the desired product during thermal cracking is the light liquid fraction.
One additional kinetic theory that deserves to be mentioned is the theory
based on the Eyring equation. The essence in this theory is captured by the fol-
lowing phrase credited to Henry Eyring in 1945: "... a molecular system ... passes
... from one state of equilibrium to another ... by means of all possible intermediate
paths, but the path that is most economical in energy will be more often traveled."
The equation of the chemical reaction (6.19), which was used for the interpretation
of the kinetic theory based on the Arrhenius equation, is modified in order to ex-
plain the Eyring equation, as shown in equation (6.20).
A + B <-> A-B -> P (6.20)
where A and B - reactants

A---B - transition complex
P - products
It is obvious that the difference between equation (6.19) and (6.20) is that
the formation of the transition complex A—B is an equilibrium reaction. This
means, for example, that by reaction (6.20) shown for thermal cracking, the tran-
sition complex is an unstable compound that reacts immediately to products or
back to reactants. The reaction velocity of the transition complex formation can be
Energy
A-B
A+B
Reaction patch
Fig. 6.2: Definition of activation energy.
270 Chapter 6
[A] • [B] - k., • [A-B] - k2 • [A-B] (6.21)
where [A] and [B] - concenlration of reactants

[A---B] - concentration of transition complex
k[ - reaction velocity constant for the formation of transition complex
from A and B
k .1 - reaction velocity constant for the consumption of the transition
complex to form A and B
k2 - reaction velocity constant for the formation of product P from the
transition complex
The transition complex is an unstable compound that is independent of its

reaction velocity. It is also permanently in equilibrium with reactants A and B. It
means that the terms k, • [A] • [B] and k., • [A---B] in equation (6.21) are equal to
each other. Hence, equation (6.21) can be rewritten more simply as equation
(6.22).
= -k 2 -[A-B] (6.22)
The reaction velocity constant k2 can be calculated based on statistical ther-

modynamics. This is presented in equation (6.23).
(6.23)
where k2 - reaction velocity constant

k,, - Boltzmann constant (1.381 -10"23 J • K"1)
h - Planck constant (6.626- 10 ~34 J • s)
Because k2 depends only on temperature, and this is a compound independ-

ent value, it is often called the universal constant of transition complex formation.
The value of k2 at room temperature for all types of reactions is approximately 6 •
lO^sec'1.
The concentration of the transition complex at certain reaction times can be
determined by the kinetic equation. It can also be determined by other means. It
was shown earlier that the formation of the transition complex from reactants is an
equilibrium reaction. This implies that the concentration of the transition complex
can be determined based on the mass law for the equilibrium reactions as pre-
sented in equation (6.24).
[A-B] = K= • [A] • [B] (6.24)
where K= - equilibrium constant

Equation (6.22) can be rewritten based on equations (6.23) and (6.24) to the
form in equation (6.25).
(6.25)
From a comparison of the classical kinetic equation (6.10), it is obvious that

equation (6.25) can be written in a more simple form as equation (6.26) where the
Eyring reaction velocity constant is calculated using equation (6.27).
(6.26)
where k - Eyring reaction velocity constant
k=K=-VT/h (6.27)
It was shown earlier in equation (6. 12) that the equilibrium constant depends
on the thermodynamic characteristics of the reaction system. This dependency can
be rewritten as in equation (6.28) for the transition complex.
AG= = - R - T - l n ( K = ) (6.28)
Where AG= - activation Gibbs energy at temperature T

K= - equilibrium constant
The basic form of the equation for the calculating of the Gibbs energy was
given by equation (6.14). However this equation must be rewritten by equation
(6.29) to calculate the activation Gibbs energy.
AG= = AH=-T-AS= (6.29)
where AG= - activation Gibbs energy at temperature T

AFT - activation enthalpy at temperature T
AS= - activation entropy at temperature T
The activation enthalpy in the case presented in equation (6.26) can be de-
scribed as the enthalpy difference between the reactants and the transition com-
plex. This is presented in Figure 6.3.
272 Chapter 6
Potential energy
A-B
A+B AH=
Reaction patch
Fig. 6.3: Definition of activation enthalpy.
The meaning of the activation entropy can be explained in the same way as
was done for the activation enthalpy. Activation entropy is presented as the differ-
ence between entropy of reactants and entropy of transition complex.
The thermodynamic meaning of activation Gibbs energy is the thermody-
namic possibility of reaction from reactants to transition complex. However, the
value of the activation Gibbs energy can be interpreted as a measure of the stabil-
ity of the transition complex. The less the activation Gibbs energy is, the more
stable is the transition complex formed during the reaction. The reaction velocity
depends on the concentration of the transition complex, which increases with its
increasing stability. There are three important consequences regarding the reaction
system which depend on the activation Gibbs energy:
AG = > 0 - reaction is impossible
AG= = 0 - equilibrium reaction, there is no change of reactants concentrations
AG= < 0 - reaction happens spontaneously
The equilibrium constant K= can be calculated based on equations (6.28) and

(6.29) as shown in equation (6.30).
= -AH=/R-T + (6.30)
The Eyring equation can be written based on equations (6.27) and (6.30) as
shown in equation (6.31).
k = (kb • T / h) • exp(-AH7R • T) • exp(AS7R) (6.31)
Equation (6.31) must be rewritten as a linear equation, as it is shown by

equation (6.32), for the practical determination of the activation parameters.
ln(k) = ln(kb • T / h) - AH=/R • T + AS=/R (6.32)
However, equation (6.32) must be rewritten as shown in equation (6.33).
ln(k/T) = ln(kb / h) - AH=/R • T + AS=/R (6.33)
All the thermodynamic parameters can be determined graphically as shown

in Figure 6.4.
ln(k/T)
0
1/T
Fig. 6.4: Graphical determination of the thermodynamic parameters of the Eyring equa-
tion.
Activation enthalpy is determined from the value of the angle, a, as given

by equation (6.34).
AH" = R • tan(cc) (6.34)
Activation entropy is determined from the point of intersection, b, by equa-

tion (6.35).
(6.35)
However, the use of the Eyring equation instead of Arrhenius equations

must be done very accurately. If it is impossible to draw the line over the experi-
mental points as used in the diagram shown in Figure 6.4, the use of the Eyring
equation for calculating the kinetic parameters should be discontinued. The high
value of the error in the Eyring equation method is often caused by the fact that in
real reaction systems, especially complicated systems such as the cracking of
crude oil, many reactions take place at the same time. This leads to the inappropri-
274 Chapter 6
ateness of using this theory by crude oil chemists in many cases. However, the
Eyring equation gives much more information about the mechanism of the reac-
tions occurring in the system in comparison to the Arrhenius equation. As was
shown earlier, both theories have their advantages and disadvantages. Hence, the
application of any of the theories must be decided in every case based on the com-
plexity of the reactions occurring within the reaction system and the importance of
studying the reaction mechanism for the system.
More about kinetic evaluation of chemical reactions and the different types
of chemical reaction can be found in references 13-16 at the end of part III of this
book.
The kinetic evaluation of the chemical reactions can be carried out by much
more complicated models than has been presented. The evaluation with such mod-
els is often possible by numerical methods alone. There are many programs and
special software packages in the market which can be used for kinetic evaluation.
References 17-20 show a few programs and methods which can be used for the
evaluation of cracking processes.
Thermal cracking units provide a severe treatment to the feed and, often,
convert up to 50% of the incoming feed to naphtha and light diesel oils.
To obtain a more severe treatment of the feed during thermal cracking, a
two-stage cracking unit is employed. A schematic of such a unit is shown in Fig-
ure 6.1.
In the scheme (Fig. 6.5), the feed (heavy residue from atmospheric rectifica-
tion) passes to the bottom part of tower T3 and to the upper part of the low-
pressure evaporator T4. The feed in T4 mixes with the heavy gas oil vapors and
then passes to T3. The feed from the bottom of T3 passes to oven Ol for the heavy
feed.
Tower T3 has a blind tray in its middle section. The vapor from the bottom
part of the tower can pass through this tray to the upper section of the tower, but
the liquid from the upper section cannot pass to the bottom section. The liquid
from the upper section of tower T3 passes to the deep cracking oven O2.
The cracked products from both the ovens are directed to the reaction tower
Tl. The mixture of vapor and liquid from Tl passes to the high-pressure evapora-
tor T2. In T2 the cracking residue is separated from the vapor. This residue passes
to the low-pressure evaporator T4, and is partly evaporated. The evaporator T4 has
a blind tray in the middle section similar to that of tower T3. The vapor product
(heavy gas oil) is partly condensed in the upper section of T4 and mixed with the
fresh feed. The non-condensed part leaves the cracking unit as kerosene - gas oil
fraction 2.
The volatile product from T2 passes to the rectification tower T3. The gas 1
and gasoline fractions leave the upper section of tower T3. The gasoline fraction
passes to the rectification tower T5 for further fractionation into fractions of light
gasoline 3 and gasoline fraction 4.
feed
Fig. 6.5: Two-stage thermal cracking unit:

O land O2-Oven
Tl - Reaction tower
T2 - High pressure evaporator
T3 - Low pressure evaporator
T4 - Rectification tower
1. Gas, 2. Kerosene - gas oil fraction, 3. Light gasoline, 4. Gasoline, 5. Residue
The last product of the thermal cracking unit is the cracking residue 5, the
bottom product of the low-pressure evaporator T4.
Thermal cracking processes can only convert up to 50% of the feed, as
stated previously. Catalytic cracking was developed in order to improve the con-
version level of the heavy feed.
6.2 CATALYTIC CRACKING
The use of thermal cracking units to convert gas oils into naphtha began in
1913. These units produced small quantities of unstable naphtha and large
amounts of by-product coke. While they succeeded in providing a small increase
in gasoline yields, it was the commercialization of the fluid catalytic cracking
process in 1942 that really established the foundation for modern petroleum re-
fining. The process not only provided a highly efficient means of converting high-
boiling gas oils into naphtha to meet the rising demand for high-octane gasoline,
but it also represented a breakthrough in catalyst technology.
The use of a catalyst in the cracking reaction increases the yield of high-
quality products under much less severe operating conditions than in thermal
cracking. Several complex reactions are involved, but the principal mechanism by
276 Chapter 6
which long-chain hydrocarbons are cracked into lighter products can be explained
by the carbonium ion theory. According to this theory, the catalysts can be classi-
fied into two groups as follows:
• catalysis on metals
• catalysis on acid catalysts
Before we look at the mechanism of catalytic cracking on catalysts, it is

appropriate to give a definition of a catalyst. Catalysis is derived from the Greek
word "katalysis" meaning destruction or weakening. A catalyst is a substance that
changes the rate of a chemical reaction but remains chemically unchanged at the
end of the reaction.
All the catalytic processes can be divided into heterogeneous and homoge-
nous catalytic processes. All the reactions take place on the surface of the catalysts
during heterogeneous catalysis. Thus, for this type of catalysis, it is especially
important to select catalysts that have as large a surface area as possible. This
means that porosity of the catalyst must be as high as possible since high porosity
is generally responsible for a large surface area.
The reaction mechanism in a heterogeneous catalytic process is more com-
plicated than the mechanism in a non-catalytic reaction. In the first place, there is
the influence of many physical stages of the catalysis on the reaction itself and on
the reaction velocity. The main stages of the catalytic reaction can be represented
as follows:
1. diffusion of reactants through the liquid or gas film on the surface of the
catalyst particle,
2. diffusion of reactants into the pores of the catalyst,
3. adsorption of the reactants on the inner surface of the catalyst pores,
4. chemical reaction on the inner catalyst surface,
5. desorption of products from the inner catalyst surface,
6. diffusion from the inner catalyst surface through the pores to the external
catalyst surface,
7. diffusion of products through the liquid or gas film on the external sur-
face of the catalyst particle into the reactor zone.
All these reaction steps are presented graphically in Figure 6. 6. From Figure
6.6, it is obvious that catalysis is a very complicated physical and chemical proc-
ess. Also, each of the seven catalysis steps shown can proceed with a different
velocity. The slowest stage is called the rate limiting step of the process, because
this limits the overall velocity or rate of the process. The general velocity of the
chemical catalytic reaction has the same value as the velocity of the slowest step
of the catalytic process. This is why the reaction velocity of a catalytic reaction is
called the effective reaction velocity.
Fig. 6.6: Model of heterogeneous catalysis.

Black points - products
White points - reactants
Depending on the velocity of each of the various steps of catalysis, it is

usual to divide it into the following three regimes of catalysis:
1. Kinetic regime - Reaction velocity is the slowest step of the catalytic
process. The surface of the catalysts is used fully and most efficiently in
this type of catalysis because the pore surface area and the external sur-
face areas are used equally;
2. Pore diffusion regime - Diffusion in the pores is the slowest step in this
type of catalysis. Reaction takes place mainly on the external surface of
the catalysts,
3. Film diffusion regime - Diffusion through the film on the surface of the
catalysts is the slowest step of the catalytic process. Reaction proceeds
only on the outside surface of the catalyst.
Table 6.1 shows a comparison of the most important process constants for
different regimes of catalysis.
According to the modern view on catalysis, a catalytic reaction can be repre-

sented as in equation (6.36).
R + X -» R- X -» P-X -> P +X (6.36)
where R - reactant
X - catalyst
R—X - transition complex of reactant with catalyst
P-X - transition complex of product with catalyst
P - product
278 Chapter 6
Table 6.1: Comparison of some process parameters for different catalysis re-
gimes.
Reaction velocity Mass transfer coefficient Pore diffusion coefficient
constant
Kinetic regime small large large
Pore diffusion medium large small
regime
Film diffusion large small very small
regime
From equation (6.36), it is clear that this reaction has more than one activa-
tion energy. There are at least two activation energies. It is remarkable that each of
the activation energies is smaller than the activation energy of the reaction without
catalyst. Figure 6.7 shows a comparison of a non-catalytic reaction and a catalytic
reaction.
It is obvious from Figure 6.7 that every chemical reaction can proceed and
react from reactants to products only after it has been able to go over the reaction
barrier, which is equal to the activation energy. It is to be seen that the non-
catalytic reaction only has one activation energy, EA. The reaction path of the
catalytic reaction proceeds over three energetic barriers: E A i, EA2 and EA3- How-
ever, the adsorption energy of the reactants on catalyst, the activation energy of the
catalytic reaction and the desorption energy of products from catalyst are each
much smaller than the activation energy of the non-catalytic reaction. Conse-
quently, a catalytic reaction proceeds faster than a non-catalytic reaction. Catalysts
can be compared to a leader that leads the reaction over more energetically effec-
tive states than happens by non-catalytic reactions.
There are three theories of catalysis that are used in modern science to ex-
plain the mechanism of catalytic reactions. These are:
- geometric theory
- electron theory
- chemical theory
The main idea of the geometric theory of catalysis is the assumption that the
activity of the catalyst depends on the geometrical form of the crystal grid of the
catalysts. Catalysts with crystal grid similar in form to the reactant molecules are
usually more active than catalysts with crystal grids different from the reactant
molecules.
Energy
Reaction patch
Fig. 6.7: Definition of activation energy during a catalytic process:

EA - activation energy of the non-catalytic reaction of R to P
EAI - adsorption energy of reactants on catalyst
EAZ - activation energy of catalytic reaction of R to P
EAS - desorption energy of products from catalyst
Electron theory is based on the property of the electrons of catalyst to trans-

fer electrical charge from catalysts to reactants. According to this theory, this
means that the catalyst's activity is due to their ability to transfer electrical charge
to the reactants thereby weakening the bonds in reactant molecules.
The last theory is based on the assumption that catalyst is a chemical sub-
stance which can form a chemical substance or transition complex with one reac-
tant, and then the other reactant reacts with this substance with the regeneration of
the catalyst and the formation of product. The activation energy of such reaction is
smaller than a direct reaction of reactants to products.
More about catalysis and modeling of reactions during catalytic cracking
can be found in references 21-27 at the end of part III of this book.
In the mechanism involving catalysis on metals during catalytic cracking,
the catalyst promotes the removal of a negatively charged hydride ion from a
paraffin compound. The mechanism in this type of catalysis is illustrated in Figure
6.8.
As a result of the interaction between the catalyst and the hydrocarbon
molecule, one part of the molecule is bonded with the catalyst via a strong double-
electron bond. Another part of the molecule is bonded with the catalyst via a weak
one-electron bond. The two surface compounds formed are unstable and are thus
very reactive. This explains the high velocity of catalytic reactions. Typical metal
catalysts are Fe, Co, Ni, Ru, Rh, Re, Ir and Pt. The activity of the metal catalysts is
explained by the non-saturated d-shell (or d-level) orbital that acts as a free radical
during thermal cracking.
280 Chapter 6
Fig. 6.8: Catalysis on metals.
Another type of catalysis is that on acid catalysts. The mechanism in this

type of catalysis is based on the addition of a positively charged proton (H+) to an
olefm compound. This results in the formation of a carbonium ion, a positively
charged molecule that has only a very short life as an intermediate compound. It
transfers the positive charge through the hydrocarbon. The reaction of the acid
catalysts (HX) and olefm is depicted in the reaction equation (6.37).
HX + CH3-CH=CH-R -> X + CH3-CH2-CH+-R (6.37)
Hydrocarbon ion transfer continues as hydrocarbon compounds come into

contact with active sites on the surface of the catalyst that promote the continued
addition of protons or removal of hydride ions. The result is a weakening of car-
bon-carbon bonds in many of the hydrocarbon molecules and a consequent
cracking into smaller compounds.
The main reactions of the carbon ion is the cracking of the C-C-bonds. This
reaction proceeds in the same as was shown for thermal cracking.
Olefins crack more readily than paraffins since double C=C bonds are more
friable under reaction conditions. Iso-paraffins and naphthenes are cracked more
readily than normal paraffins, which in turn are cracked more readily than aro-
matics. In fact, aromatic ring compounds are very resistant to cracking, since they
readily deactivate fluid cracking catalysts by blocking the active sites of the cata-
lyst (see the next part). The reactions postulated for olefm compounds apply prin-
cipally to intermediate products within the reactor system, since the olefm content
of catalytic cracking feedstock is usually very low.
The most important difference between catalytic cracking and thermal
cracking is in the reaction velocity of certain reactions that occur during the
cracking. For example, the reactions involving the cracking of paraffins proceed
with a reaction velocity a thousand times larger than for thermal cracking [4]. The
following reactions of cyclic saturated hydrocarbons proceed by catalytic cracking
with noticeable velocity [4]:
Ring destruction with the formation of olefins is shown in reaction (6.38):
(6.38)
Isomerization of rings is shown by reaction (6.39):
(6.39)
Migration of alkyl side chain is shown by reaction (6.40):
(6.40)
And the typical aromatization reaction is presented by equation (6.41):
+ H2 (6.41)
The aromatic hydrocarbons only have a negative influence in catalytic

cracking as a result of polycondensation and coke formation on catalyst surface. It
should be noted that the destruction of aromatic ring without previously saturating
the unsaturated bonds is impossible even in catalytic cracking. However, aromatic
compounds are not absolutely non-reactive during catalytic cracking. The most
important reactions of aromatic compounds during catalytic cracking are isomeri-
zation reactions represented by reaction equations (6.42) and (6.43).
The isomerization reactions shown in equation (6.42) can proceed selec-
tively depending on the catalyst used in the process. Aluminosilicates are typical
for selective isomerization of aromatic compounds, because they have well de-
fined pore sizes depending on the type of aluminosilicate. The mechanism of se-
lective isomerization can be explained based on Figure 6.9.
282 Chapter 6
(6.42)
(6.43)
Fig. 6.9: Model of selective isomerization during catalysis cracking on aluminosilicate.
From Figure 6.9, it is obvious that a strictly defined size of catalyst pores
allows only the molecules with size less than the pore size to leave the catalyst
pore. This leads to the selective isomerization of aromatic compounds as shown in
the example in Figure 6.9.
The catalysts used during catalytic cracking or any other catalytic processes
have two main properties that determine the choice for the right catalyst for the
process. These are
• catalyst activity
• catalyst selectivity
Catalyst activity shows how intensively the catalysts promote the reaction.
Selectivity shows the ability to promote the desired reaction and inhibit any other
reaction that leads to by-products.
Typical modern catalytic cracking reactors operate at 480-550°C and at
relatively low pressures. At first, natural silica-alumina clays were used as cata-
lysts, but by the mid-1970s, zeolites and molecular sieve-based catalysts were
used. Zeolite catalysts give more selective yields of products, while reducing the
formation of gas and coke.
There are three basic functions in the catalytic cracking process:

• Reaction: Feedstock reacts with the catalyst and cracks into different hydro-
carbons.
• Regeneration: The catalyst is reactivated by burning off the coke.
• Fractionation: The cracked hydrocarbon stream is separated into various
products.
A modern catalytic cracking unit employs a finely divided solid catalyst that
has properties analogous to a fluid when it is agitated by air or oil vapors. The
principles of operation of the cracking unit are shown in Figure 6.10. In Figure
6.10, a reactor and regenerator are located side by side. The oil feed is vaporized
when it meets the hot catalyst at the feed-injection point, and the vapor flows up-
ward through the riser reactor at a high velocity, providing a fluidizing effect for
the catalyst particles. Catalytic reaction occurs exclusively in the riser reactor.
Coke, a byproduct of cracking, is deposited on the catalyst particles. Since
these deposits impair reaction efficiency, the catalyst must be continuously put
through the regenerator, where the carbon is burned with a current of air. The high
temperature of the regeneration process (675-785°C) heats the catalyst to the de-
sired reaction temperature for re-contacting fresh feed in the unit.
In order to regenerate the activity of the catalyst completely, a small amount
of fresh catalyst is added to the system from time to time. Figure 6.11 depicts
typical reactor-regenerator sections of a catalytic cracking unit used in petroleum
refineries.
Regenerator Reactor
Fuel gas
Propane/ propene
Bu tane / butyl ene
Gasoline
Kerosene
Diesel
Residue
Fig. 6.10: Catalytic cracking.
The three types of catalytic cracking processes in operation in modern refin-

eries are:
• Fluid catalytic cracking (FCC)
• Moving-bed catalytic cracking
• Thermofor catalytic cracking (TCC)
284 Chapter 6
The catalytic cracking process is very flexible, and operating parameters can
be adjusted to meet changing product demand. In addition to cracking, catalytic
activities include dehydrogenation, hydrogenation, and isomerization.
The most common process is fluid catalytic cracking (FCC) in which the oil
is cracked in the presence of a finely divided catalyst maintained in a fluidized
state by the oil vapors. The fluid cracker consists of a catalyst section and a frac-
tionating section that operate together as an integrated processing unit. The cata-
lyst section contains the reactor and regenerator. The fluid catalyst is continuously
circulated between the reactor and the regenerator using air, oil vapors, and steam
as the conveying media (see Fig. 6.11).
waste gas product waste gas product
steam
25 «—
air steam feed
a) Complex two-step catalyst regeneration

b) Simple, direct regeneration of catalyst
Fig. 6.11: The reactor-regenerator sections.
A typical FCC process involves mixing a preheated hydrocarbon charge

with hot, regenerated catalyst as it enters the riser leading to the reactor. The
charge is combined with a recycle stream within the riser, vaporized, and raised to
reactor temperature (500-550°C) by the hot catalyst.
The moving-bed catalytic cracking process is similar to the FCC process.
The catalyst is in the form of pellets that are moved continuously to the top of the
unit by conveyor or pneumatic lift tubes to a storage hopper, then flow downward
by gravity through the reactor, and finally to a regenerator. The regenerator and
hopper are isolated from the reactor by steam seals. The cracked product is sepa-
rated into recycled gas, oil, clarified oil, distillate, naphtha, and wet gas.
In a typical thermofor catalytic cracking unit, the preheated feedstock flows
by gravity through the catalytic reactor bed. The vapors are separated from the
catalyst and sent to a fractionating tower. The spent catalyst is regenerated, cooled,
and recycled. The flue gas from regeneration is sent to a carbon monoxide boiler
for heat recovery.
In a recent investigation involving the promotion of catalytic cracking, it

was shown that ozonolysis of heavy oil fractions and catalytic upgrading of fuel
distillates are good methods for increasing the degree of oil refining as well as
improving the quality of the oil product.
A low temperature cracking (350°C) of the ozonated crude oil raw material
initiated by ozonides and sulfoxides leads to a significant increase of distillate
fraction yield and a significant decrease in the sulfur content of the products.
More about catalytic cracking can be found in many references [28-32] at
the end of part III of this book.
6.3 VISBREAKING
The demand for light fractions grows all the time, at the same time the re-
quirement for heavy residual fuel oils declines. Furthermore, many of the new
sources of crude petroleum have yielded heavier crude oils with higher natural
yields of residual fuels. As a result, refiners have become even more dependent on
the conversion of residue components into lighter products.
In 1930, large volumes of residue were being processed in visbreaking units.
This simple process unit basically consists of a large oven that heats the feedstock
to a temperature in the range of 450 to 500°C. The residence time in the furnace is
carefully limited to prevent much of coke formation from taking place and clog-
ging the oven tubes. The heated feed is then charged to a reaction chamber, which
is kept at a pressure high enough to permit cracking of large molecules, but re-
stricts coke formation. The process fluid from the reaction chamber is cooled to
inhibit further cracking and then charged to a rectification tower for separation
into components.
Visbreaking units typically convert about 15% of the feedstock to naphtha
and diesel oils and produce a lower-viscosity residual fuel.
More details about the chemistry of visbreaking are given in chapter 8.
6.4 COKING
Coking is a severe thermal cracking process. Coke formation decreases the

feed conversion during thermal cracking, and the cracking reactor has to be fre-
quently cleaned because of the coke formed on the reactor walls. This negative
influence of coke formation reaction can be decreased if a process is used in which
coke is one of the products required. Coking is such a process. Cokers (the coking
units) produce no liquid cracking residue, but yield approximately 30% of coke.
Much of the low-sulfur coke from the coking process is employed to produce
electrodes for electrolytic smelting of aluminum. Most of the lower-quality coke is
286 Chapter 6
burned as fuel in admixture with coal. Coker economics usually favor the conver-
sion of residue into light products even if there is no market for coke.
All the existing coking units can be classified into three main types:
• Discontinuous coking
• Delayed coking
• Continuous coking
Discontinuous coking is the oldest coking process. A simple metal cube is

the equipment for this process. In the first step, the feed is loaded in the cube re-
actor. Then the reactor is heated. Light product is formed when a temperature of
approximately 300°C is reached. Then the temperature of the vapor phase in-
creases quickly from 300°C to approximately 445-460°C. After this temperature,
there is a slow down in the increase of the vapor temperature. This means that no
more volatile products are being formed. At this stage, coke formation is finished.
In the next step, the temperature of the reactor is approximately 460°C. Such
a high temperature is required for drying the coke (i.e. removing the volatile prod-
uct). After about three hours of drying, steam is injected into the reactor. The cube
reactor is cooled by steam until the temperature reaches approximately 250-
200°C. Air is then used for further cooling. At the temperature of approximately
200-150°C, the coke is evacuated from the cube reactor. The evacuation is done
using mechanical equipment only. At the present time, discontinuous coking is
used very rarely and at old refineries.
The next coking process is delayed coking. This process is a quasi-
continuous process that involves two main steps:
• Coking
• Decoking
In the coking step, the feed is heated to approximately 475 to 520°C in an

oven with a very low residence time and is discharged into the bottom of a large
vessel called, a "coke drum" for extensive but controlled cracking. The coke drum
is not heated. That means that the feed is heated only in the oven. The cracked
volatile product rises to the top of the drum and is drawn off. It is then charged to
the product fractionator for separation into naphtha, diesel oils, and heavy gas oils
for further processing in the catalytic cracking unit. The heavier product remains
and, because of the retained heat, cracks ultimately to coke. Once the coke drum is
filled with solid coke, it is removed and replaced by another coke drum.
Decoking is a routine daily occurrence accomplished by a high-pressure
water jet. First, the top and bottom heads of the coke drum are removed. Next, a
hole is drilled in the coke from the top to the bottom of the drum. Then, a rotating
stem is lowered through the hole, spraying a water jet sideways. The high-pressure
jet cuts the coke into lumps, which fall out to the bottom of the drum for subse-
quent loading into trucks or railcars for shipment to customers. Typically, coke
drums operate on 24-hour cycles, filling with coke over one 24-hour period fol-
lowed by cooling, decoking, and reheating over the next 24 hours.
The final coking process is continuous coking. During this coking, the feed
is heated in the reactor by contact with a hot medium. Coke formation proceeds on
the surface of the medium particles. After coking in the reactor, the medium with
coke on the surface passes to the regenerator. Coke is combusted in the regenera-
tor, and the heat generated by coke combustion is used for heating the medium.
The heated medium (usually ceramic particles) passes back to the coker.
More details concerning the coking chemistry and the equipment for coking
are given in chapter 8.
6.5 HYDROPROCESSING
It was shown in previous sections that it is impossible to convert a hundred

percent of the crude oil residue to light fractions by using both thermal and cata-
lytic cracking processes alone. The main reason for this is that cracking reactions
need to be accompanied by hydrogen transfer reactions in order to stabilize the
product. It is obvious that light fractions such as gasoline or diesel fractions are
more hydrogen rich than coke and residue by-products of thermal or catalytic
cracking processes. This means that hydrogen transfer proceeds from heavy frac-
tions to light cracking products during the cracking processes. However, the com-
plete conversion of cracking feed to light fractions is impossible because of the
shortage of hydrogen in the feed. Also, heteroatom compounds present in the feed
tend to form coke on the catalysts. The elimination of heteroatom compounds
requires hydrogen, which thereby limits hydrogen transfer to the light fractions.
Catalytic hydroprocessing is a hydrogenation process used to remove het-
eroatom compounds (i.e., compounds containing nitrogen, sulfur, oxygen, and/or
metals) from liquid petroleum fractions. These compounds adversely influence
equipment and catalysts in the refinery and the quality of the finished product,
especially on the ecological properties of the product. Hydroprocessing units are
installed prior to units for processes such as catalytic reforming so that the expen-
sive platinum catalyst is not contaminated by untreated feedstock. Hydroprocess-
ing is also used prior to catalytic cracking to reduce sulfur and improve product
yields, and to upgrade middle-distillate petroleum fractions into finished kerosene,
diesel fuel, and heating fuel oils. In addition, hydrotreating converts olefms and
aromatics to saturated compounds.
All the reactions that take place during hydroprocessing can be classified
into four large groups:
• Reactions of sulfur containing compounds
• Reactions of nitrogen containing compounds
• Reactions of oxygen containing compounds
• Reactions of hydrocarbons
288 Chapter 6
The hydroprocessing of sulfur containing compounds proceeds with the

formation of hydrogen sulfide. An example of this reaction is shown in the reac-
tion equation (6.44).
2R-SH + 3H2 -» 2R-H + 2H2S (6.64)
Sulfides and disulfides are hydrogenated in two steps. The reactions for the
hydrogenation of sulfides and disulfides are shown in the reaction equations (6.45)
and (6.46).
2RSR + 2H2 -»2R-SH + 2RH + 3H2 -> 2R-H + 2RH + 2H2S (6.45)
RSSR + H2 -> 2R-SH + 3H2 -> 2R-H + 2H2S (6.46)
The hydrogenation of the cyclic sulfide proceeds with ring destruction
+ H2 -> CH3-CH2-CH2-CH3 + H2S (6.47)
The next important class of heteroatom containing compounds are those that
contain nitrogen. The hydrogenation of these compounds proceeds with the for-
mation of ammonia (6.48).
C6H5NH2 + H2 -> C6H6 + NH3 (6.48)
The hydrogenation of cyclic nitrogen containing compounds proceeds very

slowly and with a very low conversion. This reaction proceeds in four steps shown
in the reaction equation (6.49).
2H2 H2 -» CH3-CH2-CHrCH2-NH2
X
N "
+ H2 -T CH3-CH2-CH2-CH3 + NH3 (6.49)
During the hydrogenation of oxygen containing compounds, hydrocarbons

and water are formed. An example of this reaction is shown in the reaction equa-
tion (6.50).
R-COOH + 2H2 -> R-CH3 + 2H2O (6.50)
The hydrogenation of hydrocarbons involves the saturation of the non-

saturated bonds (6.51), which are formed during all the cracking processes shown
in the previous sections.
CH3-CH=CH-R + H2 -» CH3-CH2-CH2-R (6.51)
The velocity of this reaction (6.51) as well as that for most hydrogenation
reactions is very slow without using a catalyst. Moreover, reaction (6.51) is an
exothermic reaction, meaning that there is a thermodynamic limitation in that the
conversion in this reaction decreases with increasing temperature of the process
(see section 6.1). Hydrogenation of many hydrocarbons is already impossible at
temperatures over 400°C. In section 6.1, it was shown that pressure has a large
influence on reactions that proceed with a volume change. It is obvious from all
the hydroprcessing reactions shown that this process proceeds with a volume de-
crease, meaning that hydroprocessing must be carried out under a hydrogen pres-
sure that is as high as possible.
As mentioned already, the majority of hydroprocessing reactions are exo-
thermic reactions. However, the hydroprocessing of light fractions from the cata-
lytic cracking unit can have a relatively small exothermic heat effect, approxi-
mately 80 kJ/kg. On the other hand, the hydroprocessing of more unsaturated and
heteroatom rich feed can have an exothermic heat effect of up to 500 kJ/kg. It has
therefore become essential that most modern hydroprocessing plants have heat
exchangers to take out the heat during the process.
Modern hydroprocessing is carried out with the use of catalysts. The typical
catalysts for this process are oxides and sulfides of nickel, cobalt, molybdenum,
and vanadium. Recently, new catalysts for hydrotreatment have been developed
based on metal cluster compounds.
In a typical catalytic hydroproceesing unit (Fig. 6.12), the feedstock 1 is de-
aerated and mixed with hydrogen 2. This is preheated in a fired heater O to the
temperature of 350-400°C and then charged through a fixed-bed catalytic reactor
R. In the reactor, the sulfur and nitrogen compounds in the feedstock are converted
into H2S and NH^. The reaction products leave the reactor and, after separation in
the hot separator Tl and cooling to a low temperature, enter the liquid/gas separa-
tors T2 in which wash water 3 is used to remove the ammonia and hydrogen sul-
fide. The sour water 4 leaves the separator in the bottom section of the equipment.
The overhead gas from the cold separator T2 is charged to the high-pressure
scrubber T3 to remove hydrogen sulfide from the recycled gas. It is chemically
absorbed in an amine solution 5. The purified recycle gas is mixed with fresh
hydrogen 2 to compensate for the losses in the hydrogenation reactions. The recy-
cled gas compressor routes the gas back to the reactor loop. The liquid product
streams are sent to a rectification tower T4 where the volatile product is hydro-
treated naphtha.
The bottom product from the T4 is sent to the vacuum rectification tower T5
for further rectification. The bottom product from vacuum tower T5 is the middle
distillate.
Hydrotreating processes differ depending upon the feed utilized and the
catalysts used. Typical catalysts for hydroproceesing were described in the pre-
ceding section.
290 Chapter 6
Fig. 6.12: Hydroprocessing unit.

O - Oven
R - Reactor
Tl - Hot separator
T2 - Liquid/gas separators
T3 - High-pressure scrubber
T5 - Vacuum rectification tower
1. Feed, 2. Hydrogen, 3. Wash water, 4. Sour water, 5. Amine solution, 6. Hydro-
gen sulfide rich amine solution, 7. Gases 8. Hydrogenated product
Depending on the feed used, hydroprocessing can be used for the treatment
of middle fractions, for example, to improve the burning characteristics of distil-
lates, such as kerosene. Hydrotreatment of a kerosene fraction can convert aro-
matics into naphthenes.
The hydroprocessing of heavy oil fractions, for example, lubricating oil
hydroprocessing, uses a catalytic treatment of the oil with hydrogen to improve
product quality. The objectives in mild hydroprocessing include saturation of
olefins and reduction of the acid nature of the oil. Mild oil hydrotreating also may
be used following solvent processing.
Hydrotreating also can be employed to improve the quality of pyrolysis
gasoline, a by-product from the manufacture of ethylene. Traditionally, the outlet
for this gasoline has been motor gasoline blending, a suitable route in view of its
high octane number. However, only small portions of untreated pyrolysis gasoline
can be used for blending owing to its unacceptable odor, color, and gum-forming
tendencies. The quality of pyrolysis gasoline, which is high in diolefin content, can
be satisfactorily improved by hydroprocessing, whereby conversion of diolefins
into mono-olefins provides an acceptable product for motor gasoline blending.
Just like any catalytic process in the crude oil industry, the big problem in
hydroprocessing is the deactivation of the catalyst during the process. There two
main mechanisms of catalyst deactivation during hydroprocessing:
1. deactivation by coke formation on catalyst surface
2. deactivation by heavy metals deposition on catalyst active centers
Deactivation by coke formation can take place by many mechanisms. For

example, coke or similar compounds such as polyaromatic compounds can be
adsorbed on the surface of the catalyst as shown in Figure 6.13.
»Jx.
Mo Mo Mo Mo Mo Mo
Fig. 6.13: Catalyst deactivation by absorption of coke or similar compounds.
Coke formation on the catalyst proceeds in same way as was shown in sec-
tion 6.1 for thermal cracking. However, the presence of the catalyst changes the
mechanism of the polycondesation reaction. Coke formation in all catalytic proc-
esses proceeds by the ion mechanism and not by the radical chain mechanism
applicable for thermal processes. One example of a possible pathway for coke
formation is shown in reaction (6.52).
Catalyst can also be deactivated by adsorption of asphaltenes during the
hydroprocessing of heavy crude oil residues.
All heavy crude oil residues have heavy metals such as Ni, V or Fe in their
structrure. These metals are bonded as organometalic compounds. At high
temperatures and for hydrogenation reactions, these compounds are cracked and
heavy metals are deposited on the catalyst surface. These metals can also react
with hydrogen sulfur from the gas phase to form metal sulfides. The deposition of
sulfides of iron, vanadium or nickel leads to irreversible poisoning of the catalyst.
This is the difference between catalyst deactivation by metals and deactivation by
coke; the former leads to an irreversible loss of the catalyst activity.
292 Chapter 6
[<oHo>r-»
(6.52)
Hydroprocessing is one of the most important processes in crude oil

processing. However, as a result of the continuous changes in crude oil quality in
the world market, it has become necessery to modify the hydroprocessing
technology. Reports of new catalysts or new types of hydroprocessing appear
every year in the literature. References 33 and 34 at the end of part III of this book
show the most modern developments in this area and give references to some
articles reporting about the newest technologies in the area of hydroprocessing of
crude oil.
6.6 REFORMING
Reforming is the most widespread process for rearranging the hydrocarbon

molecules from petroleum fractions. The initial process, thermal reforming, was
developed in the 1920s. Thermal reforming employed temperatures of 510-565°C
at moderate pressures to obtain gasoline with octane numbers of 70 to 80 from
heavy naphtha with octane numbers of less than 40. The product yield, although of
a higher octane level, included olefins, diolefins, and aromatic compounds. It was
therefore inherently unstable in storage and tended to form heavy polymers and
gums, which caused combustion problems.
By 1950, a reforming process was introduced that employed a catalyst to
improve the yield of the most desirable gasoline components, while minimizing
the formation of unwanted heavy products and coke. In catalytic reforming, as in
thermal reforming, a naphtha-type material serves as the feedstock, but the reac-
tions are carried out in the presence of hydrogen, which inhibits the formation of
unstable unsaturated compounds that polymerize into higher-boiling fractions.
The main reaction that occurs during catalytic reforming is the aromatization
reaction. However, the aromatization reaction involves many simple reactions that
are presented in the following set of reactions (6.53):
-H2
(6.53)
From the reaction (6.53) line 1, it can be seen that aromatization proceeds
initially from paraffin through olefms, diolefins and triolefins. From this example,
it is obvious that less unsaturated compounds are formed during catalytic reform-
ing. They change their structure under the influence of the catalysts from unsatu-
rated and chemically unstable olefins to stable aromatic compounds (see (6.53)).
Chrome oxide, copper chromide and aluminum-molybdenum (MoO3/AlO3)
were the first catalysts used for the reforming process. This catalyst promotes all
the reactions that occur during reforming. This catalyst thus belongs to the cata-
lysts with very low selectivity. During the reforming, as with every other catalytic
process in crude oil refining, coke forming occurs, leading to a very fast deactiva-
tion of the catalyst. During reforming, the most frequent reactions that occur are
cyclization reactions that can proceed further until aromatics are formed. How-
ever, recent investigations have shown that cyclization is the last step in these
processes. In the case of the reaction of naphthene side-chains, cyclization can
actually be the last reaction (6.54)
(6.54)
From both reactions (6.53) and (6.54), it can be seen that reforming pro-
ceeds with the formation of a high amount of hydrogen. However, reforming is
carried out under a hydrogen atmosphere in order to reduce coke formation. Be-
cause hydrogen is one of the reforming products, the high hydrogen content in the
reaction zone slows down the reforming reactions as well. This is why it is so
important to choose the hydrogen pressure in the reforming reactor so that the
reforming reactions will proceed fast enough for industrial applications.
294 Chapter 6
In modern refineries, platinum is the most widespread active catalyst; it is

distributed on the surface of an aluminum oxide carrier, the process is called "plat-
forming". Small amounts of rhenium, chlorine, and fluorine act as catalyst pro-
moters. In spite of the high cost of platinum, the process is economical, because of
the long life of the catalyst and the high quality and yield of the products obtained.
Platforming is carried out under the atmosphere of a hydrogen containing gas
(hydrogen content up to 95%). The principal reactions during platforming are the
same as during the described reforming: the breaking down of long-chain hydro-
carbons into smaller saturated and unsaturated chains, the formation of iso-
paraffins. Formation of ring compounds (cyclization) also takes place, and the
naphthenes are then dehydrogenated into aromatic compounds. The hydrogen
liberated in this process forms a valuable by-product of catalytic reforming. The
desirable end products are iso-paraffins, aromatics and naphthenes, having high
octane numbers. The main reactions of hydrocarbons during reforming can be
shown by the scheme given in Figure 6.14.
There are many different commercial catalytic reforming processes used
nowadays in the petroleum industry:
• Platforming
• Powerforming
• Ultraforming
• Thermofor catalytic reforming
A catalytic reformer comprises a reactor section and a product-recovery

section (see Fig. 6.15). The feed preparation section is more or less standard. Here,
the feedstock is prepared to the desired specification by combination of hydro-
treatment and distillation.
In a typical reforming unit, the naphtha charge after the heater is first passed
over a catalyst bed in the presence of hydrogen to remove any sulfur impurities.
The desulfurized feed is then mixed with hydrogen and heated to a temperature of
500-540°C in the heater. The gaseous mixture passes downward through catalyst
pellets in a series of three to five reforming reactors (Figure 6.15 reactor includes
the reactor section of three or five reactors and catalyst regenerator).
After leaving the final reactor, the product is condensed to a liquid and
passed to a rectification tower, where the light hydrocarbons produced in the re-
actors and the hydrogen rich gases are removed by rectification. The reformated
product is then available for blending into gasoline without further treatment. The
hydrogen leaving the product separator is compressed and returned to the reactor
system.
The reformed gasoline has an octane number between 90 and 100. At the
higher octane number level, product yields are smaller, and more frequent catalyst
regeneration is required. During the course of the reforming process, small
amounts of coke are deposited on the catalyst, causing a gradual deterioration of
the product yield pattern. Some units are semi-regenerative facilities. That is, they
must be removed from service periodically to burn off the coke and rejuvenate the
catalyst system. However, increased demand for high octane fuels has also led to
the development of continuous regeneration systems, which avoid periodic unit
shutdowns and maximize the yield of high octane reformates.
a1ky1-eye1opentane
polymerization
products
coke
Fig. 6.14: A scheme of the reaction mechanism for catalytic reforming.

296 Chapter 6
fuel gas
1 ' ^~~^
lig
light fraction
reactor
I
reformate
reactor section product-recovery section
Fig. 6.15: Row scheme of a reforming unit.
Continuous regeneration employs a moving bed of catalyst particles that is

gradually withdrawn from the reactor system and passed through a regenerator
vessel, where the carbon is removed and the catalyst rejuvenated for reintroduction
to the reactor system.
More about the reforming process can be found in references 4, 35, 36 at the
end of part III of this book.
6.7 ISOMERIZATION
The steadily increasing demands for premium gasoline requires higher ca-
pacities for isomerization, reforming and alkylation. In addition, the more stringent
legislation on aromatics in reformulated gasoline is an important incentive for
refineries to saturate benzene and remove naphthenes in isomerization units. The
first widespread use of isomerization was during the Second World War, because
of the great demand for aviation gasoline, and afterward the quantities of isobutane
available for alkylation feedstock were insufficient. This deficiency was remedied
by isomerization of the more abundant normal butane into isobutane. The isomeri-
zation catalyst is aluminum chloride supported on alumina and promoted by hy-
drogen chloride gas.
The main reaction of the isomerization process is isomerization (6.55).
(6.55)
The real reaction mechanism on the surface of the catalyst particle can be
represented by a more complicated multistage reaction (6.56):
dehydro- protonation
genation
isomerization
(6.56)
Commercial processes have also been developed for the isomerization of

low-octane normal pentane and normal hexane to the corresponding higher-octane
isoparaffins. Here the catalyst is usually enhanced with platinum. As in catalytic
reforming, the reactions are carried out in the presence of hydrogen. Hydrogen is
neither produced nor consumed in the process but is employed to inhibit the unde-
sirable side reactions of coke formation. Molecular sieve extraction and distilladon
usually follow the reactor step. Though this process is an attractive way to exclude
low-octane components from the gasoline blending pool, it does not produce a
final product of sufficiently high octane to contribute much to the manufacture of
unleaded gasoline.
Figure 6.16 shows a typical isomerization unit.
The feed after hydrotreating and drying in absorber 1 passes to reactor 2.
Reactor 2 is a fixed bed reactor. Together with the feed in reactor 2 the promoter
(HC1) is within 10"*% of the feed. The liquid product from reactor 3 is separated
from the propane fraction in separator 3. The octane number of the product from
this unit is approximately 90, according to the research octane method.
298 Chapter 6
feed
C3
H2
product
Fig. 6.16: The isomerization unit.

1. Absorber
2. Reactor
3. Separator
6.8 ALKYLATION
The light gaseous hydrocarbons produced by catalytic cracking are highly

unsaturated and are usually converted into high-octane gasoline components in the
alkylation process. In alkylation, the light olefms (propylene and butylene) are
induced to combine, or polymerize, into molecules of two or three times their
original molecular weight. The catalysts employed for this are of an acid nature.
High pressures are required at temperatures ranging from 175 to 230°C. Alkylated
gasolines derived from propylene and butylene have octane numbers above 90
and, with the addition of lead additives, above 100.
Alkylation reactions also produce a longer chain molecule by the combina-
tion of two smaller molecules, one being an olefin and the other an iso-paraffin
(usually isobutane).
The main reaction of the alkylation process is shown in the reaction equation
(6.57).
(6.57)
Actually, reaction (e6.57) proceeds on the surface of the catalyst according

to a more complicated mechanism involving three stages.
In the first stage, the olefin reacts with the catalyst, for example sulfuric acid
(6.58).
+
+ H 2 S0 4 HSO4 (6.58)
Next hydrocarbon ion reacts with iso-butane (6.59).
(6.59)
In the second stage, the butyl ion reacts with the olefin (6.60).
(6.60)
The third and last stage is most complicated. First of all, the migration of the
hydrogen atom proceeds at this stage (6.61).
(6.61)
Next, isomerization reaction proceeds very quickly at the third stage of

alkylation (6.62).
(6.62)
All the carbon ions formed at this stage finally react with iso-butane in the
first stage with the formation of stable molecules and new carbon ions.
All the alkylation units used in the industry can by classified into different
groups according to the catalyst used:
• sulfuric acid alkylation
• hydrofluoric acid
300 Chapter 6
In sulfuric acid alkylation, concentrated sulfuric acid of 98 percent purity

serves as the catalyst for the reaction that is carried out at 2 to 7°C. Refrigeration is
necessary because of the heat generated by the reaction. The octane numbers of
the alkylates produced range from 85 to 95. An example of sulfuric acid alkylation
is shown in Figure 6.17.
The feed (olefms and iso-butane) passes to reactor 1 (Fig. 6.17) where this is
mixed with the sulfuric acid from vessel 2. The temperature in the reactor is ap-
proximately ± 1°C. The product from the reactor passes to separator 3 and then to
distillation tower 4. The product is fractionated into alkylate (desired product) and
n-butane in tower 4. In tower 6, the iso-butane is separated from the propane and
passes as recycled iso-butane back to the reactor.
Hydrofluoric acid is also used as a catalyst for many alkylation units. The
chemical reactions are similar to those in the sulfuric acid process, but it is possi-
ble to use higher temperatures (between 24 and 46°C), thus avoiding the need for
refrigeration. Recovery of hydrofluoric acid is accomplished by distillation. An
example of the hydrofluoric acid alkylation unit is shown in Figure 6.18.
n-C 4
AA alkylate
olefins
Fig. 6.17: Sulfuric acid alkylation unit.
1. Reactor, 2. Vessel, 3. Separator, 4. Distillation tower, 5. Compressor, 6. Gas separation

tower
olef ins
Fig. 6.18: Hydrofluoric acid alkylation unit.

1. Reactor, 2. Separator, 3. Distillation tower, 4-5. Separation towers
The feed and recycled iso-butane pass to reactor 1 (Fig. 6.18). The product
from the reactor passes to separator 2, where this is separated to acid and the prod-
uct. The product is then distilled into an alkylate (desired product) fraction and the
volatile product containing the hydrofluoric acid vapor and the rest of the iso-
butane. This volatile product passes to the next separation tower 4 where this is
separated into propane with the hydrogen sulfide from the product and the bottom
product directed to reactor 1. The propane with the hydrogen sulfide passes to the
separation tower 5, the bottom product of which is pure propane.
6.9 BLENDING
We have concluded the discussion on the main petroleum treatment proc-

esses. However, after petroleum is treated using all the processes described in
chapters 5 and 6, there is still a last operation to be performed. This is the blending
of the product, from different units to produce market products. These are then
delivered to gas stations and car services.
A very interesting technology for blending diesel fuels has been developed
by Total-Fina-Elf company. Not only are diesel fractions from different units
blended, but also the diesel fuel blend and a small amount of water are mixed
together. The name of the new generation of diesel fuel is "Aquazole". It exists as
an emulsion of water in diesel fuel.
It is well known that water vapor can be a burning catalyst. In "Aquazole",
this property of water has been used for the first time for burning motor fuels. One
of the positive effects achieved with this fuel is the improvement of the ecological
properties of the diesel fuel. It has been shown that by using this fuel, up to 30%
less NOX formation and up to 50% less emission of particulates have been
achieved. Also, the blending of diesel fuel with water leads to a more economical
302 Chapter 6
use of diesel fuel. Accordingly, the fuel requirements for trucks have been reduced
by up to 4%.
In the example of "Aquazole", it has been shown that even the simplest
process such as blending that is carried out in the crude oil refinery can have a
large influence on the quality of the crude oil products and the economics of the
process.
Environmental Issues Facing the
Refining Industry
7.1 INTRODUCTION
Many ecological problems that arise in the crude oil industry were already
discussed in chapter one of this book. Thus, the objective of this chapter is to show
that in order to develop an appropriate technology for crude oil treatment, not only
are economically rational decisions required, but also ecologically acceptable
decisions are needed. Nowadays it has been very important to change the world-
view on environmental issues, such that everyone understands that our environ-
ment is a very sensitive system that must be protected.
The first steps that need to be taken in the direction of environmental devel-
opment of the crude oil industry were already done more than thirty years ago. In
January 1, 1970 in the USA, a new ecological law called the National Environ-
mental Policy Act (NEPA) was accepted. The main objectives of this law are to
ensure that the necessity to estimate all the possible influences of any industrial
activity on the environment is carried out, and to decrease the negative influence
of the industry on the biosphere. The highlights of this law are given as follows.
An analysis of the influence of the industrial activity on the environment must be
done before starting the activity. Also, the analysis must be done not only by spe-
cialists from the industry, but also by independent specialists from the area where
this industrial activity is to be carried out.
This new ecological system based on NEPA, called Environmental Assess-
ment or Environmental Impact Assessment, was started in the USA. The next
country that started using an ecological law in order to change industrial policy
was Canada. Then, many European countries started their ecological policies
because of the clear necessity for environmental protection. Now almost all the
countries around the world use environmental laws in their industrial policies.
303
304 Chapter 7
This chapter thus deals with the ecological consequences of crude oil treat-
ment and the use of crude oil products. It also deals with the methods currently in
place to improve the ecological outlook of the crude oil Industry.
7.2 METHODS OF CLEANING CRUDE OIL CONTAMINATED WATER

AND SOIL
It is well known that it is almost impossible to transport, store and treat

crude oil without spills and losses. Crude oil contaminates both water and soil
through the above mentioned avenues. It is difficult to prevent spills resulting from
failure or damage on pipelines. It is also impossible to install control devices for
controlling the ecological properties of water and the soil along the length of all
pipelines. The soil suffers the most ecological damage in the damage areas of
pipelines.
Crude oil spills from pipelines lead to irreversible changes of the soil prop-
erties. The most affected soil properties by crude oil losses from pipelines are
filtration, physical and mechanical properties. These properties of the soil are
important for maintaining the ecological equilibrium in the damaged area.
Natural filtration of petroleum through the soil creates the so-called chro-
matographic effect resulting in crude oil differentiation and fractionation; heavy
components containing asphaltenes, resins and cyclic compounds are accumulated
in upper soil layers, while the light compounds penetrate deeper into the bottom
mineral layers of the contaminated soil. The possibility of self-cleaning in differ-
ent soils is different and depends on the contaminated area. For example, accu-
mulation of crude oil contaminants in clay soils can be more extensive than in
sandy soils. Damage on pipeline leads to an irreversible change of the ecological
system in the contaminated area. This is why it is necessary to remove crude oil
from the soil as fast as possible.
The cleaning of the soil is usually done in two steps:
- mechanical step
- biological step
The first operation during the mechanical step of soil cleaning after the
damage on a pipeline is to minimize the size of the affected area (i.e. the area of
contact between crude oil and the soil should be made as small as possible). This
can be done by leading the petroleum spill to natural containments. This is the
simplest way but is not reasonable all the time. It is not always possible to find
natural containment near the place of pipeline damage. Then, such an operation as
described above can actually result in the contamination of a larger soil area while
trying to lead crude oil to a natural containment. Thus, if it is impossible to find a
nearby natural containment, then it is necessary to build a dam around the place of
damage in order to prevent the spread of crude oil to other areas.
Environmental Issues in the Refinery 305
Special pumps are used for removing crude oil from the surface of the soil.
Then, the surface of the soil must be collected and utilized or disposed of. In very
rare cases where the crude oil contamination penetrates very deep into the soil
layer, typically over ten meters, it becomes necessary to completely burn the soil
layer. After burning up the contaminated soil, it is replaced with fresh soil because
the ecological system of the burnt soil had been completely destroyed by burning.
Natural adsorbents such as peat or sand are used to simplify the removal of
crude oil from the soil surface. Example of the dam and control system on pipeline
place of damage is presented in Figure 7.1.
Fig. 7.1: Place of pipeline damage during the restoration of the soil.
l.Dam
2. Crude oil and natural adsorbent layer
3. Water
4. Crude oil
5. Station of ground water sample extraction
6. Borehole to ground water
7. Soil layer
8. Ground water
Water can enter the dam area in Figure 7.1 from rain or snow coming into
the damage area. Crude oil film, 4, is collected by special pumps from the dam.
The upper layer of the soil together with crude oil adsorbed on natural adsorbent is
removed from the damage area by a dredger and either disposed of or put into use.
Often, in order to ensure that crude oil is successfully removed from the damage
area, ground water analysis is performed in analyzing stations installed near the
dam. It is important to control the quality of ground water in the damage area
because if the crude oil contamination reaches the ground water it can be spread
further to areas around the damage area and contaminate a wider area than was at
the time of pipeline damage [38].
Biological self-restoration of the soil after crude oil contamination is a very
long process. Usually, it takes over twenty years before the ecological system of
the contaminated area reaches a new ecological equilibrium. However, the process
306 Chapter 7
can be accelerated simply by loosening the soil. This action minimizes the oxygen
deficiency in the soil caused by formation of crude oil film on the surface.
Soil and water contamination can occur not only by damage of pipelines. A
majority of crude oil treatment processes need water either as cooling medium or
heating agent in heat exchangers, or simply as a reagent. These avenues lead to
oil-water contacts, which are responsible for formation of waste water that must be
cleaned before it is released back to the environment. There are many different
methods used for cleaning waste water. These can be classified as follows:
- mechanical method
- chemical method
- physical chemical method
- biological method
The types of contamination that emanate from the oil industry and can affect
natural water can be classified as follows:
- mechanical contamination: characteristic of this type of contamination is the
presence of a high concentration of insoluble solid particles in water,
- chemical contamination: characteristic of this type of contamination is the
presence of organic or inorganic pollutants in water; this type of water
contamination is especially typical of the crude oil industry,
-bacteriological or biological contamination are represented by contamina-
tion by bacteria or foreign biological material in certain ecological systems;
this type of contamination is atypical of the crude oil industry, and can only
occur through improper selection and use of biological cleaning methods,
- radioactive pollutions, this type of pollution is not usually present in the
crude oil industry,
- thermal pollution, this type of pollution is present by releasing a warmer
process water into the colder natural pools, ponds, or other surface waters;
although the potential is there, this type of pollution occurs very rarely in
the crude oil industry.
The choice of method and technological scheme for water cleaning in in-
dustry depends on many factors. However, the most important factor is the level of
cleanliness of the water as required by legislation in the area. Most modern indus-
try processes work with a closed water loop or circuit during production. In this
case, water must be only as clean as is needed for the process. In order to have
universal applicability, the old plants must be replaced with new and more eco-
logical based processes. For ecologically based processes, water in the circuit only
needs to be cleaned to as high a degree as is technically desired and economically
feasible.
The main objective in the mechanical method of water cleaning is to remove
insoluble or solid contaminants from waste water by settling and filtration. Me-
chanical solid contaminants are separated by grids or fine filters depending on the
size of the contaminant particles. Liquid contamination from crude oil or its prod-
ucts must be separated from the water in special reservoirs by settling. The me-
chanical cleaning allows the separation from industrial waste water up to 95% of
contaminants. A schematic of the mechanical cleaning system is shown in Figure
7.2.
Crude oil
Solid pollutants
Water
Fig. 7.2: Principle of mechanical water cleaning.
The principle in mechanical water cleaning by settling is separation with

regard to density differences of the mixture constituents (see Figure 7.2). The
lightest constituents such as crude oil are collected at the top of the separating
container and the heaviest at the bottom of the separator.
The main idea in the chemical method of water cleaning is the addition of
special chemicals that react with the contaminants to form insoluble heavy resi-
dues. These residues can be easily separated from the waste water by settling using
the principles discussed for mechanical cleaning.
Fine colloidal or soluble inorganic contaminants are removed from water by
physical-chemical methods of waste water cleaning. The main methods used are
coagulation, oxidation, sorption, extraction and electrolysis methods.
Biological cleaning methods are based on the principles of natural cleaning
of the waste water. However, only waste water cleaned by mechanical and chemi-
cal or physical-chemical cleaning can be treated by this method. There are many
different methods of biological water cleaning. However, the most used methods
are the biological filter and biological pool methods. In the first method, the bio-
logical material used for cleaning is deposited on a carrier material as a thin film.
The waste water is filtered through this material and the contaminants are de-
stroyed biologically by special types of bacteria. The main objective in the bio-
logical pool method is that the waste water should be cleaned in the same way as
for self-restoration in natural ecological water systems such as lakes. This means
that the waste water is dumped in a special pool in which optimal biological con-
ditions are created for the fastest biological self-restoration of the water.
In modern refineries, it is very rare to use only one of the water cleaning
methods. Usually, complicated schemes including many cleaning steps are used.
For example, mechanical cleaning is usually used as the first step for waste water
308 Chapter 7
cleaning in almost all modern crude oil refineries. The chemical cleaning is used
only in special cases if it is necessary to remove any contaminant which cannot by
removed by the physical-chemical method. Biological cleaning of waste water is
used only in the case where the water must leave the industrial water circuit and be
returned to natural lakes or pools.
The physical-chemical methods of waste water cleaning are the most im-
portant and most popular as they are included in almost all industrial technological
schemes of waste water treatment. Oil-water emulsion destruction by coagulation
of the disperse phase is the most popular method used as a second step for water
cleaning in water treatment processes in modern crude oil refineries. The objective
in this method is to destroy the stable oil-water emulsion by addition of inorganic
electrolytes. NaCl, H2SO4, FeSO4, Fe2(SO4)3, FeCl3, CaO, A12(SO4)3 can be used
as inorganic electrolytes. These electrolytes can be used separately or in combina-
tion with each other depending on the type of contaminants. These electrolytes,
when added, result in a decrease of the electrokinetic potential of oil-water emul-
sion and the destruction of the structural-mechanical barrier preventing the desired
coagulation of oil drops in water. It is important to note that some electrolytes are
able to recharge the oil droplets in the emulsion with the formation of an unstable
colloidal system. This type of emulsion is called opposite emulsion. Thus, it is
very important to determine the optimum concentration of electrolyte needed for
application for successful waste water treatment. The use of many electrolytes
allows considerable flexibility in this regard, and also leads to increased cleaning
efficiency. Currently, aluminum sulfate is the most popular electrolyte used for
waste water cleaning.
The coagulation intensity during cleaning by physical-chemical methods can
be increased by additional influence of factors such as electromagnetic field, tem-
perature or ultrasound. Ultrasound is used only in special cases because of the
deficit of knowledge of such processes. On the other hand, the influence of tem-
perature and electromagnetic field has been well investigated and widely used in
industrial waste water treatment plants. The use of such technologies in the crude
oil industry is relatively rare because of the high cost of a process that uses an
electromagnetic field. However, the use of such a technology can undoubtedly
improve the quality of water leaving the industry.
Very often, special filter systems are used for the separation of crude oil
from water as a form of waste water cleaning. The principle in such filtration
plants is not just ordinary filtration but is adsorptive filtration. The filter in such a
plant consists of a layer of adsorbents. Adsorbents usually used are oxidative ad-
sorbents or activated natural fibers.
A general scheme of a waste water treatment plant is presented in the exam-
ple shown in Figure 7.3. The scheme presented in Figure 7.3 is a very general
presentation of the possible water cleaning system in the refinery. Depending on
the amount of water and the type of contaminants, it can look different than what
is shown in Figure 7.3. However, the pool-collectors and collectors for technical
water, which were not described previously, are always part of every scheme of
the water circuit in refinery. The need for these elements is based on the possibility
that the formation waste water or need for technical water in the refinery can be
larger or smaller than the performance of the capacity of the water cleaning plant.
It must be noted that the cleanliness of the technical water from the waste water
cleaning plant is not sufficient for it to be released into natural pools. However, it
can be used in the refinery water circuit again.
Physical-chemical
Mechanical clean-
ing cleaning
Pool - collector
Collectors for tech-

nical water
Gross filtration
Fig. 7.3: A general scheme of industrial water circuit with water cleaning.
7.3 METHODS OF AIR AND GAS CLEANING USED IN THE CRUDE

OIL INDUSTRY
The atmosphere of our planet is a very sensitive system, such that even little
changes in the concentrations of the same gases present in the atmosphere can
strongly change the ecological equilibrium not only in the area of formation of the
pollutants, but also in areas many kilometers around. Using methods of preventing
the damage done by gas pollution as was shown for soil and water contamination
in section 7.2 is impossible because of the very high speed of spreading in the
environment for gaseous pollutants. This is why it is important to control the qual-
ity of the waste air or gas leaving the industrial circuit.
All the types of gas pollutants can be divided into:
- Mechanical particles (solid and liquid) in the form of aerosols
- Gaseous and vapor pollutants
The first group consists of solid particles of inorganic and also liquid drop-
lets (e.g. fog) all of which could be in the form of aerosols. Dust is a stable colloi-
dal system containing more large particles than smokes and fogs. The concentra-
310 Chapter?
tion in dusts in terms of number of particles in 1 cm3 is small in comparison with

smokes and fogs. The second group, gaseous and vapor pollutants contained in
industrial waste gas, is much more extensive than the first group. Acids, halogens
and halogen containing substances, gaseous oxides, aldehides, ketones, spirits,
hydrocarbons and many other components of industrial waste gases are part of this
group.
The complete removal of pollutants from industrial gases is often impossible
or uneconomical. This is the reason for the development of tables, which limit the
concentration of dangerous pollutants. If the waste gas contains more than one
pollutant, a new limit of concentrations for the gases must be calculated by equa-
tion (7.1)
Ci/CLI + CZ/CLZ+ ... + CVCu, = 1 (7.1)
where Q, C2, Cn - real concentration of gases 1, 2 . . .,n

CLI , Ci2, Ctn - standardized limit of concentrations of gases 1,2 . . . ,n
If it is impossible to achieve the limit of concentration by cleaning methods,

sometimes the dilution of the pollutants in the higher layers of the atmosphere is
applied. This reduces emission of gases in the bottom layers of the atmosphere by
venting or shooting the waste gases through a tall pipe. The pollutants are thereby
dispersed in the top layers of the atmosphere. The theoretical definition of con-
centration of pollutants in the bottom layers of the atmosphere depends on the
height of the pipe and other factors connected with the laws of turbulent diffusion
of pollutants in the atmosphere. There is no accurate method for such an evalua-
tion. Consequently, empiric equations such as equation (7.2) are used such calcu-
lations.
L
L
AFm
Where CL - standardized limit of concentration of the gas in the bottom lay-

ers of the atmosphere
CHL - calculated limit of concentration of the gas in the higher layers
of the atmosphere
H - height of the pipe [m]
V - volume velocity of the gas stream from the pipe [m3/s]
At - temperature difference between waste gas and atmosphere [K]
A - coefficient specific for the pollutant and atmosphere
F - sedimentation coefficient for the pollutants in the atmosphere
m - coefficient of the output conditions of the gas from pipe
The last coefficient in equation (7.2) must be calculated by equation (7.3).

1.5*103co2D
m= -, (7.3)
H 2 At
where co - velocity of gas output from the pipe [m/s]

D - diameter of the pipe [m]
H - height of the pipe [m]
At - temperature difference between waste gas and atmosphere [K]
However, the method using the dilution of the pollutants in the higher layers
of the atmosphere does not really save the environment from the contaminants. It
only moves the pollutants from the area of formation to other areas. Consequently,
it is better not to use this method if it is possible.
All the methods for gas cleaning can be classified into the following three
classes:
- mechanical cleaning
- electrostatic coagulation method
- cleaning using ultrasound
The mechanical methods can be classified into dry and humid methods. The
dry methods can be different such as in:
- gravitational settling
- centrifugal settling
- filtration
Gravitational settling is based on settling of the pollutant particles by gravity

through movement of dusty gas at low speed with no change in the direction of
flow. The process is carried out in pipe settlers and settling chambers. A set of
horizontal trays at a distance of 40-100 mm from each other is installed in settling
chambers, which split the gas flow into flat jets. This is done to reduce the height
of particles settling in settling chambers. Productivity of settling chambers can be
P= A •w (7.4)
where S - area of horizontal section of the chamber

w - speed of particles settling under the influence of gravity [m/s]
Gravitational settling method is effective only for pollutant particle size

larger than 50-100 microns. This method is suitable only for preliminary cleaning
of gases.
Centrifugal methods of gas cleaning are based on the action of centrifugal
force that arises from rotation of flow of dirty gas in the cleaning chamber or by
312 Chapter?
rotation of parts of the chamber. Cyclones of various types are used as centrifugal
chambers. Cyclones are the most frequently applied units for the cleaning of aero-
sols (solid particles in gas) in the industry. Cyclones are characterized by their
high productivity in comparison to gravitational settling units. The size of the
particle that can be separated by this method can be approximately calculated by
empirical equation (7.5).
(7.5)
2Nco( Pp - P(! )
where |i - viscosity of the gas

D - diameter of the end pipe at the cyclone
N - effective number of gas rotations in the cyclone
co - gas velocity at the input into the cyclone
pp- particle density
p g - gas density
The next method for dry gas cleaning is filtration. Filtration is based on
passage of dirty gas through various filtering fabrics such as cotton, wool, chemi-
cal fibers, fiber glass, etc. or through other filtering materials such as ceramics,
metal ceramics, porous filters from plastic, etc. Special fibrous materials such as
fiber glass or wool are often used for gas cleaning. Fabric filters are applied for gas
cleaning at the temperature of waste gas of 60-65°C. Depending on colloidal
structure of initial waste gas, up to a 85-99% degree of cleaning can be achieve by
this method. The hydraulic resistance of the filter is about 1000 Pa.
The use of fiber filters allows the achievement of a degree of cleaning up to
99.9%. Using fiber glass as a filter material allows the cleaning of the waste gas at
a temperature up to 275°C.
Filtration is the most frequently used method for fine cleaning of waste
gases in industry. However, the energy needed for this method is higher than the
energy required for settling methods. Thus, this method should only be used in the
case where a high degree of cleaning is really needed.
Humid cleaning of waste gases is the next group of cleaning methods for
waste gases. This is based on washing of gas by a liquid (usually by water). The
contact surface area of liquid with particles in the waste gas stream should be as
large as possible, and the mixing of waste gas with liquid should also be as inten-
sive as possible. This is a universal method of particles of dust, smoke and fog
from industrial gases. It is the most widespread method used as a final stage of
mechanical cleaning. There are many different devices that are developed to use
the humid method of gas cleaning as a rational cleaning method.
Towers with special packings are used and they are characterized by their
simplicity of design and operation, stability in work, small hydraulic resistance
(300-800 Pa), and a rather small need of energy. In such devices, it is possible to
clean gases with initial gas pollution up to 6 g/m3. The efficiency of one step of
cleaning for this device for waste gas with pollutant particle size over five microns
is usually between 70% and 80%. The disadvantage of this method is that the void
volume of the packed tower is quickly blocked by dust, especially at a high initial
dust content.
Humid cyclones are used for cleaning large volumes of gas. They have
small hydraulic resistance - 400-850 Pa. The efficiency of gas cleaning for waste
gas with pollutant particle size of 2-5 microns is approximately 50%.
Foam devices are used for cleaning waste gas from pollutants with polydis-
perse colloidal structure. Intensive foam formation by this method is created by
linear speed of gas between 1 and 4 m/s. Foam cleaners have high efficiency of
gas cleaning and small hydraulic resistance (app. 600 Pa). For pollutants with
particle size over 5 microns, up to a 99% degree of cleaning can be achieved for
foam gas cleaners.
The scrubber is the most effective device for waste gas cleaning. However,
it consumes a large amount of energy for it to work. The speed of the waste gas
into a narrowing pipe can be up to 100-200 m/s, and in some special devices, it
can be up to 1200 m/s. At such a speed, the waste gas is highly dispersed into
smallest drops. This leads to an intensive collision of pollutant particles with drops
of liquid, and catching of these particles under the action of inertial forces. Scrub-
bers are universally small-sized units ensuring cleaning of fogs up to 99-100%,
waste gases with pollutant particles with size between 0.01 and 0.35 microns up to
50-85%, and waste gases with pollutant particles with size between 0.5-2 microns
up to 97%. The degree of cleaning for waste gases with particle size between 0.3
and 10 microns can be calculated by equation (7.6).
(76)
Where r) - degree of cleaning

K - coefficient
L - volume of liquid introduced into the gas [dm3/m3]
((> - inertia coefficient
One example of the scrubber is presented in Figure 7.4.

314 Chapter 7
Fig. 7.4: Example of a scrubber.

1 - waste gas,
2 - washing liquid,
3 - clean gas,
4 - liquid with pollutants.
The biggest disadvantage of all humid methods of gas cleaning is the for-
mation of a large amount of liquid residue, which must be utilized or disposed of.
If in the general scheme of the cleaning plant in the refinery, there is no plant for
utilizing such residues, this method will only lead to transfer of pollutants from
gas into water.
The electrostatic cleaning of gases serves as a universal method which is
suitable for cleaning all types of waste gases that contain solid or liquid pollutants,
including fogs of acids. The method is based on the ionization of pollutant parti-
cles in the waste gas by passing the gas through an electrical field of a high volt-
age created by electrodes. Settling of the particles occurs in settling electrodes.
The industrial electrofllters consist of a number of plates or pipes through which
the waste gas passes. Between the settling electrodes are hung wire electrodes,
which have voltages of 25-100 kV. The theoretical equation for calculating the
degree of cleaning of waste gas in tubular electrofllters is presented in equations
(7.7) and (7.8).
l-e (7.7)
2ul
where t| -degree of cleaning

y - coefficient calculated by equation (7.8)
u - particles velocity
1 - length of electrode
r - radius of settling electrode
0) - velocity of waste gas
The degree of cleaning that can be achieved by this method is up to 99.9%,

depending on the type of pollutants in the waste gas.
Cleaning using ultrasound is a relatively new method of gas cleaning and
used very rarely at industrial scale. The degree of cleaning that can be achieved by
this method is approximately the same as was shown for electrostatic settling
methods.
Waste gases do not only contain solid or liquid particles as pollutants. They
also contain gaseous and vapor contaminants. These pollutants are also dangerous
to the environment. These pollutants cannot be separated from the waste gas by
any of the methods described before. The methods for waste gas cleaning from
gaseous and vapor pollutants can be classified into three major classes:
- absorptive methods
- adsorptive methods
- catalytic methods
The absorption of pollutants from waste gases by liquids is applied in the oil
industry for the extraction of gases such as sulfur dioxide, hydrogen sulfide and
other sulfur containing compounds, nitrogen oxides, acids (HC1, HF, H2SO4),
various organic compounds such as phenol, and volatile solvents.
All the absorptive methods are based on selective solubility of the gas com-
ponents in the washing liquid. There are two different methods of absorption:
- physical absorption
- chemical absorption
All the absorptive cleaning methods used in modern industry are continuous
methods. The washing liquid is usually regenerated and used in the cleaning again.
Heating or decreasing the pressure is usually used for regenerating the washing
liquid. One example of absorptive gas cleaning plant is presented in Figure 7.5.
316 Chapter 7
Fig. 7.5: Absorptive gas cleaning unit.

1 - waste gas,
2 - washing liquid,
3 - clean gas,
4 - liquid with pollutants,
5 - gas,
6 - vapor,
I - absorber,
II - cooler,
III - heater,
IV - regenerator.
Absorbents, used in an industry can be estimated by the following parame-

ters:
1. Absorbent capacity, it means solubility of a certain pollutant in an ab-
sorber depending on temperature and pressure;
2. Selectivity characterized by different solubility of different gases and
speeds of their absorption;
3. Minimal pressure of the absorbent vapor, in order to prevent pollution of
cleared gas by absorbent vapors;
4. Cost;
5. Absence of corrosive effects on the material of construction of the
equipment.
Water, solutions of ammonia, salts of manganese, oil and so on are used in

modern industry as absorbents for gas cleaning.
Adsorptive methods are based on the selective adsorption of pollutants from
the waste gas on the surface of an adsorbent. These methods are used in modern
industry more often as the most used universal method for cleaning waste gas
from toxic pollutants. Adsorbents usually used are activated coal, silica gel, alu-
minum gel and synthetic zeolite.
Industrial adsorptive cleaning plants usually work continuously. However,
the adsorbent is a solid material, which makes it difficult to transport continuously
from adsorber to regenerator. In order to circumvent this difficulty, modern ad-
sorptive cleaning plants make use of at least two absorbers. When one adsorbent is
working, the other adsorbent is switched to the regenerating regime. In that way, it
is possible to carry out the cleaning continuously. One example of an adsorptive
cleaner is shown in Figure 7.6.
Fig. 7.6: Adsorptive gas cleaning unit.

1 - waste gas,
2 - clean gas,
3 - vapor,
4 - vapor and gas,
5 - condensed pollutant,
6 - condensed vapor,
I -filter,
II - adsorber,
III - cooler,
IV - separator.
318 Chapter?
The next class of gas cleaning methods is the catalytic cleaning method. The
main difference of this method from all the other methods described in this chapter
is the fact that with this method pollutants are not separated from the waste gas but
transformed into compounds that are not dangerous vis-a-vis the environment. The
reactions of pollutants to new products take place in presence of catalysts. This is
why this cleaning method is called the catalytic method.
The best example for the use of the catalytic method in the oil industry is the
cleaning of waste gas of H2S and the production of sulfur as a byproduct. The
transformation of hydrogen sulfide to sulfur proceeds according to the reaction
given in equation (7.9).
H 2 S+1/2O 2 = H2O + S (7.9)
Catalytic methods of gas cleaning are used very often in modern industry as
a result of the possibility of very deep cleaning of the waste gas. Up to 99.9% of
pollutant can be separated from the waste gas by this method. However, the disad-
vantage of this method is the formation of new compounds, which must be use-
able. In the example shown of waste gas cleaning from the H2S, the formed by-
product can be used in the chemical industry. However, the amount of sulfur
formed in crude oil refineries is often so high that it cannot be moved completely
to the chemical industry. It then becomes important to find new ways of using
sulfur.
The last method of gas cleaning is the thermal method. This method was
very intensively used in the past. However, it has been the desire recently to re-
duce the number of such plants in modern refineries. The main idea of this method
is that of burning the waste gases thereby destroying the pollutants.
Using only one of the described methods in the refinery for waste gas
cleaning is impossible. Modern refineries have different schemes in their techno-
logical structure for gas cleaning, each consisting of many methods. It is only the
use of many methods in combination that will allow us to achieve the needed
cleanliness of the gas with optimum use of energy and chemical recourses of the
refinery.
7.4 CONCLUSION TO PART III
The main processes involved in crude oil refining were shown in part III of
this book. Now is the time to show how all these processes can be combined in
one crude oil refinery. However, it must be noted that every crude refinery is built
uniquely and there are no two crude oil refineries in the world having the same
technological scheme of processes used. The technological scheme of the refinery
must be chosen based on the properties of crude oil that the refinery is supposed to
treat. Nevertheless, it is possible to classify all modern refineries in two groups:
- working by fuel variant

- working by oil variant
This classification is very much simplified, but it can help us to understand

the tendencies in the development of the modern crude oil industry. From the
names of both these groups, it is obvious towards which type of products they are
oriented.
The fuel working crude oil refineries produce only fuels. In these refineries,
crude oil is treated with a deep transformation of heavy fractions into light fuel
fractions as much as is possible. The most important processes in these refineries
are catalytic cracking, hydrotreatment of fuel fractions, hydrocracking and all
destructive processes. In these refineries, no lubricants or lubricating oils are pro-
duced.
The oil-oriented refineries often have no processes for secondary treatment
of heavy fractions of crude oil. Thus, these refineries produce mainly lubricants
and lubricating oils, but still produce fuels. The main processes in these types of
refineries are processes that improve the quality of lubricating oils such as depar-
affinization, hydrotreatment of heavy crude oil fractions, etc.
Depending on the sulfur content in the crude oil, both types of crude oil
refineries can have the plants for catalytic waste gas cleaning with the production
of sulfur in their technological structure. If more sulfur is produced than the refin-
ery can sell to the chemical industry, it is often reasonable to install plants for
sulfuric acid production inside the refinery.
Because of the necessity to decrease the use of thermal methods for gas
cleaning, new methods of using organic pollutants from waste gases have been
developed. Thus, the installation in many modern refineries of plants for methanol
production. The light gas from secondary processes is used for processes in such
plants.
In part III of this book, the complexity of modern refinery was shown and
the fundamentals of most important processes were explained. The crude oil in-
dustry is a very fast developing industry. In order to attempt to keep abreast with
new developments, additional information have been given in references at the end
of part III of this book. For more detailed discussions, it may be necessary to look
at further references recommended in these references. It is almost impossible to
show all the most modern developments of crude oil industry in one book. Also,
this is not the object of the book. Instead, we propose to prepare the reader for
independent search for information in articles, scientific communications, letters,
etc. because these contain the most factual information about the newest develop-
ments in the field of crude oil treatment.
In the next part (part IV) of this book, the fundamentals of the most modern
developments in the area of secondary crude oil treatment such as co-processing
are shown. These are based on the latest research results and have not yet been
applied at industrial scale so far. These technologies therefore constitute the possi-
ble future technologies for crude oil refineries.
320 Chapter 7
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28 P G Smirniotis, E Ruckenstein. Catalytic Cracking of Gas Oil: Effect of the

322 Chapter 7
Amount of Zeolite Composite Catalysts, J. Chemical Engineering Commu-

nications, Vol. 116, 171-191, 1992.
29 P G Smirniotis, E. Ruckenstein. Comparison of the Performance of ZSM-5,

b-Zeolite, Y, USY and Their Composites in the Catalytic Cracking of n-
Octane, 2,2,4-Trimethylpentane and 1-Octene. Industrial & Engineering
Chemistry Research, Vol. 33, 800-813, 1994.
30 M L Occelli, H Eckert, M Kalwei, A Wolker, A Auroux. The effects of

steam-aging temperature on the properties of an HY zeolite of the type used
in FCC preparations, in "Fluid Catalytic Cracking V: Technology for Next
Century", M L Occelli, P. Oi'ConnorEds.; Elsevier, Amsterdam, 2001.
31 A Brait, K Seshan, H WeinstabI, A Ecker, J A Lercher. Evaluation of

commercial FCC catalysts for hydrocarbon conversion II. Time-on-stream
behavior of n-hexane conversion and comparison of n-hexane conversion to
MAT. J Applied Catalysis A: General 169, 315-329, 1998.
32 M Absi-Halabi, J Beshara, H Qabazard, A Stanislaus. Catalysts in petroleum

refining and petrochemical industries. Proceedings of the 2nd International
Conference on Catalysts in Petroleum Refining and Petrochemical Indus-
tries, Kuwait, April 22-26, 303-365, 1995.
33 M Absi-Halabi, J Beshara, H Qabazard, A Stanislaus. Catalysts in petroleum

refining and petrochemical industries. Proceedings of the 2nd International
Conference on Catalysts in Petroleum Refining and Petrochemical Indus-
tries, Kuwait, April 22-26, 99-293, 1995.
34 M C Obala, S S Shih. Catalytic hydroprocessing of petroleum and distillates.

Based on the proceedings of the AIChE Spring National Meeting, Houston,
Texas March 28 - April 1, 1993, Marcel Dekker, Inc., New York, 1993.
35 W Keim, J Herwig. Einsatz eines Mikro-Kreislaufreaktors zur Bestimmung

kinetischer Konstanten von Reforming-Katalysatoren. J. Chem. Soc., Chem.
Commun., 1592, 1993.
36 W Keim. Schwefelbestandigkeit von Pt-Ir-L-Zeolith-Reforming-

Katalysatoren. IG-Chemie, 30.11. 1993/94.
37 Internet publication: Wenn TotalFinaElf Wasser in sein Dieselol mischt.

http://www.totalfinaelf-service.de/home/Bibliothek/index.htm, 2002.
38 Internet publication: I B Shumilova, N G Maximovich, S M Blinov, L N

Kuznezov. Vozmozhnye puti borby s posledstviyami razlivov nefti, Nauka,
2002.
Part IV
HEAVY OIL PROCESSING -
CHEMISTRY OF ASPHALTENES
OVERVIEW
From the title given to part IV of this book, it is obvious that in the next two
chapters we will be engaged in studies involving the chemistry of the heaviest
compounds of crude oil - asphaltenes. The presence of these compounds in crude
oil leads to many problems during crude oil treatment. In this part of the book,
these problems and ways to circumvent them are discussed.
The present trend in the petroleum industry shows an increasing demand for
light products such as gasoline, jet fuel and diesel fuel. In order to meet the market
demand, refineries convert a portion of their residual heavy oils into light fractions
by destructive processes as was highlighted in chapter 6. This conversion also
results in the production of modern heavy fuels, which contain a greater concen-
tration of sulfur, vanadium, and asphaltenes.
Asphaltenes are considered to be part of the "bottom of the barrel". They
constitute the non-volatile, high molecular weight fraction of petroleum. In addi-
tion, since asphaltenes are non-soluble in heptane, they remain in the solid form in
crude oil as well.
The chemistry of asphaltenes is very complicated and it is the least studied
field of crude oil chemistry. Because of the complexity of asphaltenes' structure,
there is no information about the exact chemical structure of an asphaltene mole-
cule. It is natural that only the average asphaletene molecular is possible as given
in the literature. The use of such a chemical structure (i.e. average molecular
structure) for the asphaltene molecule is warranted because of the wide molecular
weight range and the diversity of chemical groups in the structure of asphaltenes.
The chemistry and understanding of the nature of asphaltenes is as fascinat-
ing as it is complicated. Many properties of asphaltenes are still not fully investi-
gated. This, perhaps, is the object of the next generation of crude oil chemists; that
325
326 Part IV
is to discover more fully new properties of asphaletenes, and also, to find out ways
to convert these compounds to useful crude oil products.
In the next two chapters, the reader will be exposed to the main problems
that arise for the crude oil industry due to the presence of asphaltenes in crude oil.
The reader will also be exposed to the latest results of investigations of various
possibilities for conversion to useful products of asphaltenes and heavy oil.
8
Chemistry of Crude Oil Asphaltenes
8.1 INTRODUCTION
For many years, crude oil has been the cheapest source of liquid fuels in
many countries. The balancing between product yield and market demand without
manufacturing large quantities of low-commercial-value fractions has long re-
quired processes for the conversion of hydrocarbons of one molecular weight
range and/or structure into another molecular weight and/or structure. Basic proc-
esses for this are the so-called "cracking" processes in which relatively heavy
hydrocarbons are broken down (i.e. cracked) into smaller, lower-boiling fractions.
In the present market, there is increasingly less high quality crude oil but more
bitumen with a very high content of asphaltenes. This is why one has to realize
that heavy bitumen and/or vacuum residues from petroleum refineries have value
as an alternative feed for the production of liquid fuels. In Canada, for example,
60% of all crude oil sources are in the form of bitumen (tar) sands [1]. But by
using almost all the existing cracking processes, coke formation is inevitable. This
makes all these processes non-economic; i.e., the present thermal treatment proc-
esses cannot completely solve the problem of production of fuel fractions from
heavy residues of crude oils.
Reactions that lead to coke formation are polycondensation reactions in-
volving the heaviest and most highly aromatic compounds of crude oil - the as-
phaltenes. Asphaltene is derived from the word "asphaltu" meaning "to split", and
adopted later by the Greeks, signifying "firm", "stable" or "secure". Asphaltenes
are present in crude oil in its original state as the so-called "native asphaltenes".
Asphaltenes are also found in larger amounts in residual fractions because, there is
an increasing trend to extract large portions of light fractions from crude oil by
cracking and visbreaking, while asphaltenes stay in the heavy residues [2].
The classic definition of asphaltenes is based on the solution properties of
petroleum residuum in various solvents. Broadly speaking, asphaltenes are insolu-
ble in paraffin solvents but soluble in aromatic solvents. Structurally, asphaltenes
327
328 Chapter 8
are condensed polynuclear aromatic ring systems bearing mainly alkyl side-
chains. The number of these rings in oil asphaltenes can vary from 6 to 15.
The presence of asphaltene in crude oil causes problem [3] for:
• Oil recovery (in the oil reservoir, in the well, in the pipeline).
• Visbreaking processes (degraded asphaltenes are smaller in size, more aro-
matic and less soluble in maltene than original asphaltene. This leads to coke
formation).
• Blend of mineral oil residue (flocculation of asphaltenes).
• Storage (sludge and plugging due to further oxidation, among other things).
• Preheating (the preheating of fuel oils prior to their burning encourages the
precipitation of asphaltenes and coking).
• Combustion (poor combustion causes boiler fouling, poor heat transfer and
stack solid emission).
All these problems arise from the sedimentation of asphaltenes. Sedimenta-

tion begins when asphaltenes achieve a predetermined size of asphaltene mole-
cules and/or asphaltene particles. The growing of asphaltene molecules is caused
by polycondensation reactions. Lowering the solubility of asphaltenes in oil causes
polycondensation. This implies that in the case of deep cracking of asphaltene,
polycondensation reactions cannot take place.
The objectives of this chapter are twofold. First is to show the fundamentals
of the chemistry and process engineering of asphaltenes during thermal treatment
for achieving deep asphaltene cracking to increase and/or improve distillable
yields of crude oil. The second is to present the current major processes for utili-
zation of heavy oils and residuum fractions.
8.2 PROBLEMS OF CRUDE OIL RESIDUE TREATMENT WITH

RESPECT TO ASPHALTENES
The presence of asphaltene in crude oil causes problems for oil treatment as
follows [4]:
• Asphaltenes formed as a result of thermal treatment are smaller in size, but
more aromatic and less soluble in maltene than the original asphaltene. This
leads to coke formation on the pipe walls resulting in very high heat con-
sumption since coke has a very low thermal conductivity. Coke formation on
pipe walls can also result in blocked pipes and this will lead to a high pressure
drop in the pipes.
• Catalytic treatment: deactivation of catalysts is caused by coke formation, and
also catalysts are poisoned by the heavy metals from asphaltenes
• In blending of mineral oil residue asphaltenes can be flocculated
• Storage (sludge and plugging due to further oxidation, among other things)
Chemistry of Crude Oil Asphaltenes 329
• Preheating (the preheating of fuel oils prior to their combustion encourages

the precipitation of asphaltenes and coking).
8.2.1 Coke Formation and Reduction of Heavy Metals
Generally the mechanism of coke formation can by described be polycon-

densation reactions of asphaltenes or asphaltenes with aromatic or unsaturated
compounds. In the simplest form all these reactions can be represented by the
following reactions:
As + As —» coke + gas
As + n • Ar -» coke + gas
As + n • olefins -» coke + gas
where As: asphaltene molecule

Ar: aromatic compound
gas: hydrogen or hydrocarbon gas.
Polycondensation of asphaltenes proceeds quickly only if asphaltenes are

flocculated from the maltenes. It is appropriate to obtain a better understanding of
the mechanism for flocculation and, consequently, that of polycondensation. In
this context, the original colloidal model of petroleum of Pfeiffer and Saal [5] can
be used to explain any characteristics of crude oil residues and asphaltenes. One
form of this model is shown in Figure 8.1. According to the present version of this
model, asphaltenes associate to form microscopic solids that are dispersed by
amphiphilic resins. The resins are attracted to asphaltenes on one end of the resin
molecule and to small ring aromatics on the other end. While small ring aromatics
act as solvent for asphaltene-resin dispersion, saturates act as a non-solvent. Thus,
this model is neither a solution nor a colloidal model, but a hybrid of both. A mod-
ern corroboration of this model is that the addition of resins to asphaltenes in tolu-
ene reduces its radius of gyration, measured by small angle X-ray scattering
(SAXS) [6]. Furthermore, the addition of low concentrations of amphiphilic model
compounds greatly increases asphaltene solubility. As most models, this is an
oversimplification that enables an approximation of reality within a certain degree
of accuracy. Once the limitations are determined by comparing with actual data,
directions for improving the model are usually suggested.
With the hybrid model of petroleum, it can be seen that asphaltenes are held
in a delicate balance that can be easily upset by the addition of alkanes or the re-
moval or upgrading of resins or small ring aromatics. It has not generally been
known, but the blending of crude oil residues with other compounds can change
the delicate balance and precipitate or stabilize asphaltenes. When crude oil resi-
dues are thermally processed, the side chains are cracked off asphaltenes and res-
330 Chapter 8
ins. This causes resins to combine and form more asphaltenes, and the asphaltenes
to become less soluble [7]. This strongly accelerates the polycondensation reac-
tions and leads to coke formation. In addition, if the thermal conversion is carried
far enough, the asphaltenes can precipitate as a liquid crystalline phase or carbona-
ceous mesophases and very quickly combine to form coke [7]. On cooling, the less
soluble asphaltenes with fewer resins as natural dispersants can precipitate from
the product [8].
mmm
maaam
maRRRam
maRAARam
maRAARam
maRRRam
maaam
mmm
Fig. 8.1: Colloidal dispersion - solution hybrid model of petroleum:
A - asphaltenes
R - resins
a - aromatic compounds
m - maltenes
During the thermal treatment of crude oil vacuum residue, asphaltenes un-
dergo polycondensation reactions that consequently lead to coke formation. As
was mentioned earlier, this results in a high pressure drop since the pipes are
blocked by coke, and to higher heat consumption since the coke has a very low
thermal conductivity. This is why every thermal cracking process has to be
stopped periodically in order to clean off the coke. In contrast to thermal cracking,
catalytic cracking is affected adversely by deactivation of the catalysts due to coke
formation and by catalyst poisoning by reactions with heavy metals. Coking can
be rapid but can be controlled by continuous regeneration as in FCC catalysts, or
slowed down by subjecting to monthly or yearly maintenance, as in hydrotreating
catalysts.
The heavy metals in crude oil residues are agglomerated, first of all, in as-
phaltenes in the form of porphyrin compounds. One example of this compound is
presented in Figure 8.2:
.R1
R
"\
\ ,
N — Me--N
//
R"
\
R1,„/ R
Fig. 8.2: Example of porphirin compound.
Vanadium, nickel and iron generally represent the heavy metal (Me) in the
asphaltenes in Figure 8.2. The molecular weight of this type of compound varies
between 420 and 520, i.e. from C27N4 - C33N4 [10]. During catalytic treatment
of the crude oil residues, the destruction of asphaltenes and the formation of non-
bonded heavy metals occur. A possible mechanism of catalyst poisoning will be
presented in a later part of section 8.2.
8.2.2 Treatment Possibilities for Crude Oil Residues
Treatment for crude oil residues is intended to minimize the adverse effects
of the presence of asphaltenes during thermal processing. Generally, two types of
treatment possibilities are available. There are physical and chemical treatments.
The physical treatment essentially involves deasphalting whereas the chemical
treatment includes thermal processes such as visbreaking and coking.
8.2.2.1 Physical treatment - deasphalting
Feedstocks for cracking processes are now usually the vacuum residue or
heavy distillates from vacuum distillation.
Heavy oils and residues contain substantial amounts of asphaltenes, which
preclude the use of these residues as fuel oils or lubricating stocks. Subjecting
these residues directly to thermal cracking is economically advantageous, since, on
the one hand, the final result is the production of lower-boiling fractions; on the
other hand, asphaltenes in the residue are regarded as coke-forming constituents
and may even promote coke formation from the compounds of the residue.
332 Chapter 8
Furthermore, to avoid catalyst poisoning or reduction in catalyst activity, it

is essential that as much nitrogen and heavy metals as possible are removed from
the feedstock. It has been shown [9] that a greater part of the heteroatoms (nitro-
gen, oxygen and sulfur) and the heavy metals are contained in or associated with
asphaltenes. It is necessary for the cracking processes that asphaltenes are re-
moved from the cracking feedstock.
There are a number of thermal processes, such a visbreaking and coking,
that are directed at upgrading feedstock by the removal of asphaltenes. There is
also the method of deasphalting with liquid hydrocarbons or gases such as pro-
pane, butane or iso-butane. This is very effective in the preparation of vacuum
residues as cracking feedstock.
Fig. 8.3: Propane deasphalting.
In general, propane deasphalting (see Fig. 8.3) or modifications of this proc-

ess are extraction processes in which the desirable oil in the charge is dissolved in
liquid propane and the asphaltenes remain insoluble. In practice, a solvent
deasphalting unit associated with an oil refinery mixes residual oil produced by a
refinery with a light hydrocarbon solvent for producing two liquid product
streams. One stream is substantially free of asphaltenes and contains deasphalted
oil and solvent, and the other stream contains asphaltene and solvent within which
some deasphalted oil is dissolved. These product streams are fed to a solvent re-
covery section that extracts most of the solvent from the product streams. The
resultant solvent-free deasphalted oil is returned to the refinery for conversion to
gasoline, jet fuel, lubricating oils; and the resultant solvent-free asphaltene can be
combined with a diluent, such as diesel fuel, for conversion to residual fuel. In
some units, the solvent recovery section includes a supercritical solvent recovery
section that removes a large percentage of solvent from the product streams, fol-
lowed by an evaporative solvent recovery section that removes the balance of the
solvent. In other units, only the evaporative solvent recovery section is used. In
both cases, the output of the evaporative solvent recovery section is deasphalted
oil product and asphaltene product having acceptable levels of the solvent. In an
evaporative solvent recovery section, each of the liquid product streams of
deasphalted oil and solvent or asphaltene and solvent is first flashed to produce a
vaporized solvent stream and a reduced solvent liquid product stream. Each of the
reduced solvent liquid product streams so produced are then subjected to serial
flashing and/or stripping until the final product stream is free of solvent to the
desired degree. The vaporized solvent produced in this manner is condensed and
reused.
In order to reduce the amount of heat lost as a result of the condensation of
the vaporized solvent, the temperature at which flashing operations are carried out
is kept as low as possible. Thus, the flash drums to which the solvent containing
product streams are applied operate to produce solvent vapor at about 100°C. Heat
contained in these vapors is of such low quality that economic recovery is not
practical. As a consequence, such heat is extracted from the solvent by air or water
cooling, and is lost to the environment.
The solubility of propane decreases with increasing temperature and is
markedly influenced by pressure. Generally, the extraction temperatures can range
from 50 to 90°C with a pressure of 25 to 40 bar. Propane:oil volume ratios ranging
from 4:1 to 10:1 are normally used. Butane alone may also be employed as sol-
vent, but is usually mixed with propane.
8.2.2.2 Chemical treatments
As the availability of lighter crude oil sources diminishes, refiners are being
forced to deal with heavier crude oil feedstocks. This comes at a time when ex-
ploring for oil and gas formations is becoming increasingly more expensive while
there is an increasing demand for refined products, particularly transportation
fuels, such as gasoline and diesel fuel. Refiners are faced with the need for finding
conversion processes to convert the heavy crude oil feedstocks and the various
crude oil residues (residue) that result from the normal refining processes to more
useful and profitable lighter products while minimizing the production of heavy
fuel oils and coke.
Existing processes for converting heavy crude feedstocks and residue to
useful, lighter products include fluid catalytic cracking, residue catalytic hy-
drocracking, thermal cracking, delayed coking, and fluidized bed coking. Vis-
breaking and coking were presented in chapter 6 as processes for treating residue
fractions. In this section, we present some details concerning their chemistry as
well as equipment used to carry out the processes.
334 Chapter 8
8.2.2.3 Visbreaking
Visbreaking as a mild form of thermal cracking significantly lowers the

viscosity of heavy crude-oil residue without affecting its boiling point range. Resi-
due from the atmospheric distillation tower is heated to 425-510°C at mild pres-
sure and mildly cracked in a heater. It is then quenched with cool gas oil to control
overcracking, and flashed in a distillation tower. Visbreaking is used to reduce the
pour point of waxy residues and to reduce the viscosity of residues used for
blending with lighter fuel oils. Middle distillates may also be produced, depending
on product demand. The thermally cracked residue tar that accumulates in the
bottom of the fractionation tower is vacuum flashed in a stripper, and the distillate
is recycled.
Figure 8.4 shows the principle of visbreaking. The feed in this Visbreaking
unit is preheated against steam and visbreaker residue to higher than 300°C. The
feed is then charged to the reaction section which consists of the heater and the
soaking drum. In the heater, the raw material is further heated to more than 450°C
and partially vaporized. The maximum temperature is limited to prevent coke
formation. A mild thermal cracking process takes place in the heater. The severity
of cracking depends on the temperature - the main process variable. The heater
effluent is sent to the soaking drum, where additional residence time is provided to
crack to the desired conversion. The soaking drum is adiabatic whereas the crack-
ing reactions are endothermic. Consequently, the fluid outlet temperature is ap-
proximately 20°C lower than the inlet temperature. The maximum cracking sever-
ity is determined by the stability of the produced fuel oil. The effluent of the reac-
tion section enters the fractionation column at a temperature of more than 400°C.
In the fractionator, gas, naphtha, light and heavy gas oil are separated from the
residue. Alternatively, the gas oil fraction can be included with the visbreaker
residue, removing only gas plus naphtha from the visbreaker effluent. The alterna-
tive procedure minimizes the need for lighter cutter stock to meet viscosity speci-
fications.
The main reactions of the crude oil vacuum residue during visbreaking are
cracking reactions. These kinds of reactions can be described by the following
equation (8.1):
CnH2n+2 ~~* C(n-x)H2(n-x)+2 + CXH2X (8.1)
The basic structural changes in asphaltene composition during visbreaking

are as follows:
• aromatic carbon content increases.
• the number of aromatic and naphthenic rings in the average molecule
slightly decreases.
• the number of side chains and their lengths also decrease.
gas
feed
Fig. 8.4: Visbreaking unit.

O - oven
D - soaking drum
T - rectification tower
S - stripper
V - separator
Two contrasting processes that relate to asphaltenes take place during vis-
breaking:
1) cracking of asphaltenes that results in a decrease in both their content and
molecular weight, but increase in their aromaticity in the oil
2) asphaltenes formation from the polar components of the feed
These processes may be expressed as resulting in a decrease and an increase

in asphaltenes content, respectively. Reactions of condensation of asphaltene pre-
cursors (resins, etc.) prevail for light stocks. For heavier stocks, cracking of as-
phaltenes plays a more significant role. Thus, any increase in asphaltene content
takes place mainly due to concentrating them in the visbreaking residue as a result
of distillation of the visbroken product.
8.2.2.4 Coking
Delayed coking is a thermal cracking process used in refineries to upgrade

and convert crude oil residue known as vacuum tower bottom product (i.e. the
bottoms fraction from a vacuum rectification tower) into liquid and gas product
streams leaving behind a solid concentrated carbon material, coke. The vacuum
towers referred to are generally used to further fractionate virgin atmospheric-
336 Chapter 8
reduced crude oil (see chapter 5). Typically, the vacuum tower bottom product
from such vacuum rectification towers generally includes all the fractions boiling
above a selected temperature. Usually, this temperature can be as low as 450°C.
But often, it is set at 510°C.
A fired heater with horizontal tubes is used in the coking process to reach
thermal cracking temperatures of 485 to 505°C. By using short residence times in
the furnace tubes, coking of the feed material is thereby "delayed" until it reaches
large coking drums downstream of the heater. Three physical structures of coke:
shot, sponge, or needle coke can be produced by delayed coking. These physical
structures and the chemical properties of the coke determine its end use, which
includes being burned as fuel; calcined for use in the aluminum, chemical, or steel
industries; or gasified to produce steam, electricity, or gas feedstocks for the petro-
chemical industry. The technology of coking can be broken into three stages:
1) The feed undergoes partial vaporization and mild cracking as it passes
through a coking oven.
2) The vapors undergo cracking as they pass through the coke drum to frac-
tionation facilities downstream where products of gas, naphtha, jet fuel and
gas oil are separated. The coke remains in the drum.
3) The heavy hydrocarbon liquid trapped in the coke drum is subjected to suc-
cessive cracking and polycondensation until it is converted to volatile product
and coke.
Delayed coking is the only main process in a modern petroleum refinery that
is a batch-continuous process. The flow through the tube oven is continuous. The
feed stream is switched between two drums. One drum is filling with coke while
the other drum is being steam-stripped, cooled, decoked and warmed up (see
chapter 6). The overhead vapors from the coke drums flow to a rectification unit.
The rectification tower has a reservoir in the bottom where the fresh feed is com-
bined with condensed product vapors (recycle) to make up the feed to the coker
heater.
According to Elliott [10], delayed coker design objectives are:

• High in-tube velocities resulting in maximum inside heat transfer coefficient
• Minimum residence time in the oven
• A constantly rising temperature gradient
• Optimum flux rate with minimum practicable maldistribution based on pe-
ripheral tube surface
• Symmetrical piping and coil arrangement within the furnace enclosure
• Multiple steam injection points for each heater pass
In contrast to delayed coking, fluid coking is a continuous process which

uses the fluidized solids technique to convert vacuum residue to more valuable
products, and coke formed during this kind of coking is a byproduct of the process
[11]. The residue at the temperature 480-570°C is coked by being sprayed into a
fluidized bed of hot, fine particles, which permits the coking reactions to be con-
ducted at higher temperatures and shorter contact times than can be employed in
delayed coking (see chapter 3). Moreover, these conditions result in decreased
yields of coke; better quantities of more valuable liquid product are recovered in
the fluid processes.
8.2.3 Coke Forming Reactions During Residue Treatment
A wide variety of reactions occur during the thermal treatment of crude

residue, as was shown earlier. However, not all these reactions lead to the forma-
tion of coke. In this section, we will look at the reactions that are involved in coke
formation for both the catalytic treatment process and the purely thermal treatment
process.
8.2.3.1 Catalytic treatment
Hydrocarbons that react on a catalyst surface may not always follow the
expected reaction pathway. Some compounds adsorb strongly on the surface and
form a coke deposit. This explains why deactivation by coke formation is some-
times called, "self-poisoning". Coke can also be formed by products that are not
taking part in the main reactions. A simple form of a possible reaction scheme for
coke formation during the catalytic treatment of crude oils is given in reaction
equation (8.2). The mechanism of coke deposition is a very complex multi-step
reaction sequence. The reaction path consists of adsorption, dehydrogenation,
polycondensation, and cyclization of hydrogen-deficient fragments [12]. It is not
possible to find a general coking mechanism. Different reaction schemes have
been proposed for different systems. Butt and Petersen [13] discuss a carbanion
mechanism for formation of higher aromatics from benzene and naphthalene on
cracking catalysts. Petersen and Bell [14] propose that coke can be formed from
methylcyclohexane on a platforming catalyst via a doubly bonded intermediate
that is converted to a six-bonded coke precursor.
Olefin1 + Olefin" -» heavier Olefin - n • H2 -> coke (8.2)
Figure 8.5 shows a working metal catalyst surface. On the surface there are
reactants, products, coke in the form of polymers, and different hydrocarbon frag-
ments that may react to coke if they are not removed from the surface [15]. The
carbonaceous layer is not the only form of coke. On iron surfaces, coke can grow
as whiskers with a little metal crystallite.
338 Chapter 8
carbonion hydrogen
olymers
coke
Fig. 8.5: Carbonaceous deposits on the surface of a working metal catalyst.
Coke that accumulates on a catalyst may cause deactivation either by cov-

ering active sites or by physically blocking the pores in the catalyst (see Fig. 8.6).
When the active sites are covered, the activity can drop rapidly even with rela-
tively slow coking. It is important that the coke accumulation occurs slowly so that
the pore mouth is not blocked, cutting off the rest of the pore. When coke is
formed on a catalyst, the degree of deactivation can vary greatly for different re-
actions. The coke may block some sites on the catalyst in preference to others
[16].
The effect of coke formation can be reduced either by preventing coke from
being formed, or by removing it as soon as it has been produced. Steam is known
to reduce the coking rate [17] and it is also possible to remove coke already on the
catalyst by adding steam [18] or by burning off the coke from the catalyst.
High hydrogen pressure can prevent coke formation, since hydrogen is a
product of polycondensation reactions (coke formation). If alkali and alkaline-
earth metals or their oxides are added to the catalyst, these promoters may increase
the gasification of coke on the catalyst [19]. Less coke will be formed on a less
acidic support [16].
Catalyst
Coke
Fig. 8.6: Coke on a supported metal catalyst.
Different catalysts may form coke at different rates. There has been a report
[16] of studies conducted on the effect of coke formation on platforming catalysts
with different metal dispersions. In the report, it was found that small crystallites
had a stronger resistance to coke deposition than larger ones. The explanation for
this fact was that cyclopentadiene (cyclopentane in nitrogen was used as feed)
adsorbed more strongly on the big crystallites and formed coke. The effect was
due to less electronic interaction with the support than for smaller crystallites.
Another study [7] on promotion of reforming catalysts with lithium found out that
the promoted catalysts became more stable against coke formation.
Catalyst poisoning or diffusion blocking by coke formation can have similar
effects on catalyst activity. Assigning a cause to one or the other is an important
first step in poisoning studies. Poisons mask active sites or change the selectivity
of the catalyst for particular reactions or reaction types by reaction with any com-
pounds of feedstock. Poisons are usually metals or multiple-bond light-gas mole-
cules. In the case of vacuum residue treatment, metals are agglomerated in the
asphaltenes. This means catalyst poisoning can be prevented by the removal of
asphaltenes from the process. To differentiate between poisoning and diffusion
blocking, one can first increase the temperature. Heavy product residue will
evaporate off with heating, leaving elemental carbon or poisoning as the culprit.
340 Chapter 8
Substituting an oxidizing gas for the inert gas would remove carbon at high tem-
perature. Such a treatment and the resulting mass and conversion data would show
the relative contributions of poisoning, coking, and heavy product retention.
8.2.3.2 Thermal treatment
In contrast to catalytic treatment, coke formation during thermal treatment

leads only to pipe blocking and poor thermal conductivity of the reactor walls. The
most important difference between coke formation in catalytic and thermal treat-
ment is that a free radical mechanism in coke formation is not possible in the case
of thermal processing.
The rate or velocity of coke formation is, first of all, a function of the feed-
stock characteristics. Seidel [1] reported about the tendencies of different compo-
nents of heavy vacuum residues to coke formation. The following sequence shows
a descending tendency to coke formation during thermal treatment:
asphaltenes > resins > light aromatics > olefins > naphthenes > paraffin
A comparison between the activation energies for coke formation from light aro-
matics (52-58 kJ/mol) and from asphaltenes and resins (34- 47 kJ/mol) shows that
the reaction velocity of coke formation from light aromatics grows faster with
increasing temperature than for coke formation from asphaltenes or resins.
Figure 8.7 shows a possible chemical path from paraffins (the most stable
compounds against coke formation) to coke [1, 20]. It is evident that direct coke
formation from paraffin or naphthenes is impossible. Coke formation can occur
only during thermal cracking of paraffinic fractions by the many complicated
reactions from paraffins to light and then to heavy aromatics. The utilization of
vacuum residue paraffinic compound mixtures in thermal cracking processes can
lead to flocculation of the asphaltenes from the maltenes. Flocculated and agglom-
erated asphaltenes form a melted crystalline mesophase on the reactor walls and
this reacts very quickly to coke. Flocculation of asphaltenes is possible from mix-
tures with aromatic compounds as well. There is a report [12] about the phenome-
non of self-association in asphaltene/aromatic mixtures that has been confirmed
through measurements of surface tension.
paraffin
paraffin olefin
I I
light hydrocarbons light hydrocarbons
+ +
hydrogen
hydrogen
V
lig
aromatics
resm
aromatics coke
V
asphaltene
Fig. 8.7: Scheme for coke formation.
It has been shown [21] that, at low concentrations (below the critical micelle for-
mation concentration), asphaltenes in solution are in a molecular state. Above the
critical micelle concentration, however, asphaltene micelle formation occurs in a
manner similar to that in surfactant systems where surfactant monomers are more
uniform in their structure and less polydisperse. Now, it is obvious that coke for-
342 Chapter 8
mation during thermal treatment is a result of displacing the equilibrium colloid

solution of asphaltenes in maltenes towards asphaltene flocculation and finally to
polycondensation and coke formation.
8.3 METHODS OF ANALYSIS OF CRUDE OIL RESIDUE
8.3.1 Methods and Main Definitions for the Determination of Coke

Formation Tendency
Asphaltenes are derived from the root word "asphalt", a "sticky tar-like
substance found naturally in petroleum crude oil." Asphaltenes are complex, high
molecular weight aromatic compounds suspended within the fuel. They have high
melting points and high carbon/hydrogen ratios with low calorific values.
During the refining process, a portion of the asphaltenes is coked to form
carbon residue. The actual percentage depends on the refining process. For this
reason, the commonly held assumption that asphaltenes in the fuel can be esti-
mated by knowing the Conradson Carbon Residue is erroneous. In actual fact, the
asphaltenes vary widely from Conradson Carbon Residue levels and have to be
analyzed separately.
The term "carbon residue" is used to designate the carbonaceous residue
formed after evaporation and pyrolysis of a petroleum product. The residue is not
entirely composed of carbon, but is a coke that can be further changed by pyroly-
sis. The term is used to indicate the relative tendency of a residue to form carbon
deposits that may foul reactor pipes.
There are three tests used to measure carbon residue: Conradson Carbon
Residue (CCR), Microcarbon Residue (MCR) and Ramsbottom Carbon Residue
(used primarily with distillate fuels). CCR and MCR results are closely correlated,
though MCR is considered to be more accurate and is becoming the predominant
test procedure in test laboratories. The MCR test is also quicker to run and uses a
smaller sample of residue. The standard test method for determining Carbon Resi-
due (Micro Method), ASTM D4530 (ISO 10370:1993) states: "A weighed quan-
tity of sample is placed in a glass vial and heated to 500°C under an inert (nitro-
gen) atmosphere in a controlled manner for a specific time. The sample undergoes
coking reactions and volatiles formed are swept away by the nitrogen. The carbo-
naceous type residue remaining is presented as a percentage of the original sample
as micro carbon residue. The term carbon residue may be misleading as the resi-
due may contain elements other than products from carbon decomposition (such as
ash) in many kinds of residue. The ash content of a residue oil is the non-
combustible residue found in the residue. These are organometallics from the
crude oil, inorganic contaminants or metallic catalyst fines used in the refining
process".
Values obtained by the method of Ramsbottom Carbon Residue are not

numerically the same as those obtained by ASTM Method D524, or Test for
Ramsbottom Carbon Residue of Petroleum Products nor have satisfactory correla-
tions been found between the results of the two methods for all materials which
may be tested, because the carbon residue test is applied to a wide variety of pe-
troleum products.
All vacuum residues have carbon residue, which is a result of the refining
process or asphaltene presence. The only way to reduce the percentage of carbon
residue is to blend the residue with asphaltene free substances.
8.3.2 Analytical Characterization of Heavy Oil Residues and Asphaltenes
8.3.2.1 Solution analysis
The method of solution analysis is based on differences in solubility of the

vacuum residue compounds (pseudo-compounds) in different solvents. Figure 8.8
shows an example of the scheme for solution analysis in which the following
solvents are used:
• Pentane
• Toluene
• Tetrahydrofuran (THF)
Four fractions of pseudo-compounds are obtained by solution analysis of

crude oil residue or its cracked product. During solution analysis of the cracking
product from thermal treatment of vacuum residue or mixtures of vacuum residue
and plastics (such mixtures were used in our investigation), a first step of solution
analysis is soxhlet extraction. In the soxhlet extractor, the liquid/solid product is
extracted with fresh warm solvent (THF) that does not contain the extract. This
can increase the extraction rate, as the sample is contacting fresh warm solvent.
The sample is placed inside a cellulose thimble and placed in the extractor. The
extractor is connected to a flask containing the extraction solvent, and a condenser
is connected above the extractor. The solvent is boiled, and the extractor has a
bypass arm that the vapor passes through to reach the condenser, where it con-
denses and drips into the sample in the thimble. Once the solvent reaches the top
of the siphon arm, the solvent and extract are siphoned back into the lower flask.
The solvent reboils, and the cycle is repeated until the sample is completely ex-
tracted, and the extract is in the lower flask.
After completion of extraction, the cellulose thimble is placed in a drying-
oven at 120°C. After drying, the solid remainder in the cellulose thimble is
weighed. The extract contains the liquid product and solvent (THF). THF is dis-
tilled from the product and reused in a subsequent analysis.
344 Chapter 8
reaction product
liquid / solid
Soxhlet-Extraction
withTHF
filtration
w i t h pentane
I
filtration
w i t h toluene
Fig. 8.8: Scheme of solution analysis.
The rest of the THF is removed from the product by drying at room temperature.
This can proceed from one through any number of days. Figure 8.9 shows a typi-
cal progression of this drying process.
The following balance equation (8.3) is used for the definition of the amount
of liquid product:
liquid product — mfee(jstocjc — mremajn — nigas (8.3)

THF reduction in the liquid product
1 2 3 6 7 8 9 10 11 12 13 14
time [day]
Fig. 8.9: Typical progression of THF reduction in the liquid product.
The drying of the extract has to be complete if equation (8.4) is to be satis-

fied.
(8.4)
After the soxhlet extraction and drying of the extract are completed, the
extract is dissolved in pentane first. An ultrasound bath can be used to improve
solving. This solution of extract in pentane is filtered. After filtration, the extract is
separated into two fractions: pentane soluble fraction or filtrate and the remainder.
The pentane soluble fraction is composed of compounds that have similar polarity
as pentane or the liquid at the filtration temperature. The remainder contains the
asphaltene fraction and precoke. This remainder is dissolved in toluene in the
same manner as the extract was solved in pentane, and then filtered. The asphal-
tene fraction is the filtrate after filtration with toluene, and precoke is the remain-
der. The solvents (pentane and toluene) are removed from the filtrates by distilla-
tion at 40°C and normal pressure for pentane distillation, and 70 mbar for toluene
distillation.
The described example of solution analysis was shown for the analysis of
crude oil vacuum residue, but this method can be successfully applied for different
kinds of feed. In our investigation, we used this method for the analysis of mix-
tures of vacuum residue and plastics, and pure plastics. In the case of the plastic or
product of its cracking analysis, one has to consider that what is left behind after
soxhlet extraction is the heavy plastic fraction or non-cracked plastic.
346 Chapter 8
Table 8.1 shows the results of solution analysis for the vacuum residue (Bi-
tumen 200 Elf) and plastics that were used in our investigation:
Table 8.1: Results of solution analysis for the different kinds of feedstock.
TWrl pentane soluble toluene soluble TUP soluble remainder

JTvCU
(wt.%) (wt.%) (wt. %) (wt%)
Bitumen B200E 70.70 28.40 0.90 0.00
polystyrene 1. 11 51.34 43.45 4.10
Polypropylene 0.00 0.00 0.00 100
Polyethylene 0.00 0.00 0.00 100
PVC 9.70 5.98 45.78 38.54
Based on the results shown in table 8.1, it is obvious that during solution
analysis of the cracking product of polyethylene and polypropylene, only non-
cracked plastics remain completely in the remainder. In contrast to polyethylene
and polypropylene, polystyrene and PVC are over 40 wt. % soluble in THF.
8.3.2.2 Coagulation analysis
Similar to solution analysis, the method of coagulation analysis is based on

the different solubilities of vacuum residue compounds (pseudo-compounds) in
the different solvents. The following solvents were used for the analysis of feed-
stock:
• n-heptane
• toluene
• mixture of iso-butanol and cyclohexane (4:1)
• mixture of acetone and chlorinemethylene (1:2)
• iso-butanol
Figure 8.10 shows the general scheme for coagulation analysis that was used
for analysis of crude oil vacuum residue in our investigation.
During coagulation analysis, the ratio of the coagulation agent to the sub-
stance is 40 to 1 based on recommendations by many authors that this ratio is the
optimum for this kind of analysis [1, 22]. The coagulation of the asphaltene frac-
tion in the scheme is done according to the Golde method (DIN 51595, IP 143/57)
recommended as the most exact method of asphaltene definition [1, 23, 24].
Bitumen
Coagulation n-heptane Mixture of Mixture of iso-butanol

agent: iso-butanol and acetone and
cyclohexane chlorinemethy-
(4:1) lene (1:2)
\l V
f f
flocculated asphaltene hard paraffin soft oil
fraction resin resin
Fig. 8.10: Scheme of coagulation analysis for vacuum residue.
In the first step of the Golde method, the substance is dissolved in n-heptane
in the ratio of n-heptane:substance = 1:40. The asphaltene fraction is flocculated
from the dissolved sample after 24 hours of coagulation. After this, asphaltenes are
filtered from the maltenes. And the rest of maltenes or resins, which stay in the
asphaltenes during flocculation with n-heptane at room temperature is extracted by
soxhlet extraction (see preceding section). In the next step, the hard resin fraction
is coagulated from the maltenes in the same manner as the asphaltenes from the
vacuum residue, but during this step, a mixture of iso-butanol and cyclohexane is
applied as coagulation agent. In the case of hard resin coagulation, the coagulation
agent with the solved substance is not filtered, but removed from the glass with a
pipette, and the product (hard resin) is not extracted, but only dried. The coagula-
tion agent is distilled from the rest of the sample, and the rest is analyzed in the
next analysis step in the same manner. The analyses proceed until only the oil
fraction stays.
An example of the results of this analysis for Bitumen 200 Elf is presented
in table 8.2. Coagulation analysis for the vacuum residue was carried out for three
samples (1,2 and 3), which were taken from three different levels of the container;
since bitumen is a colloid solution, the result of the coagulation analysis can differ
depending on the level in the container. From table 8.2, it is evident that the ana-
lyzed vacuum residue represents the colloidal stable solution, because the values
of the amount of all fractions are approximately the same for all levels. For each
348 Chapter 8
Table 8.2: Results of coagulation analysis for Bitumen 200 Elf.

asphaltene hard resin paraffin soft resin oil
l.a) 11.25 21.03 0.82 14.86 52.03
b) 11.24 22.49 0.83 15.54 49.90
c) 11.25 21.59 0.81 14.86 51.48
mean of 1 11.25 21.70 0.82 15.09 51.13
2. a) 11.17 20.83 0.93 15.20 51.86
b) 11.16 20.19 0.92 15.54 52.18
c) 11.18 19.01 0.94 15.13 53.73
mean of 2 11.17 20.01 0.93 15.30 52.59
3. a) 11.06 19.22 0.94 15.13 53.64
b) 11.07 19.46 0.93 15.20 53.34
c) 11.08 19.41 0.95 15.07 53.49
mean of 3 11.07 19.36 0.94 15.14 53.49
mean 11.16 20.36 0.90 15.18 52.40
sample, coagulation analysis was carried out three times (a, b and c). It is also
obvious from table 8.2 that the method of coagulation analysis is very reproduci-
ble since the difference between analyses a, b and c is very small.
For the characterization of the product of thermal treatment of vacuum resi-
due and mixtures of vacuum residue and plastics, a simpler method of coagulation
analysis was used, since the method described earlier is very complicated to use
for the given number of samples. The scheme of coagulation analysis for the
product of thermal processing is represented in Figure 8.11:
During the analysis shown in Figure 8.11, the sample is broken down into
four fractions:
• Maltene
• Asphaltene
• Precoke
• Remainder
The remainder during this analysis is coke, in the case of thermal treatment
of pure vacuum residue, and coke and non-cracked plastics, in the case of the
thermal treatment of mixtures of crude oil vacuum residue and plastics.
Product
Soxhlet extraction
with n-Heptane
I
solve
in toluene
Fig. 8.11: Scheme of the coagulation analysis for the product of thermal treatment.
8.3.2.3 Distillation method
Distillation analysis is based on the fractionation of the sample by boiling

temperature. This type of analysis can be carried out only up to a maximum tem-
perature of approximately 350°C, since at higher temperatures cracking of the
heavy organic components occurs.
Figure 8.12 shows the composition of the asphaltene fraction after the dif-
ferent solution analyses and distillation. From Figure 8.12, we see that the depth of
distillation can be controlled by the level of vacuum. With a higher vacuum, less
non-asphaltic compounds stay in the residue.
350 Chapter 8
100
5?
$
.o
'35
&
o
o
• asphaltenes I polar aromatics

dnaphthenic compounds I saturated compounds
Fig. 8.12: Analysis methods.
1 - vacuum distillation
2 - deep vacuum distillation
3 -flocculationwith propane
4 - flocculation with pentane
5 -flocculationwith heptane (Golde method)
8.3.2.4 Chromatography
Chromatography is based on the differential adsorption ability of the vac-

uum residue components on an adsorbent (see chapter 2). As a first step, the
solved vacuum residue is adsorbed on the adsorbent and then different compo-
nents in the sample are desorbed using solvents of various polarities. An example
of a scheme for chromatographic analysis (E. D. Radchenko) is shown in Figure
8.13 [1].
vacuum residue
chromatography on silica gel

- VlUVSJ-llUVVSt^l UL/11 y V/ll Olll^tl gvl 1
compounds unsaturatedx:ompounds asphaltene <ind resin
I
treatment with carbomid
I
n-paraffin iso-paraffin
Fig. 8.13: Vacuum residue chromatography on silica gel.
13
8.3.2.5 C-NMR analysis
Nuclear magnetic resonance (NMR) is a phenomenon that occurs when the

nuclei of certain atoms are immersed in a static magnetic field and exposed to a
second oscillating magnetic field. Some nuclei experience this phenomenon, and
others do not, depending on whether they possess a property called, "spin". Spin is
a fundamental property of nature like electrical charge or mass. Spin comes in
multiples of 1/2 and can be + or -. Protons, electrons, and neutrons possess spin.
Individual unpaired electrons, protons, and neutrons each possess a spin ofl/2.
When placed in a magnetic field of strength B, a particle with a net spin can
absorb a photon of specific frequency. The frequency C depends on the gyromag-
netic ratio, y, of the particle (see equation (8.5)).
•o = B • y (8.5)
For 13 C,y= 10.71 MHz /T
Almost every element in the periodic table has an isotope with a nonzero
nuclear spin; the spin for carbon (13C) is Vi. In order to understand how atoms with
spin behave in a magnetic field, let us consider carbon. Think of the spin of this
carbon as a magnetic moment vector, causing the proton to behave like a tiny
magnet with a north pole and a south pole. When the carbon is placed in an exter-
nal magnetic field, the spin vector of the particle aligns itself with the external
352 Chapter 8
field, just like a magnet would. There is a low energy configuration or state where
the poles are aligned N-S-N-S, and a high-energy state N-N-S-S.
The NMR analysis is a continuous wave experiment. There are two ways of
performing this experiment. In the first, a constant frequency continuously probes
the energy levels of the molecules while the magnetic field is varied. The energy
of this frequency is represented by the blue line in the energy level diagram.
The continuous wave experiment can also be performed with a constant
magnetic field and a frequency that is varied. The magnitude of the constant mag-
netic field is represented by the position of the vertical blue line in the energy level
diagram.
Nuclear magnetic resonance spectroscopy is the use of the NMR phenome-
non to study physical and chemical properties of matter. As a consequence, NMR
spectroscopy finds applications in several areas of science. NMR spectroscopy is
routinely used by chemists to study materials. Solid state NMR spectroscopy is
used to determine the molecular structure of solids. In our investigation, NMR
spectroscopy was used to determine the molecular structure of asphaltene mole-
cules.
Asphaltene and/or coke molecules contain carbon. Unfortunately, the 12C
nucleus, which is contained in crude oil residues, does not have a nuclear spin, but
the ' C nucleus does, due to the presence of an unpaired neutron. This is why only
13
C can be used in C-NMR analyses.
The result of 13C-NMR analyses for the asphaltenes and hard resins in Bi-
tumen 200 Elf is presented in table 8.3. From table 8.3, it is evident that asphalte-
nes (heavier fraction) have a higher aromaticity in comparison to hard resins and at
the same time a lesser amount of paraffin side chains. This shows that asphaltenes
have a higher tendency to coke formation in comparison with hard resins (see
section 8.2).
Table 8.3: Results of I3C-NMR analysis for asphaltenes and hard resins (% of C
in the chemical group to total C in the sample).
hard resin asphaltene

-CH3 5.2 3.5
a-CHj 13.3 9.2
a-CH2 6.3 4.6
-(CH2)n>4- 14.5 11.8
-CH2-hridgc 10.9 8.9
->CH 7.6 6.9
*-*pn>toned aromatic 27.0 36.2
^— alcil. anvnatics and v-ixjnd. arnmalics 14.5 18.8
^-phoio) Aronatics 0.6 0.0
Aromaticity of the fraction 42.1 55.0
8.3.2.6 Ultimate analysis
In our investigation, we used VARIO EL analytical unit for ultimate analy-

sis. In this analysis, the data concerning the amount of carbon, hydrogen, nitrogen
and the other heteroatoms are obtained. The applied kind of ultimate analysis is
based on oxidation of the sample at 960°C, at which the oxides of carbon, hydro-
gen and nitrogen are determined. Sulfur determination is very important for crude
oil vacuum residues in addition to ultimate analysis, since many authors have
reported that feedstock with a higher sulfur content has a stronger tendency to
coke formation during thermal or catalytic treatment. The results of ultimate
analysis and sulfur determination for feedstock used in our investigation is shown
in table 8.4.
The ratio of H / Catomic can be calculated from the obtained data by the fol-
lowing equation (8.6).
H/Catomic=12-H/C (8.6)
where H - amount of hydrogen in the sample (wt. %)

C - amount of carbon in the sample (wt. %)
This value shows the quality of the product or the depth of hydrogenation of the
feedstock. The higher the H / Calomic ratio, the more deeply hydrogenated the feed-
stock is. Feedstock with a H / CatomjC ratio higher than two can be used as hydrogen
donor during thermal or catalytic treatment of the heavy feed. These values of the
H / Catomic ratio are presented in table 8.5.
Table 8.4: Results of ultimate analysis and sulfur determination (wt.%).
Feedstock carbon hydrogen nitrogen sulfur oxygen

C H N S Oditf
Bitumen-B200E 85.24 10.17 0.60 3.25 0.74
Asphaltene 84.58 7.50 1.50 6.42
Hard resin 84.46 8.90 0.85 5.79
Paraffin 79.85 9.70 0.54 9.91
Soft resin 84.40 10.25 0.52 4.83
Oil 84.73 11.21 0.34 3.72
Polystyrene 92.29 7.71 0.00 0.00 0.00
Polypropylene 85.81 14.19 0.00 0.00 0.00
Polyethylene 85.83 14.14 0.00 0.00 0.03
354 Chapter 8
Table 8.5: H / Ca,nmic ratio for the feedstock used.

Feedstock H/CaKjmii;
Bitumen 1.43
Polystyrene 1.00
Polypropylene 1.98
Polyethylene 1.97
From the table 8.5, it is evident that polypropylene and polyethylene have
H/Catomic ratio of approximately two, which means that these plastics can be used
as hydrogen donors during the co-processing of crude oil vacuum residue and
plastics.
8.3.2.7 Molecular weight determination
Vapor pressure osmometry has become the prevalent method for determin-
ing asphaltene molecular weights. However, the value of the molecular weight
from vapor pressure osmometry must be weighed carefully since, in general, the
measured value of molecular weight is a function of temperature and the solvent
molecular properties (see next section). The vapor pressure osmometry method is
suitable for the determination of the average molecular weight of high molecular
substances, which are soluble in different organic solvents.
An example of a vapor pressure osmometer is shown in Figure 8.14. Two
thermistors, connected to measure the difference, are suspended in a thermostated
measuring cell filled with the saturated vapor of the solvent. The measuring
probes, which are first covered with solvent droplets, adapt to the cell temperature.
Thus, there is no temperature difference between them. Exchanging the
solvent droplet of one of the probes by a droplet of the solution leads to condensa-
tion of solvent vapor due to the lower vapor pressure of the solvent above the
solution. Thereby, the released condensation enthalpy increases the temperature of
the solution droplet, which simultaneously leads to an increase of the vapor pres-
sure. After reaching the vapor pressure equilibrium of the solution droplet, a rela-
tively stable temperature is obtained at the solution droplet. This temperature is
converted by the measuring system to a direct voltage signal and is thereby at the
user's disposal as a measuring value. The resulting relative measured value is
nearly proportional to the osmolal concentration of the solutions. However, it may
be affected by heat loss and the nonideal behavior of the polymer solutions.
Fig. 8.14: Osmometer.
By calibrating with solutions of known molality and statistical calculations

of the measured value, the nonlinear behavior may be eliminated. Figure 8.15
shows an example of the calibration line for benzile, which was used in our inves-
tigation. Kc-,1 (calibration coefficient) is defined from the calibration line, as is
shown in Figure 8.15. The molecular weight is calculated by equation (8.7):
M = Kou / K (8-7)
K in this equation (8.7) is found in the same manner as K^ from the dia-
gram for the investigated sample. Figure 8.16 shows an example of this diagram
for asphaltenes from Bitumen 200 Elf.
Defined molecular weights for the different fractions from Bitumen 200 Elf
are presented in table 8.6.
356 Chapter 8
asphaltene
5 10 15
concentration, Cwt tg/kg]
Fig. 8.15: Definition of K^,.
calibration
5000
4500 -
4000 - 3031
3500 -;.
3000
2500 --
2000 --
1500
1000
500
0
0 0,02 0,04 0,06
molar concentration
Fig. 8.16: Definition of K.

Table 8.6: Molecular weight for different fractions of Bitumen 200 Elf.
Fraction Molecular weight
Asphaltene 1440
Hard resin 1220
Paraffin 1090
Soft resin 1150
Oil 607.5
From table 8.6, it is evident that the heaviest fraction of crude oil vacuum
residue is the asphaltene fraction. The hard resin fraction has approximately the
same molecular weight as asphaltenes. From the molecular determination and 13C-
NMR analysis of asphaltenes and hard resins (see preceding section), it is obvious
that these two fractions have approximately the same chemical properties. Oil is
the lightest fraction of the crude oil residue, and this is why this fraction is not as
important as the asphaltene and resin fractions from the chemical perspective of
coke formation.
8.3.3 Temperature Influence on Molecular Weight Determination
In the preceding section, the vapor pressure osmometry method for the de-
termination of the molecular weight was described. It is important that the value of
the molecular weight from vapor pressure osmometry be weighed carefully since,
in general, the measured value of the molecular weight is a function of tempera-
ture and the solvent molecular properties. This influence of the temperature and
solvent can be explained by a very high tendency of asphaltenes to micelle forma-
tion. Figure 8.17 shows one example of micelle formation from two asphaltene
molecules.
Fig. 8.17: Example of micelle formation.

358 Chapter 8
It is obvious that the solubility of asphaltenes in a given solvent increases as the

temperature of measurement is increased. For example, the molecular weight of
the asphaltenes from Bitumen 200 Elf is 1440 mol/g defined at 60°C and 10050
mol/g defined at 37 °C. It is clear that at 37°C, asphaltenes were not completely
solved in the toluene and the defined molecular weight is probably the molecular
weight of the micelles which are formed from 6 to 8 asphaltene molecules. The
molecular weight of 1440 is very close to the molecular weight of asphaltenes
reported in many references [1,9].
In order to provide a good explanation of asphaltene chemistry, it is par-
ticularly important that all measurements of molecular weights are carried out at
the same temperature, because values of molecular weight defined at different
temperatures cannot be compared with each other. Doing so can lead to wrong
results. All the molecular weight determinations in our investigation were carried
out at the temperature of 60°C, since the molecular weight defined at this tem-
perature is closest to values provided by other authors (see above).
Processing of Heavy Crude Oils and
Crude Oil Residues
9.1 INTRODUCTION
This chapter of the book is devoted to investigations on the processing of

heavy crude oil residues. There are many processes already used in the oil industry
for this purpose, but usage of the existing or developed processes has not been
based on economic justifications all the time, because of the presence of asphal-
tene in heavy crude oil or residue (see section 8.1).
Methods to treat crude oil vacuum residue with a co-feed that will initiate
the cracking of the residues constitute the main topic presented in this chapter.
These methods are new and have not yet been applied in industry. However, based
on the results of this investigation, many new properties of asphaltenes have been
elucidated, which can be employed for deeper treatment of the crude oil.
This chapter as well as chapter 8 is engaged in asphaltene chemistry. In this
chapter, however, the reader will see some practical applications of the asphaltene
chemistry to heavy crude oils or vacuum residues.
One of the objects of this chapter is to show how many potential possibili-
ties of crude oil treatment are yet to be discovered. Again, it will attempt to answer
the question whether it is still possible to develop processes which can strongly
increase the production of light fractions from crude oil; that is to increase the
deepness of crude oil treatment.
359
360 Chapter 9
9.2 CHEMISTRY AND REACTION OF ASPHALTENES DURING CO-

PROCESSING OF CRUDE OIL RESIDUE AND PLASTICS
9.2.1 Change of Asphaltene Structure During Thermal Processing
Crude oil residues and bitumen are colloidal disperse systems. In these sys-
tems, high-molecular solid structure units (asphaltenes) are dispersed in an oily
phase (maltenes) (see section 8.2). In industrial thermal cracking processes, these
units precipitate as coke. Coke formation is caused by polycondensation reactions
of aromatic cores of asphaltenes, which lose the paraffinic periphery. The main
objective of a substantial portion of this chapter is to show how deep cracking of
bitumen at low temperature can be achieved without coke formation (i.e., without
polycondensation of asphaltenes). The main reactions of asphaltenes that lead to
coke formation are described. Also described are ways to reduce the negative
influence of these reactions on the process.
The behavior of asphaltenes during thermal treatment of pure vacuum resi-
due (VR) is remarkable. At 400°C, the molecular weight of the asphaltenes de-
creases to a residence time of 30 minutes and then increases up to almost double
the value of the molecular weight of native asphaltenes (see Fig. 9.1).
15 20 25 30 35 40
residence time [min]
Fig. 9.1: Molecular weight of asphaltenes versus residence time during co-processing.
Processing of Heavy Crude Oil and Residue 361
The reduction in molecular weight as the reaction proceeds is attributed to

cracking of the paraffinic periphery. This cracking can be described by the fol-
lowing equation (9.1):
AR-CH2-CH2-CH3 -» AR-CH=CH2 + Cft, (9.1)
Following this explanation, the decrease by about 30 wt.% in molecular

weight has to be directly proportional to the content of paraffinic chains in the
asphaltene molecule. I3C-NMR analysis of native asphaltenes for bitumen B 200
Elf showed an amount of 29 wt.% of paraffinic periphery in the asphaltenes. This
means that after a residence time of 15 minutes (at 400°C), the aromatic cores of
native asphaltenes (see Fig. 9.2) are what are left of the original asphaltene. The
strong tendency of aromatic asphaltene cores to polycondensation reactions has
been reported in the literature [1]. Polycondensation reactions are reactions that
lead to nascence of products heavier than the feedstock and gas. Generally, poly-
condensation reactions of asphaltenes can be described by the following equation
(9.2):
n • Ac -» -[Ac]-n + A • H2 + B • CxHy (9.2)
In contrast to the results at 400°C, no reduction in asphaltene molecular

weight was observed for residence times up to 40 minutes for reactions conducted
at 425°C (see Fig. 9.2). This means that at higher temperatures, polycondensation
reactions proceed faster than decomposition reactions. At any temperature, the
determined molecular weight of asphaltenes shows that it reaches equilibrium as
the reaction proceeds. This implies that at a longer residence time, the molecular
weight of. the asphaltene fraction will not increase any further because after
achieving equilibrium molecular weight, they become less soluble in the maltenes.
This leads to their flocculation from the maltenes fraction (Fig. 9.2) and, finally, to
coke formation.
The decrease in molecular weight at longer residence times shows that poly-
condensed asphaltenes contribute to the molecular structure that can be decom-
posed at 425°C. The chemical path for the formation of such asphaltenes can be
described, for example, by reaction (9.3):
R1 - AR = CH2 + CH2 = Ar -» R1 - AR = CH - CH = AR + H2 (9.3)
R represents a paraffinic side chain. This means that R1 can be cracked in

the same way as was shown in reaction (9.1). At 425°C, the cracking of naph-
thenic and/or aromatic rings is not possible as this reaction requires a temperature
of over 550°C. However, it is especially interesting that hydrogen transfer and
hydrogenation of aromatic cores of asphaltenes take place by the mechanism de-
scribed in reactions (9.4-6) [9].
362 Chapter 9
This means that cracking of the paraffmic periphery (reaction (9.1)) is the
only reaction that can cause the reduction of the molecular weight of asphaltenes
at this temperature level. In other words, during polycondensation of asphaltenes
at 425 °C, it is not only the aromatic cores of native asphaltenes that react. As-
phaltenes with paraffmic chains also undergo a reaction (reaction (9.3)).
paraffin
asphaltene flocculated asphaltene
Fig. 9.2: Scheme of asphaltene flocculation.
—> + H- (9.4)
+ H- (9.5)
—» (9.6)
The fact that at the low temperature no cracking of naphthenic rings occurs
(which could lead to the nascence of olefins) permits us to say that the quality of
the product formed is better if crude oil is thermally processed at a low tempera-
ture. This is because the chemical stability of naphthenes and aromatics is higher
in comparison with olefins that arise during the cracking of naphthenes at higher
temperature.
On account of the tendency of the asphaltene core to polycondensation, the
increase in molecular weight at residence time over 15 minutes and a reaction
temperature of 400°C can be explained by polycondensation of aromatic cores of
asphaltenes (reaction (9.2)). Polycondensation reactions affect coke formation.
This is noticed at 40 minutes residence time. By the thermal treatment of Bitumen
200, approximately 1 wt.% coke (based on water free feed) was formed. The fact
that coke formation begins at the temperature of 400°C only if asphaltenes attain a
very high molecular weight in comparison to higher temperature levels is caused
by the formation of a stable steric colloid with the resins. This stable colloid is not
cracked at the temperature of 400°C as deeply as at higher temperature levels. The
formation of such a colloid is represented in Figure 9.3:
flocculated asphaltene resin asphaltene steric colloid
Fig. 9.3: Scheme of formation of asphaltene steric colloid.
At 450°C, asphaltenes achieve the equilibrium molecular weight at a resi-

dence time of 15 minutes (see Fig. 9.1). At this temperature, the molecular weight
of asphaltenes is reduced by 33 wt.%. This molecular weight degradation implies
the complete decomposition of the paraffinic periphery of the asphaltene mole-
cule. At 450°C, the flocculation and polycondensation of asphaltenes to coke
begins with the transformation of asphaltenes to the aromatic core of native as-
phaltenes. This is caused by a faster change of asphaltene solubility in maltenes
and a higher reaction rate of polycondensation at this temperature level than at
lower temperatures. The formation of a stable colloid solution via reaction (Fig.
9.3) is not possible either, since coagulation analysis has shown that resins are
already completely cracked at a residence time of 15 minutes and a temperature of
450°C.
364 Chapter 9
Based on the knowledge about the possible reactions of asphaltenes during

thermal processing of pure bitumen, we can suggest the following general scheme
of asphaltene reactions during thermal treatment (9.7):
Gas <— Maltene <-» Resin <-> Asphaltene -» Coke (9-7)
1
The reaction of coke to gas proceeds only if the coke was formed via the
mechanism described by reaction (9.3), i.e. if paraffin side chains are available in
the coke structure. These side chains can be cracked via reaction 9.1.
Based on 13C-NMR analysis, ultimate analysis and molecular weight deter-
mination (table 9.1), a model of the average molecule was built for native asphal-
tene (Fig. 9.4a) and asphaltene from visbreaking at 425°C and a residence time of
30 minutes (Fig. 9.4b). These figures show clearly that during the thermal treat-
ment of crude oil residue, only the cracking of paraffmic chains can cause asphal-
tenes reactivity to yield coke.
In the same way, a model of asphaltenes as a product of the thermal treat-
ment of VR/plastics blends was investigated (Fig. 9.5a-c). The destruction of aro-
matic cores of asphaltenes can be clearly observed during the co-processing of VR
and plastics. This can explain the minimization of coke formation during the co-
cracking of VR and plastics.
Table 9.1: Data for development of the average molecule model of asphaltenes.
C-Atom VR VR VR/PP/PS VR/PE/PP/PS/PVC

(wt. %) after after after
visbreaking visbreaking visbreaking
-CH3 4.9 4.9 4.6 4.6
cx-CH3 9.5 9.5 8.6 9.7
a-CH2 0.0 0.0 3.1 3.5
-(CHjW 9.1 9.1 5.5 7.0
-CHl-brdjes 2.8 2.8 4.1 5.4
->CH 3.9 3.9 5.4 4.2
^protoned arotnaucs 44.4 44.4 46.7 43.8
aJcyl. aromalio.
23.1 23.1 20.5 20.2
*-cond. arcmatics
^-phairi aramatiui 2.2 2.2 1.4 1.5
(wt. %) ultimate analysis
C 84.58 86.15 85.70 81.65
H 7.50 4.34 4.94 4.77
N 1.50 1.32 1.49 1.80
Odifleraice 6.42 8.19 7.87 11.78
molecular weight determination
Molecular weight 1430 1270 350 380
a)
b)
Fig. 9.4: Model of the average molecule of asphaltene.

a) Native asphaltene
b) Asphaltene from visbreaking
366 Chapter 9
a)
b)
•ci
c)
Fig. 9.5: Model of average asphaltene molecule as a product of the thermal treatment of:
a) VR/PP/PS blends at 425°C and residence time 15 minutes
b) VR/PE/PP/PS blends at 425°C and residence time 30 minutes
c) VR/PE/PP/PS/PVC blends at 425°C and residence time 15 minutes
From Figure 9.5c, it is evident that during the joint cracking of bitumen and
PVC a reaction takes place between asphaltenes and chlorine. GC analysis of the
product gas of the joint cracking of bitumen and PVC has shown that these reac-
tions proceed very extensively, since in the product gas was found no hydrogen
chloride which is formed in very large amounts for the thermal cracking of pure
PVC. This shows a very high tendency of asphaltenes towards reactions with
chlorine.
The main structural elements of the asphaltene molecule can be classified

based on the data from Figures 9.4 and 9.5 as follows:
• Paraffin periphery
Bridge-ring structure
or
Aromatic structure
• Heteroatom structure
From the investigation into asphaltene chemistry, it is obvious that paraffin

side chains can be readily cracked during the thermal treatment of pure bitumen at
a relatively low temperature. Aromatic and heteroatom structures are inclined to
polycondensation reactions and finally to coke formation. Especially interesting
are bridge-ring structures since these structural elements will only be cracked
either at high temperature or by the addition of plastics to the feedstock.
368 Chapter 9
9.2.2 Evaluation of Possibilities of Various Asphaltene Reactions Based on

Thermodynamics
The reactions of the main structural elements of asphaltene were investi-

gated. First of all, it is necessary to calculate the thermodynamic possibility of the
reactions to be investigated. Using equation (9.8) does this evaluation:
AG = Gproducu - Gfeed (9.8)
AG - difference of the free enthalpy of the reaction

Gproducis - free enthalpy of the reaction product
Gfeed - free enthalpy of the feed
The values for free enthalpies can be taken from the literature [25]. But for
complicated compounds such as asphaltenes, no data are available in the literature.
Thus, for the evaluation of the reaction possibility between high molecular weight
compounds, the free enthalpy of each of the products and feed have to be calcu-
lated. One example for this calculation is given below.
Example
The free enthalpy for the following compound (Fig. 9.6) has to be calcu-
lated. The free enthalpy for such complicated compounds can be calculated based
on the knowledge of their structural elements. The values for free enthalpy of the
structural elements can be found in ref. 25. The enthalpy values for important
structures of asphaltene are presented in table 9.2.
In the example (Fig. 9.6), there are the following structural elements:
a) Aromatic bond
>C-H: seven bonds
>C-R: three bonds
>C - : four bonds
b) Acyclic bond
- CH3: three bonds
>CH 2 : one bond
c) Corrections for acyclic substitutes on aromatic core

1,2-substitutes: two substitutes.
Fig. 9.6: Example of compound used to illustrate the calculation of free enthalpy.
Table 9.2: Values of free enthalpy for structural elements (kJ/mol).
0°K 298°K 400°K 500°K 600°K 800°K 1000°K 1200°K | 1500°K

aromatic bond
>C-H 16.74 20.26 23.02 25.66 28.38 34.12 40.02 45.92 54.88
>C-R 24.11 36.67 39.10 42.82 46.80 54.75 61.79 69.45 80.50
>c- 22.14 22.73 24.28 27.17 30.47 33.70 38.43 45.84 51.45
naphthenic bond
>CH2 46.59 55.13 59.32 63.88 68.69 78.49 88.49 98.62 113.82
>CH- 52.95 68.48 74.09 80.16 86.02 97.49 109.09 120.31 136.97
acyclic bond
-CH3 -34.58 -17.33 -8.37 1.00 10.76 30.98 51.82 72.84 104.48
>CH2 -15.38 8.57 18.75 29.01 39.47 60.63 81.96 103.26 135.34
>CH- 0.75 31.23 43.49 55.51 67.60 91.51 114.91 138.22 171.46
>C< 7.28 47.89 62.79 77.23 91.34 118.71 144.84 170.41 208.09
H2C= 30.39 33.24 35.87 41.73 42.03 48.93 56.26 63.71 75.05
HO 113.69 103.81 100.51 97.37 94.19 88.07 82.09 76.27 67.69
Corrections for acyclic substitutes on aromatic core
1,2-Sub. 2.09 2.09 2.09 2.09 2.09 2.09 2.09 2.09
—
1,3-Sub. ... -2.93 -2.93 -2.93 -2.93 -2.93 -2.93 -2.93 -2.93
1,23-Sub. 4.19 4.19 4.19 4.19 4.19 4.19 4.19 4.19 4.19
heteroatom structures
>CO -128.09 -119.72 — -108.42 94.60 -- —
— —
-o- —- -99.63 — — — ... -- — --
-NH2 — -26.79 — — ... — — —
_
—
-SH 1198 -- — — —
— — —
-s- — 32.65 — — — -- — — —
In order to calculate the free enthalpy of the compound, the values of the
free enthalpies of the various bonds in the compound are added. For the shown
example at the temperature of 600°K (326.85°C):
G = 7-23.38 + 346.80 + 4-30.47 + 3-10.76 +1-39.47 + 2-2.09 = 501.87 kJ/ mol
This calculation method has a divergence of approximately ± 2.5 kJ /mol

[25].
This example shows that the free enthalpy can be calculated for every com-
pound with various difficulty levels depending on its structure. In the same way,
370 Chapter 9
free enthalpy values were calculated for the evaluation of various reaction possi-
bilities for asphaltenes.
From Figures 9.3 and 9.4, we can see that the cracking of the aromatic core
of asphaltenes can take place via the destruction of the bridge-ring system. This
cracking reaction is the reversible reaction of polycondensation (9.2) or (9.3). It
means that a gas will be used during this reaction. This gas can be hydrogen or
hydrocarbon. The reaction with hydrogen can be described by equation (9.9):
(9.9)
2 Ho
From Figure 9.7, it is evident that the destruction of the bridge-ring struc-
tures by hydrogenation of the cracked bond is thermodynamically possible only at
temperatures under approximately 25 °C. Studies [26] concerning the reaction of
asphaltenes and atomic hydrogen at low temperatures have been reported. It was
shown in the studies that the aromatic core of asphaltenes can be cracked and its
decomposition (of the aromatic core) proceeds especially extensively, if the reac-
tion occurs at a temperature below 0°C.
240
100 200 300 400 500

temperature [°C]
Fig. 9.7: Change of free enthalpy for reaction (e9.9).

This means that hydrogenation of asphaltenes cannot be responsible for

asphaltene cracking during the thermal treatment of bitumen and plastics at tem-
peratures over 400°C.
Another type of asphaltene cracking reaction is reaction with hydrocarbons.
Equations (9.10) and (9.11) can describe this type of reaction:
(9.10)
2C2H6
The use of hydrocarbons heavier than ethane requires a higher reaction

temperature (see Fig. 9.8).
(9-11)
1
From Figure 9.8, we see that only reactions with ethane and/or methyl radi-
cals are thermodynamically possible at temperatures over 300°C. All reactions
with heavier hydrocarbons or radicals are possible only at temperatures below
0°C.
Reaction (9.10) is thermodynamically possible. However, for the reaction to
proceed to a large extent, it is necessary that the methyl radical is produced on a
continuous basis with relatively high velocity. Ethane cracking at a temperature
under 500°C is thermodynamically not possible, i.e. reaction (9.10) proceeds only
very slowly with ethane. But during the common cracking of bitumen and plastics,
the methyl radical can form from cracked products of plastics and then enhance
deep asphaltene cracking. These reactions can be described by equation (9.12).
372 Chapter 9
150 -i
100
50
t 0
.c
•¥*
100 200 400 500
<D
<D -50
O>
-100
-150
temperature [°C]
Fig. 9.8: Change of free enthalpy. Solid: for reaction (9.10); doted: for reaction (9.11).
In this reaction example, the cracking products of polypropylene were used

as methyl radical donors.
(9.12)
-12
-13
1 -14
-16
-17
390 400 410 420 430 440 450 460
temperature [°C]
Fig. 9.9: Change of free enthalpy for reaction (9.12).
Figure 9.9 shows that reaction (9.12) is thermodynamically possible. In

other words, reactions such as represented by (9.12) are responsible for deep as-
phaltene cracking during the common cracking of bitumen and plastics.
Experiments with pure asphaltene structural compounds were carried out to
show the possibility and extent of asphaltene cracking via the bridged-ring struc-
tures. Flouren and dihydroanthracene were used for these experiments, since these
compounds have two different bridged-ring structures. Both experiments showed
that cracking of bridged-ring structures during the reaction of the model com-
pounds and polypropylene (PP) was possible and proceeded very extensively. One
example of the results for this investigation is presented in Figure 9.10.
From Figure 9.10, it is seen that during the thermal treatment of pure model
compounds, polycondensation is the only reaction that occurs. In contrast to this,
during the co-treatment of the model compound with polypropylene, the flouren is
decomposed. This decomposition reaction proceeds via the bridged-ring system,
because one-ring aromatic compounds were found in the reaction product in case
b) of Figure 9.10.
The aromaticity of the asphaltenes increased during their thermal treatment.
This increase proceeded via a dehydrogenation reaction, an example of which is
described by reaction (9.13):
374 Chapter 9
a)
T
b)
PP
Fig. 9.10: Sample reaction of the thermal treatment of

a) Pure flouren
b) Flouren with polypropylene
The change of free enthalpy for reaction (9.13) is presented in Figure 9.11.
10 n
-10
-30
-50
-70
-90
-110
-130
-150
0 100 200 300 400 500
temperature [°C]
Fig. 9.11: Change of free enthalpy for reaction (9.13).

From Figure 9.11, it is seen that dehydrogenation proceeds with a higher

probability at a higher temperature. Since the compounds with higher aromaticity
have a higher tendency towards coke formation, thermal treatment of bitumen or
vacuum residues has to be carried out at the lowest possible reaction temperature.
9.2.3 Hydrogen Transfer
This section discusses the possibility of deep cracking of bitumen or vacuum

residues at a low temperature.
The need for hydrogenation in the case of thermal treatment of VR is due to
the chemical instability and high tendency to coke formation of the resulting un-
saturated components [9]. During industrial thermal cracking, many alkenes are
formed which can be oxidized. The alkodienes have an especially strong predispo-
sition to oxidation reactions. Oxidized components of fuels can be polycondensed.
This leads to the formation of resins, which if precipitated can plug the pipes.
Hydrogenation can be achieved by utilization of hydrogen under high pres-
sure. This method is broadly used in modern industry. But nowadays, the use of
hydrogenation processes under hydrogen pressure is very expensive. As an alter-
native, hydrogenation can be carried out with hydrogen donors. All materials with
a H/Catomic ratio higher than 2 can be used as hydrogen donors in the thermal
treatment of oil residues [28]. This ratio is 2 for plastics such as polyethylene
and/or polypropylene, i.e. plastics may be used as hydrogen donors during the
thermal treatment of crude oil vacuum residues. The process of utilization of hy-
drogen donors makes the use of expensive hydrogen unnecessary. Also, it can be
carried out at a lower pressure than in any of the modern hydrogenation processes.
The present methods of using a hydrogen acceptor are intended to prove the
ability of the substance to be a hydrogen donor.
Shaw et al. [27] indicate that anthracene is more readily hydrogenated than
other aromatic systems (e.g. naphthalene). The hydrogenation of anthracene can
be described by the following equation (9.14):
(9-14)
After hydrogenation, the product is analyzed by GS-MS. By this method,
the ratios for dihydroanthracene/remaining anthracene as well as anthracene de-
rivatives/remaining anthracene were determined as 9 and 10, respectively. These
two values show the depth and chemical path for hydrogenation, i.e. from these
two values it can be proved which reaction (hydrogenation or alkylation) occurred
during hydrogen transfer provoked by the investigated hydrogen donor.
376 Chapter 9
The results of this investigation of hydrogen transfer are presented in table

9.3. The experiment with thermal treatment of pure anthracene (E.I) demonstrated
that a significant amount of dihydroanthracene was found in the used anthracene
after thermal treatment. Therefore, it is important to use this fact in the discussion
of the results. Experiment RE.3 is a reproducibility experiment in comparison with
E.3. It is evident that the experimental method has a good reproducibility (relative
divergence 4%).
Based on the results for runs E.2 and E.3, it is seen that hydrogenation only
has a small significance for hydrogen transfer during co-processing. Laux [3]
reported that at a temperature over 300°C, the equilibrium between hydrogenation
and dehydrogenation is displaced towards dehydrogenation because hydrogena-
tion is an exothermic reaction.
In contrast to hydrogenation, alkylation reactions proceed very extensively
(see table 9.3). In the case of plastic blends with polyethylene (PE) (E.3 anthra-
cene/PE/PP/PS blend), alkylation proceeds more extensively in comparison with
mixtures without PE (E.2 anthracene/PP/PS blend). This difference in depth of
alkylation can be explained by different reaction velocities of cracking during the
co-processing of mixtures with and without PE. At the same temperature, PE is
cracked more slowly. This implies that under the same conditions for the use of
PE, a larger amount of free radicals will stay in the liquid phase during the reac-
tion. Generally, alkylation has a reaction order of 2 or higher. Therefore, this reac-
tion is strongly accelerated by the transfer of the reaction zone from vapor to the
liquid phase.
Generally, it can be said that during co-processing, alkylation reactions are
responsible for the hydrogen transfer during the co-processing of bitumen and
plastics. Therefore, it is important to promote this reaction. It was shown that
alkylation proceeded more extensively if the reaction zone was located in the
liquid phase. This is why it is important to keep the hydrogen-rich radicals in the
liquid phase. Based on this information, the following recommendations can be
given for the reaction conditions during co-processing:
• Use plastics with small reaction velocity of cracking.

• The process can be carried out under high pressure.
• The vapor phase should permanently stay in contact with the liquid phase.
Table 9.3: Results of hydrogen transfer investigation.

Experiment number El E2 E3 RE3
Dihydroanthracene/anthracene
13 24 23 22
[mol/mol]*103
Anthracene derivatives/anthracene
0 43 112 113
[mol/mol] *10'
Additional experiments with bitumen/plastic blends have shown that at

optimum conditions, hydrogen transfer can proceed completely. This means that
no unsaturated components (alkene and/or alkadiene) will be found in the fuel
fractions (boiling point under 350°C) obtained from the co-processing product.
9.3 CO-PROCESSING WITH CRACKED PRODUCTS
The investigations of co-processing represent a special interest because

synergistic effects can take place during the joint treatment of VR and different
types of materials (plastics in our investigation). In this case, synergy is under-
stood as a positive divergence in the formation of lighter fractions. An example of
the synergy in the case of the co-processing of crude oil vacuum residue is shown
in Figure 9.12.
These synergy effects can be explained in two ways: by investigating the
process kinetics and by investigating the chemistry of the process. In our investi-
gation of the co-processing of blends of crude oil vacuum residue and plastics we
have used both methods. Data from thermo-gravimetric analysis were used for
study of the process kinetics. The dynamic method for reaction (9.15) was used for
the evaluation of the data.
Residue/PP Residue/PP Residue/PS Residue/PS

calculated real calculated real
Fig. 9.12: Synergy during the co-processing of blends of VR and PP and VR and PS:
pressure = 20 bar
reaction temperature = 425 °C
reaction time = 25 minutes
378 Chapter 9
-S+V = 0 (9.15)
S - substance
V - volatile product
In the reaction, the rate of disappearance of S may be expressed by equation

(9.16):
dX/dT= k0exp(-Ea/RT)( 1 -X)n/P (9.16)
X - conversion of S (0 < X < 1)

Ea - energy of activation
ko - frequency factor
8 - linear heating rate (20 and 10 deg./min)
The integrated form of the kinetic equation (9.17) or (9.18) is used for the
determination of kinetic parameters:
Thus, for reaction order n *1 :
0 a
10gl
° T*(1-n) - IOg »pi; ''I - (9.17)
and for the reaction order n = 1 :
(9.18)
loff
10glo
T22 PE Ea 2.3RT
These equations are solved graphically as in Figure 9.13 in which the left-hand
side of the integrated form of the kinetic equations is the ordinate and the term 1/T
is the abscissa. The graphical method involves the best approximation of the curve
to a straight line [28].
Fig. 9.13: Dynamic evaluation.
A model has been developed for the main reactions in an attempt to obtain a
better understanding of the kinetic data obtained for co-processing. The basic
principles of this model are:
• Co-processing is a process of thermal cracking of VR and plastic blends.
• Thermal cracking of organic material has a radical chain mechanism.
• The radical chain mechanism includes three phases as presented in Figure
9.14.
The first step (chain start) can be controlled either by a catalyst or change of
the reaction conditions (i.e., temperature and/or pressure). On the other hand,
however, the second step, chain growth, can be influenced by the input of more
radicals to the reaction zone. A material can be used as additive radicals if it can
be cracked at a higher reaction velocity than VR with all other conditions remain-
ing the same.
This reaction between plastic radicals and VR molecules has a theoretical
reaction order of 2 or higher during the formation of more complicated complexes.
This is higher than could be obtained from only one radical and one molecule.
This means that the increment of the reaction order during co-processing is evi-
dence of reactions between plastic radicals and VR molecules. The optimum con-
ditions for co-processing are in such ranges of pressure and temperature where the
co-cracking has the highest reaction order. On the other hand, recombination and
polycondensation reactions have a theoretical reaction order of 2 and higher, too.
But these reactions lead to the formation of heavy products that can be condensed
into the liquid phase again. This physical process leads to the reduction of the
reaction order [29].
380 Chapter 9
-> O
chain start chain growth chain termination
Fig. 9.14: Example of chain reaction.

Black - free radical
White - molecule
The reduction of the reaction order during co-processing shows that under
the selected reaction conditions, a large number of radicals stay in the reaction
zone leading to recombination and polycondensation reactions, which in turn lead
to the formation of heavy products. Therefore, cracking reactions and the activa-
tion of co-cracking is decelerated under these conditions.
We have used the method of molecular weight determination and monitor-
ing the molecular weight change during thermal processing to investigate the
chemistry of co-processing of blends of crude oil vacuum residue with different
types of plastics.
9.3.1 Co-Processing with Cracked Products from Aromatics Containing

Plastics (e.g. Polystyrene)
Polystyrene PS 168N was used in our investigation to study the influence of

aromatic containing plastics on the co-processing of mixtures of crude oil residue
and plastics.
The determined reaction orders for different pressures and various mixtures
of vacuum residue and polystyrene are shown in Figure 9.15. This example shows
that for vacuum residue/polystyrene mixtures, the optimum reaction condition is in
the range between 20-35 bar. In this pressure range, all investigated mixtures
showed a maximum reaction order, i.e. reactions with reaction order higher than 1
dominate. Alkylation reactions belong to this type of chemical process (i.e. with
high reaction order). Polycondensation also has a high theoretical reaction order,
but leads to the formation of heavy products, which can condense back to the
liquid product. This leads to smaller reaction orders [29]. During co-processing in
the pressure range above 30 bar (see Fig. 9.15), polycondensation reactions domi-
nate.
Our investigation has shown that polystyrene promotes the decomposition
reactions of asphaltenes (Figure 9.15). Remarkable is the fact that at a lower tem-
perature (400°C), the decrease in the asphaltenes' molecular weight (65%) is big-
ger than at the higher temperature (425°C, molecular weight decrease 44%). This
can be caused by the poor solubility of asphaltenes in maltenes; at higher tem-
peratures, more aromatic cracking products go to the vapor phase. On the other
hand, it can be caused by the tendency of aromatics to polycondensation reactions
(see chapter 1). We carried out experiments with vacuum residue/toluene blends in
order to prove whether asphaltene cracking is promoted by chemical activation or
by better solubility of asphaltenes in highly aromatic maltenes. Since toluene is a
thermally stable substance at the reaction temperature of 400°C, it can only influ-
ence co-processing by improved solubility of the asphaltenes in the maltenes. The
experiments with blends of VR/toluene (Figure 9.16) showed that a better solubil-
ity of asphaltenes in maltenes decelerated polycondenstion reactions and coke
formation, but this does not activate asphaltenes cracking. This means that the
solubility
3,5
2,5
0,5
0 5 10 15 20 25 30 35 40 45
pressure [bar]
-VR/PPZ=10wt.% •••••VR/PSZ=25wt.%
I]
Fig. 9.15: Graphical presentation of the reaction order as a function of pressure.

382 Chapter 9
of asphaitenes in maltene fraction influences polycondensation reactions and

shows no influence on the chemistry of asphaltene cracking.
The behavior of asphaitenes during thermal treatment of pure vacuum resi-
due (VR) is in absolute contrast to the co-processing of vacuum residue and poly-
styrene (Figure 9.16). At 400°C, the molecular weight of the asphaitenes decreases
and then increases. This reduction in the molecular weight can be explained by the
cracking of the paraffin periphery. This means that the decrease of about 30 wt.%
in the molecular weight has to be directly proportional to the content of paraffin
chains in the asphaltene molecule. The C-NMR analysis of native asphaitenes
showed that the portion of paraffin periphery in the asphaitenes was 28.66 wt.%.
After a 15 min residence time at 400°C, only the aromatic cores of native asphai-
tenes are present. The tendency of aromatic asphaltene cores towards polyconden-
sation reactions was reported in ref. 9. On account of this tendency, the increase in
molecular weight at a residence lime over 15 minutes can be explained by the
polycondensation of aromatic cores of asphaitenes. Thus, polycondensation reac-
tions affect coke formation. This is very obvious at 40 min residence time. In this
experiment, 1 wt.% coke (based on water free feed) was formed.
10 20 30 40 50
residence time [min]
Fig. 9.16: Influence of the asphaitenes' solubility in maltenes on the chemistry of as-
phaitenes cracking.
Constant parameters:
T = 400 °C
PNZcoid = 20 bar
additive concentration = 20 wt.%
9.3.2 Co-Processing with Cracked Products from Plastics Containing Paraf-

fin Groups
Polypropylene PP Novelen 1100H and polyethylene PE Lupolen LDPE

were used in our investigation for the study of the influence of the paraffin con-
taining plastics on the co-processing of mixtures of crude oil residue and plastics.
Determination of the kinetics of the co-processing of blends of vacuum
residue and paraffin containing plastics shows that the optimum pressure for the
cracking of these mixtures is the same as for the mixtures of vacuum residue and
polystyrene. Figure 9.17 shows the results of the determination of the activation
energies and frequency factors for VR and paraffin containing plastics. It is evi-
dent that PP has almost the same activation energy as VR and a higher frequency
factor than VR. Data obtained from the kinetic study for co-processing show that
the best results for co-processing (with regard to synergy) is obtained only if the
plastics and/or plastics blends used have approximately the same activation energy
but higher frequency factor than the vacuum residue. This means that PP is the
best additive to bitumen in the case of co-processing of vacuum residue-plastics
mixtures. In our last investigation on co-processing, we showed that the biggest
synergy occurs when mixtures of VR and PP or plastics blends with PP are used in
the process (Figure 9.12).
Polyethylene and polypropylene are especially interesting as additives for
the activation of the cracking reaction of vacuum residue. The data obtained from
thermo-gravimetric analysis of polyethylene and polypropylene show that vacuum
residue has its maximum cracking velocity at the temperature 456°C, polypropyl-
ene at 450°C and polyethylene at 485°C. This means that the cracking of vacuum
residue will only be activated if polypropylene is used. In the case of the thermal
treatment of vacuum residue and polyethylene mixtures, the cracking of polyeth-
ylene will be activated by free radicals from the vacuum residue (see above).
The investigation into the influence of paraffinic plastics on asphaltene
chemistry during thermal cracking showed that pure plastics affect only the equi-
librium of alkylation reactions by the increase of the paraffinic radicals in the
reaction zone (Figure 9.18). This means that asphaltene decomposition will be
slowed down. As such, there will be no decomposition to form aromatic cores
without paraffinic periphery. This decelerates polycondensation and coke forma-
tion during the thermal treatment of mixtures of vacuum residue and plastics.
However, it does not promote the cracking of the asphaltenes.
384 Chapter 9
10
15 20 25 30 35 40 45
pressure [bar]
-Ea, VR -—Ea, PE - — -Ea, PP -»-log(kO), VR —— log(kO), PE •••••• log(kO), PP
Fig. 9.17: Graphical representation of the kinetic parameters as a function of pressure.
10 15 20 25 30 35 40
resince time [min]
Fig. 9.18: Influence of paraffin containing plastics on the chemistry of asphaltene during
thermal cracking.
Constant parameters:
T = 425 °C, pN2cotd = 20 bar, additive concentration = 20 wt.%.
9.3.3 Possibilities that Exist for Carrying Out Co-Processing of Heavy Crude
Oils and Various Co-Feeds
The possibility of deep asphaltene cracking at a relatively low tempera-

ture was shown in Figure 9.16. This possibility was the base for further investi-
gation involving a new type of co-processing called stepped co-processing. The
logic in stepped co-processing is that the asphaltenes cracked during the first
step need a longer reaction time for polycondensation and formation of fine coke
than the native asphaltenes. Thus, vacuum residue can be co-treated with poly-
styrene during the first step and the product of the first step can be co-treated
with polyethylene or polypropylene during the second step. In that way, it is
possible to use the property of PS to activate asphaltene cracking at low tem-
peratures and the property of paraffinic plastics to improve the quality of the co-
processed products with regards to hydrogen transfer. The first results of inves-
tigations on stepped co-processing are shown in table 9.4.
Table 9.4: Comparison between a two-step and a one-step co-processing.
Two step co-processing One step co-processing

Conditions
1. Step Pressure: 30 bar 35 bar
Temperature: 400 °C 425 °C
Reaction time: 15 min 30 min
Plastic: Polystyrene Polyethylene (60 %)
Polypropylene (30 %)
Polystyrene (10 %)
Concentration: 15% 20%
2. Step Pressure: 37 bar
Temperature: 450 °C
Reaction time: 15 min
Plastic: Polyethylene (83.4 %)
Polypropylene(16.6 %)
Concentration: 20%
Results
Gas [wt%] 2.63 1.97
Maltenes [wt%] 81.76 64.02
1.<180°C [wt%] - 24.56
2. 180 -350 °C [wt%] -20.44
3. 350 - 500 °C [wt%] - 15.38
4. > 500 °C [wt%] 21.38
Hard resin [wt%] 0 18.59
Asphaltene [wt%] 12.41 4.87
Coke [wt%] 3.20 10.56
386 Chapter 9
The next possibility for very deep co-processing of crude oil residues and
plastics is one that also involves vacuum residue recovery. The main idea of this
method is shown in the schematic in Figure 9.19.
Fraction
Fraction <350°C
VR/R.
Fraction <350°C
Residue
VR/P^
Fractipn<350°C
Residue
Residue
Residue
Fig. 9.19: Co-processing of crude oil vacuum residue and plastics with recovery of the
vacuum residue, at 425°C, app. 30 bar, 15 min.
VR/P- mixture vacuum residue to PP/PS (5/1), 20 wt.% of plastics
1 - 4 - steps of experiment
The results of investigations of the co-processing with recovery of the vac-

uum residue that is recycled back to the process are shown in table 9.5.
Table 9.5: Results of investigation into the co-processing with vacuum residue
recovery.
Step of experiment / Product 1 2 3 4
Boiling temperature < 150°C [%] 8.40 9.30 9.00 9.120
Boiling temperature 150-350°C [%] 15.30 16.50 16.10 16.70
Boiling temperature > 350°C [%] 75.80 73.70 74.40 73.60
Coke [%] 0.00 0.00 0.00 0.50
From the table, it is obvious that the vacuum residue from co-processing can
be recovered back to the process. The results show that it is only after the third
usage that traces of coke (0.5 wt.%) were found. Such a method can strongly in-
crease the conversion of heavy crude oils and vacuum residues into the desired
light fractions.
It is not only plastics that can be used as co-feed for co-processing. Many
different organic co-feeds were investigated in our work. For example, investiga-
tion into co-processing of crude oil vacuum residue with used fat such as organic
co-feed has shown that the optimum conditions for the mixtures of vacuum resi-
due/used fat are similar to those for co-processing of crude oil vacuum residue
with plastics. In the case with bio-based co-feed, coke free co-processing was
achieved at the temperature of 425°C, pressure 20 bar, and reaction time of 15
minutes.
9.3.4 Behavior of Heavy Metals During Co-Processing
The heavy metals in crude oil residues are agglomerated mostly in asphalte-
nes in the form of porphyrin compounds. One example of this compound was
presented in Figure 8.2.
The investigation into the behavior of the heavy metals has shown that dur-
ing the co-processing of crude oil residue and plastics more heavy metals are
transferred from light fractions to coke and asphaltenes than in the case of thermal
treatment of pure crude oil residue. This shows that the fuel fractions from the co-
processing are ecologically better than visbreaking fuels. An example of these
results is shown in Figure 9.20.
9.3.5 Conclusions of Co-Processing of Crude Oil Residue and Co-Feed
1. Co-processing is marked by reactions between asphaltenes and free radicals,

resulting from the decomposition of plastics. For very deep asphaltene crack-
ing, the temperature range for formation of free radicals and those for asphal-
tene cracking have to be similar.
2. Under optimum conditions, it is possible to achieve deep cracking without
coke formation.
3. It is possible to execute step-wise co-processing. In that way, it is possible
to achieve a high yield of the desired products without coke formation.
4. Heavy metals are transferred into the heavy fractions or coke during co-
processing. It leads to the better ecological properties of co-processing
products in comparison to visbreaking products
5. It has been shown that co-processing with different organic co-feeds (for
example used fat) is possible.
388 Chapter 9
Fe Ni Fe Ni Fe Ni Fe Ni Fe Ni Fe Ni Fe Ni Fe Ni
VR VR/PE/PP/PS VR VR/PE/PP/PS VR VR/PE/PP/PS VR VR/PE/PP/PS
t [min] 0 0 15 15 30 30 40 40
T [°C] 425 425 425 425 425 425
P [bar] 20 20 20 20 20 20
Omaltene • resin Basphaltene • coke
Fig. 9.20: Graphical presentation of heavy metals transfer between vacuum residue frac-
tions during co-processing
9.4 INDUSTRIAL METHODS OF CRUDE OIL RESIDUE TREATMENT
This section deals with current industrial methods of residue treatment.
9.4.1 Fluid Catalytic Cracking
The main task of fluid catalytic cracking is the conversion of a wide range of
both virgin and cracked hydrocarbon residues into lower molecular weight and
more valuable products.
The main advantages of this process are:
• Selective conversion of different feedstocks to a variety of high quality prod-
ucts
• Production of high pressure steam from waste heat
• Cracking under low pressure conditions
• No hydrogen feed needed
Figure 9.21 shows an example of a fluid catalytic cracking unit. In its simple
form, the Fluid catalytic cracking unit consists of three sections:
feed
Fig. 9.21: Fluid Catalytic Cracking unit:

Re - regenerator
R - reactor
S - stripper
V - separator
• Reactor section
• Fractionation
• Gas concentration
The preheated raw oil feed meets a stream of hot catalyst from the regen-
erator at the base or lower part of the reactor riser. Heat from the catalyst vaporizes
the oil, and the catalyst and oil travel up to the reactor. The cracked hydrocarbons,
separated from the catalyst in cyclones, leave the reactor overhead and go to the
fractionation column.
The spent catalyst falls down into the stripping section within the reactor.
Steam removes most of the hydrocarbon vapor and the catalyst then flows down a
standpipe to the regenerator.
The spent catalyst mixes with air and clean catalyst at the base of the regen-
erator. Here the coke deposited during cracking is burned off to reactivate the
catalyst and provide heat for the endothermic cracking reactions. The recirculating
loop of clean catalyst provides added heat for initiation of the carbon burn. The
catalyst and air flow up the regenerator riser and separate at a T-shaped head. The
flue gas is further cleaned of catalyst in cyclones at the top of the regenerator.
390 Chapter 9
Waste heat from the flue gas is used for generation of high-pressure steam in the
waste heat boiler. The regenerated catalyst flows down a standpipe to meet the raw
oil charge at the bottom or lower part of the reactor riser, and the circulation con-
tinues.
The main column is the first step in the separation and recovery of cracked
hydrocarbon vapors from the reactor. Heavy naphtha and middle distillates are
withdrawn as side cuts, the bottom product is used as fuel oil or recycle stream.
In the gas concentration section the overhead products from the main col-
umn are further separated into fuel gas, butane-propane fraction and gasoline.
Typical fluid catalytic cracking processes are operated at a reaction tem-
perature of approximately 500°C and under a pressure of approximately 3 bar in
the reaction zone.
9.4.2 Hydrocracking
The main task of hydrocracking is the conversion and desulfurization of a

wide variety of hydrocarbon feedstock into more valuable products with lower
molecular weight. During hydrocracking, the following typical products are ob-
tained: butane-propane fraction, light olefins, light naphtha, naphtha, jet fuel,
diesel, lube oil base stocks, feed for fluid catalytic cracking.
The main advantages of this process are:
• Selective conversion of different feedstocks to a variety of high quality prod-
ucts
• Simultaneous removal of sulfur and nitrogen compounds
• Produced middle distillates are valuable blending compounds for the diesel
oil pool
Figure 9.22 shows an example of a hydrocracking unit.

In a single stage hydrocracker, untreated feed and hydrogen-rich gas is
charged to the first reactor, where hydrotreating reactions convert sulfur, nitrogen
and oxygen compounds. In advance, recycle gas and feed oil are preheated sepa-
rately. The effluent from the hydrotreating reactor passes directly to the. hy-
drocracking reactor, where 40 to 80% of the reactor charge is converted into prod-
ucts. Reactor temperature control in both reactors is done using quenching by
injecting cold recycled gas between the catalyst beds.
fuel gas
feed
Fig. 9.22: Hydrocracking unit:
O - oven
H - hydrotreating reactor
C - cracking reactor
V - high pressure separator
v - low pressure separator
S - stripper
The effluent from the cracking reactor is cooled and condensed. The liquid
products are separated from the recycled gas in the high-pressure separator. Recy-
cled gas is returned to the reactors while the liquid product is sent to the low-
pressure separator. Here, most of the dissolved gases are removed before product
fractionation in the fractionation section. Unconverted oil is usually recycled to the
reactors and cracked completely to lower-boiling products. However, if desired,
the recycled oil may be withdrawn (one-through operation) to produce feedstock
for FCC or ethylene plants.
For large plants, a second stage is added to the basic single-stage hy-
drocracker. This system permits the unconverted, first-stage oil to be processed in
a separate reactor. This configuration can also be used to achieve different product
yields and product qualities. Generally, about 40-70% of the total conversion takes
place in the second stage. Hydrocracking proceeds in the temperature range 370-
430°C and under a pressure of 160-180 bar.
392 Chapter 9
9.4.3 Coking
Coking is used for the conversion of crude oil vacuum residues and cracking
residues into coke and a clean liquid product with a high H/C ratio. Typical prod-
ucts of coking are: hydrocarbon gas, naphtha, gas oil, feed oil for downstream
processing and coke.
The main advantages of the coking process are:
• High temperature flash distillation of residue oil and simultaneous coking of
non-distillable asphaltenes in a unique mixing reactor
• High yields of oil product and lower yields of gas and coke compared to con-
ventional cokers or solvent deasphalters
• Rejection of pollutants like heavy metals, Conradson Carbon Residue, sulfur
and nitrogen
• Production of a demetalized product oil with 30-40% vacuum residue content
or with 0-5% vacuum residue content
• Autothermal heat supply
Figure 9.23 shows the scheme of the coking reactor.

The coker is based on rapid heat transfer from a fine-grained heat carrier to
the feedstock. The heat carrier is produced as coke in the process itself. The main
part of the coker is the blender. Here, the solid or liquid feedstock is thoroughly
mixed with the hot heat carrier and flash distilled at approximately 500-600°C.
Mixing is achieved almost instantaneously by two rotating screws within the re-
actor which engage and thereby clean each other and the reactor walls. It is a ma-
jor characteristic of the blender that highly effective radial mixing takes place with
very little axial back mixing. The blender thus operates like a plug flow reactor in
which all particles have nearly equal residence times. The ultra short vapor resi-
dence time in the blender is shorter by an order of magnitude compared to the
coke residence time and minimizes further secondary cracking of the vaporized
product oil while most of the undesired components remain in the non-distillable
asphaltenes and are rejected to the coke.
The coke product is deposited like onionskin on the circulating heat carrier.
The gaseous and vapor coker products are withdrawn from the blender, quenched
and then condensed in a fractionator. Nearly 100% residue conversion can be
achieved if the bottom condensate fraction is recycled to the blender at a suitable
process temperature. The heat carrier coke flows from the blender into the surge
bin, from where it is fed at a controlled rate through a seal leg to the lift pipe. In
the lift pipe the heat carrier is pneumatically elevated with hot air into the collect-
ing bin. The air rate is appropriately adjusted to ensure that the circulating coke is
reheated to the required temperature by partial combustion of some coke.
coke
air
Fig. 9.23: Coker:

1-lift
2 - collector
3 - blender
4 - reactor
A gas diverter in the collecting bin separates the heat carrier coke from the
off gas. The heat carrier collected is recycled at a controlled rate via another seal
leg back to the blender.
394 Chapter 9
The seal legs are pipes that are continuously kept filled with fine-grained
coke to act as a seal between the coking reactor, i.e. the blender and the combus-
tion reactor.
Coking process proceeds at a temperature ranging from 500 to 600°C.
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Appendix A:
Conversion Factors Important for
Crude Oil Chemists
INTERNATIONAL SCALE UNITS
Everybody knows the problem arising when using the international scale
units: one often finds formulas or product properties in which non-uniform scale
units are used. In this short appendix the most important scale units for the petro-
leum specialist from around the world are collected.
Temperature:
[°C] = 0.566 • [F] - 17.778
[°C] = [K]-273.15
[°C] = 0.566 • [Rankine] - 273.15
[°C]=1.25-[Reamur]
Pressure:
[atm]=101.325-[Pa]
[atm]= 1.013-[bar]
[atm] = 1033.3 • [cm-H2O]
[atm] = 76 • [cm-Hg]
[atm] = 406.796 • [inch-H2O(39.2°F)]
[atm] = 407.189 • [inch-H2O(60°F)]
[atm] = 29.921 • [inch-H2O(39.2°F)]
[atm] = 30.006 • [inch-H2O(60°F)]
Volume:
[m3] = 103 • [liter]
[m3] = 6.29 • [barrel(oil)]
[m3] = 8.386 • [barrel(US liquid)]
[m3] = 219.969 • [gallon(UK)]
397
398 Appendix A
[m3] = 227.021 • [gallon(US dry)]

[m3] = 264.172 • [gallon(US liquid)]
Energy:
[J] = 2.39 • [calorie]
[J] = [Wh] / 3600
Density:
[kg/m3] = 3.6 • 10"5 • [Ibm/inch3]
[kg/m3] = 8.345 • 10"3 • [Ibm/gallon]
Capacity:
[mill ton/year] = 2.066-10"3-[barrel/day]
Appendix B:
Glossary
In the following glossary, the most important terms used by crude oil chem-
ists have been collected and given brief explanations.
U
C-NMR Nuclear magnetic resonance. Analysis based on measurement
of spin of 13C atoms.
Additives Chemical compounds added to crude oil products in very small

amounts in order to improve their properties.
Alkane Saturated organic compounds of general chemical formula

CnHin+2, often called paraffin.
Alkene Unsaturated organic compounds of general chemical formula

CnH2n, often called olefm.
Alkylation Catalytic process to improve octane number of gasoline frac-

tions. Based on alkylation reactions with formation of iso-
alkanes with high a octane number.
Aromatics Organic compounds that include benzene in their structure.
Asphaltene Heaviest crude oil fraction produced by solution analysis, in-

soluble in paraffinic solvents and soluble in aromatic solvents.
Atomic absorp- Elemental analysis method based on Kirchhoff law. According

tion spectros- to this law, all atoms are able to absorb light quanta with the
copy same wavelength which they are able to emit.
Atomic emission Elemental analysis method based on Kirchhoff law. According

spectroscopy to this law, all atoms are able to absorb light quanta with the
399
400 Appendix B
same wavelength which they are able to emit.
Benzene Cyclic unsaturated organic compound of general formula C6H6.
Bitumen Crude oil product used in road and building construction. Also
see vacuum residue.
Bromine number Amount of bromine that reacts with sample in the determina-
tion of the number of unsaturated bonds.
Carbon residue Carbonaceous residue formed after evaporation and pyrolysis

of a petroleum product.
Catalyst Chemical compound that accelerates the rate of a chemical
reaction. However, the catalyst is not formed or consumed
during the reaction.
Catalyst deacti- Deactivation of catalyst by physically covering the active sites

vation or by physical blocking of the pores in the catalyst by coke.
Catalyst poi- Deactivation of the catalyst by chemical reaction the active

soning sites with compounds of the reaction mixture often with sulfur
or heavy metals.
Catalytic crack- Cracking of heavy crude oil fractions using catalysts such as
ing alumino-silicates in order to achieve deep conversion of heavy
hydrocarbons of crude oil.
Cetane number Measure of the ability of diesel fuel to self-ignition under pres-
sure.
Chromatography Separating method based on differential ability of compounds

in sample mixture to adsorb or absorb on an immobilized
phase.
Coagulation Analysis based on different solubility of different compounds

analysis or crude oil fractions in different solvents.
Coker Apparatus used for coking.
Coking Conversation process used for the conversion of crude oil vac-
uum residues and cracking residues into coke and a clean liquid
product with a high H/C ratio. Typical products of coking are:
hydrocarbon gas, naphtha, gas oil, feed oil for downstream
processing, and coke.
Glossary 401
Colorimetry Analysis method based on the ability of the substances to ab-

sorb a certain wavelengths of visible light.
Complexes Analysis method based on the formation of complexes of crude

formation analy- oil compounds with other substances.
sis method
Conradson Carbonaceous residue formed after evaporation and pyrolysis

Carbon Residue of a petroleum product.
Co-processing Process having as a feed a mixture of two or more compounds

with different derivation.
Cracking Process used for conversation of heavy hydrocarbons from

heavy crude oil fractions into light crude oil fractions.
Crude oil Often called petroleum. A complex mixture of hydrocarbons

that occur in the Earth in liquid, gaseous, or solid forms.
Crude oil refm- conversion of crude oil into useful products as fuels, oils, plas-
ing tics or chemicals.
Crude oil trap Natural subsurface reservoir of crude oil. The oil is always
accompanied by water and often by natural gas; all are con-
fined in porous rock, usually sedimentary rocks such as sands,
sandstones, arkoses, and fissured limestones.
Crystallization Analysis method based on the differential crystallization tern-

analysis perature of the compounds in the sample. This method is fre-
quently used for the fractionation of lubricating oil into frac-
tions by crude oil chemists.
Delayed coking Thermal cracking process used in refineries to upgrade and

convert crude oil residue into liquid and gas product streams
leaving behind a solid concentrated carbon material, coke.
Density Mass of sample occupying a certain volume.
Diesel Mixture of flammable liquid hydrocarbons derived from crude

oil and products of their treatment and used as fuel for internal-
combustion engines. The boiling points of these heavier distil-
lates range from 180 to 350°C.
Diesel engine Internal-combustion engine in which air is compressed to a

402 Appendix B
temperature sufficiently high to ignite fuel injected into the

cylinder, where combustion and expansion actuate a piston.
Invented by German thermal engineer Rudolf Diesel
Distillation Process involving the conversion of a liquid into vapor that is

subsequently condensed back to liquid form.
Enthalpy The sum of the internal energies of all the compounds of a

thermodynamic system at certain pressure and in a certain
volume.
Entropy The measure of a system's energy that is unavailable for work.

Measure for chaos of a thermodynamic system.
Extraction Separation method based on the different solubilities of the

compounds of analyzing sample in solvents.
Fluoremetry Analysis method often called fluorescence and phosphores-

cence. Based on the ability of some substances to emit light
with a certain wavelength.
Fluorescence See fluoremetry.
Free energy See Gibbs energy.
Free enthalpy See Gibbs energy.
Friction Force that resists the sliding or rolling of one solid object over
another.
Gas chromatog- Analysis method using the principles of chromatography for

raphy samples in the gaseous or vapor state.
Gasoline Mixture of volatile, flammable liquid hydrocarbons derived

from crude oil and products of their treatment and used as fuel
for internal-combustion engines. It is also used as a solvent for
oils and fats in the petrochemical industry. Boiling temperature
of gasoline: boiling usually begins at 180°C.
Gasoline engine Internal-combustion engines that generate power by burning a

gasoline with ignition initiated by an electric spark.
Gibbs energy Full energy of a thermodynamic system including enthalpy and

entropy.
Glossary 403
Goudron See vacuum residue.
HPLC High Pressure Liquid Chromatography. Analysis method for

samples in liquid state. Used for Analysis of heavy crude oil
fractions.
Hydrocracking Type of catalytic cracking carried out under high pressure and
in a hydrogen atmosphere.
Hydroprocessing See hydrotreatment.
Hydrotreatment Catalytic process used to saturate unsaturated compounds in

crude oil products or to remove heteroatoms from crude oil
fractions. Process carried out under a hydrogen atmosphere.
Infrared spec- Analysis method based on the ability of substances to absorb

troscopy certain wavelengths of infrared light.
Iodine number Amount of iodine that reacts with sample in the determination
of the number of unsaturated bonds.
Isomerization Catalytic process to improve the octane number of gasoline

fractions. Based on isomerization reactions of n-alkanes.
Jet fuel Often called kerosene. A mixture of flammable liquid hydro-

carbons derived from crude oil and used as fuel for jet engines.
Boiling temperature of jet fuel is usually 200°C - 250°C.
Kerosene See Jet fuel.
Liquefied gas Liquefied under pressure. Mixtures of gaseous hydrocarbons

such as propene, propane, butene, and butane.
Liquid chroma- Analysis method used for characterization of crude oil products
tography based on the differential adsorption ability of the product com-
ponents on an adsorbent.
Lubricant Amorphous substance, stable colloidal mixture of lubricating

oil with solid substances, used for lubrication.
Lubrication Introduction of any of various substances between sliding sur-

faces to reduce wear and friction.
Lubrication oil Oil derived from petroleum or having synthetic nature, used for
404 Appendix B
lubrication.
Maltene Crude oil fraction produced by solution analysis, soluble in

paraffmic solvents.
Microcarbon The carbonaceous type residue remaining after sample pyroly-

residue sis at 500°C under an inert (nitrogen) atmosphere in a con-
trolled manner for a specific time. ASTM D4530.
Molecular dis- Analysis method based on the principles of distillation under

tillation very low pressures. Usually the pressure for this analysis
varies from 0.133 Pa up to 0.013 Pa.
Naphthene Organic compounds including cyclic structures as, for example,

cyclo-heptane.
Octane number Measure of the ability of gasoline to resist knocking when

ignited in a mixture with air in the cylinder of an internal-
combustion engine. There are Research Octane Number (RON)
and Motor Octane Number (MON). RON is usually 10 points
higher than MON for the same gasoline.
Olefm See Alkene.
OPEC Organization of Petroleum Exporting Countries.
Paraffin See Alkane.
Permeation Analysis method used for the determination of molecular

chromatography weight distribution of compounds in a sample mixture.
Petroleum See Crude oil.
Phosphorescence See Fluoremetry.
Photometry Analysis method based on the ability of a substance to absorb

certain wavelengths of electromagnetic radiation.
Platforming Reforming using platinum containing catalyst.
Promoter Chemical compound that improves the influence of a catalyst

on a chemical reaction.
Raman spectres- Analysis method based on the interactions of monochromatic

Glossary 405
copy infrared radiation with the shell of the atom.
Ramsbottom Carbonaceous residue formed after evaporation and pyrolysis

Carbon Residue of a petroleum product. ASTM D524.
Rectification Stepwise distillation, used for fractionating crude oil into frac-
tions. There are in existence rectification under atmosphere
pressure and under vacuum. The first is used for producing
fractions with boiling point up to 350°C. The second is used for
producing fractions with boiling point up to 550°C.
Reforming Catalytic process used to improve octane number of gasoline

fractions. Based on cyclization and aromatization reactions.
Residual fuels Fuel having boiling point over 350°C.
Sedimentation Analysis method that uses the sedimentation principle for de-
analysis termination of colloidal properties of sample.
Selectivity Property of catalyst to accelerate only the desired reaction.

Property of solvent to solve the compounds with certain prop-
erties.
Solution analysis Analysis based on the differential solubility of different com-

pounds or crude oil fractions in different solvents.
Thermal crack- Thermal splitting process of heavy crude oil fraction under
ing influence of high temperature. Proceeds according to the free
radical chain mechanism.
Thermal diffu- Analysis method based on separation of compounds in the

sion sample depending on the differential diffusion velocity for
different compounds when to the same temperature gradient.
Thin layer Qualitative analysis method that uses the principles of chro-
chromatography matography for substances in the dissolved state.
Ultimate analy- Determination of carbon, hydrogen and nitrogen content in the

sis sample.
Vacuum residue Bottom product of vacuum rectification. Often called bitumen

or goudron.
Vapor pressure Analysis method used for determination of average molecular

406 Appendix B
osmometry weight of the sample.
Visbreaking Thermal cracking process at moderate conditions used to re-

duce viscosity of residual fuels.
Viscosity Measure for cohesion.
Wear The removal of material from a solid surface as a result of

mechanical action exerted by another solid.
X-Ray fluores- Analysis method based on the ability of some substances to

cence spectres- emit light of a certain wavelength under the influence of X-
copy rays.
Index
Asphalt, 3 for colloidal properties, 153-157

Asphaltenes: evaporative, 146, 147 (see also
change in structure during processing Crude oil distillation and
of, 360-367 rectification)
chemistry of, 327-328 extractive, 147
in crude oil, 327 n-d-M method, 150-153
in crude oil residue, 327 thermal diffusion, 147-148
coke formation, reactions of, 327-331 for unsaturated compounds, 149-150
definition of, 9, 327, 342 physical properties of:
reactions of: density, 157-159
during co-processing, 360-367 refractive index, 161-163
during secondary treatment, 327-342 viscosity, 159-161
products from, 39-57
Biodiesel, transesterification, 55 prospecting of, 20-23
Crude oil distillation:
Cetane number, 49-51 atmospheric rectification, 235-251
Chromatography: packed towers in, 242-243
in crude oil chemistry, 73 rectification towers in, 236
gas, 74-95 reflux, 238-239, 244-247
anomalies in, 92-93 tray towers for, 237-240
carrier gases for, 93-94 heat exchangers in, 256-259
columns used for, 76-80 petroleum and gas preparation for, 221-
detectors for, 80-90 234
injectors for, 90-91 desalting, 234-235
liquid: petroleum drying, 227-230
adsorption, 100-101 petroleum emulsions, 222-224
affinity, 100, 102 separation of water-oil emulsions,
columns used for, 99-102 224-230
detectors in, 102-105 stabilization of petroleum, 230-231
distribution, 100-101 technological scheme for, 231 -234
gel permeation, 100-102 vacuum rectification, 251 -256
high performance, 97-107 Crude oil residue:
ion-pair, 100, 102 ash content in, 342
thin layer, 107-112 asphaltenes in,
Crude oil: co-processing of:
consequences of intensive extraction with aromatics containing plastics,
and processing of, 26-33 380-382
extraction of, 23-26 behavior of heavy metals during, 387
methods for characterization and with cracked products, 377-380
analysis of, 73-163 hydrogen transfer in, 375-377
adsorptive, 146-147 with paraffin containing plastics,
chemical analysis, 149-153 383-384
407
408 Index
with plastics, 360-367 Heavy crude oil (see Crude oil residue)
possibilities with various co-feeds, Hydrocarbons:
385-387 aromatics, 9
thermodynamics of, 368-375 asphaltenene and resins, 9
and heavy crude oil: naphthenes, 7
asphaltenes from visbreaking, 365 paraffins, 6
native asphaltene, 327, 365
problems caused by asphaltenes in, Jet fuel, 48-49
328-329
treatment of, 328 Lubricating oils and lubricants, 59-65
industrial treatment methods of: international standards for, 66-72
coking, 392-394 properties of, 65-66
fluid catalytic cracking, 388-390
hydrocracking, 390-391 Octane number, 40-42
methods of analysis of: Oil formation in world's oceans, 16-18
chromatography, 350-351 OPEC, 173
I3
C-NMR, 351-352 background on, 174
coagulation, 346-349 members of, 174
coke forming tendency, 342-
distillation, 349-350 Paraffins:
molecular weight determination, 354- associated, 6-7
358 iso-, 6
solution, 343-346 light, 5
ultimate, 353-354 molecular, 6
treatment possibilities for: normal-, 6
catalytic, 337-340 Petroleum:
chemical, 333-342 bitumen, 3
physical, 331-333 black, 3
thermal, 333-337, 340-342 classification of:
chemical, 35-37
Diesel, 49-55 by density, 37-38
Drilling, 23 technological, 39
by viscosity-gravity constant, 38-39
Environmental issues, 303-304 composition of, 5
for crude oil: compounds in:
cleaning contaminated soil, 303-306 aromatics, 9
cleaning contaminated water, 306- asphaltenes and resins, 9-10
309 metallic compounds or ash, 13
consequences of intensive extraction, metals, 13
26-32 naphthenes, 7-9
gas cleaning, 309-318 nitrogen compounds, 10-12
in the refining industry, 303-304 oxygen compounds
paraffins, 6-7
Fuels, international standards for, 58 sulfur compounds, 12-13
formation of:
Gasoline, 40-48 modern concept of, 18-26
average composition of, 45 in world's oceans, 16-18
characteristics of, 43-44 history and nature of, 3-13
Index 409
international companies: feed for, 287, 289-291

British petroleum, 197-200 function of, 287
Castrol, 200-201 of hydrocarbons, 287-289
ExxonMobil, 201-206 of nitrogen compounds, 287-288
LUKoil,214-215 of oxygen compounds, 287-288
Shell, 206-208 of sulfur compounds, 287-288
TNK, 216-217 isomerization:
Total/Fina/Elf, 208-214 catalysts for, 296-297
YUKOS, 215-216 feed for, 297
origin of, 13-16 function of, 296
producing countries, 173-195 reactions in, 297
Arabian East, 185-195 primary processes, 221 -260
Canada, 178 reforming:
OPEC, 173-175 catalysts for, 293
Russia, 178-185 feed for, 294
United States, 175-178 function of, 292
product fractions of, 33-35 reactions in, 293
white, 3 types of, 294
Petroleum treatment: secondary processes:
alkylation: bimolecular reaction, 264
catalysts for, 298-300 elementary reaction, 264
feed for, 298 monomolecular reaction, 264
function of, 298 reaction kinetics of, 263-275
reactions in, 298-299 termolecular reaction, 264
types of, 299-301 thermodynamics of, 261 -274
blending, 301-302 thermal cracking, 261-275, 333-337
catalytic cracking: visbreaking, 285, 334-335
catalysts for, 282
feed for, 275 Refinery processes, 40
functions of, 283
types of, 283-285 Spectroscopy:
catalytic processes, 276-282 atomic absorption, 139-143
coke formation reactions: atomic emission, 143-144
.catalytic, 337-340 colorimetry and photometry, 131-136
thermal, 340-342 in crude oil analysis, 126, 130, 136, 139
coking, 285-287, 335-337 143-144, 146
delayed, 335-337 infrared, 112-126
feed for, 336-337 fluorescence and phosphorescence, 136-
fluid, 336-337 - 139
types of, 335-337 NMR, 351-352
hydroprocessing: Raman, 127-131
catalyst deactivation in, 291 X-ray fluorescence, 144-146
catalysts for, 289

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Crude Oil

MARCEL DEKKER, INC. NEW YORK • BASEL

Trademark notice: Product or corporate names may be trademarks or registered trademarks

Library of Congress Cataloging-in-Publication Data

This book is printed on acid-free paper.

Distribution and Customer Service

Eastern Hemisphere Distribution

World Wide Web

Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved.

Current printing (last digit):

PRINTED IN THE UNITED STATES OF AMERICA

1 Nature and Classification of Crude Oil 3

1. History and nature of petroleum 3

2 Modern Characterization and Analysis Techniques for Crude Oil 73

2.2.2 Raman spectroscopy 127

Part II Regional Petroleum Industry 171

4 International Petroleum Companies 197

Part III Main Processes in the Petroleum Refining Industry 219

6 Processing of Light and Heavy Distillates 261

7 Environmental Issues Facing the Refining Industry 303

Part IV Heavy Oil Processing - Chemistry of Asphaltenes 325

9 Processing of Heavy Crude Oils and Crude Oil Residues 359

paraffin groups 383

In this part of the book, fundamental chemical information of interest to

1.1 HISTORY AND NATURE OF PETROLEUM

It may sound strange but petroleum refers to a mountain mineral. It

Tetracyclic naphthenic compounds are mainly isomers and substituted

The most important compounds of the class of pentacyclic naphthenes are

Special properties of asphaltenes include the tendency to associate, high

Fig. 1.1: The structure of porphine basic structural unit of porphyrins.

The above are some examples of nitrogen compounds in crude oil. It is

captans) or convert them to odorless disulfides. The amount of sulfur in petroleum

1.1.1 Origin of Petroleum

CaCO3 -> CaC2 + H2O -» C2H2

1.1.2 Oil Formation in the World's Oceans

Fig. 1.2: Anticline traps.

Fig. 1.4: Oil entrapment in a limestone reef.

1.1.3 Modern Concept of Formation of Petroleum

The characteristic feature of the modern concept of petroleum formation is

correct understanding of the genesis of hydrocarbons, they can predict what is

1.1.3.1 Crude oil prospecting

only enable us to evaluate the structure of the surface complexes of mountain

The gravimetric method is based on investigating the distribution of the

1.1.3.2 Drilling and crude oil extraction

Fig. 1.5: Example of drilling tower.

Fig. 1.6 Example of pumping extraction.

A special problem in crude oil extraction arises if high viscous petroleum or

1.1.4 Consequences of Intensive Extraction and Processing of Oil |6-8]

Initially, the adverse effects of intensive petroleum extraction were not of

An earthquake was registered in April, 1989 in Tataria with an intensity up

1.1.4.1 Dangerous fogs

Old monuments also suffer due specifically to atmospheric pollution. For

As a protective measure, the University of Kentucky (USA) has designed a

1.1.4.2 Black oceans

From 2 to 10 million tons of petroleum is released annually into the world's

1.2 GENERAL PROPERTIES AND CLASSIFICATION OF

1.2.1 Fractions and Chemical Composition of Petroleum

Petroleum is a complex mixture of various organic compounds. It consists

• Boiling begins -140°C - gasoline fraction

• 180-240°C - kerosene fraction