Crude Oil Chemistry

Vasily Simanzhenkov
University Duisburg-Essen
Duisburg, Germany

Raphael Idem
University of Regina
Regina, Saskatchewan, Canada

MARCEL DEKKER, INC. NEW YORK • BASEL

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 Preface

This book is devoted to students as well as scientists and process engineers involved 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 energy used to run most of
today’s machinery derives from petroleum. It also provokes our imagination on how the
various moving parts of machinery would operate 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 properties gives rise to the use of
very many analytical methods in the petroleum industry.
Part II (i.e. chapters 3 and 4) shows the geopolitical and economic nature of petroleum
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 important processes used in modern
petroleum refineries for processing light and heavy distillate fractions. Chapter 7 in Part
III looks at ecological problems that 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 industry.
 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 increasing
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 answered in Part IV of this
book. The chapter also introduces the presence of asphaltenes in crude oil. A list of
problems that occur during oil production, transportation, 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
engineering. 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

iii
Preface

1
Part I Classification and Characterization of Crude Oil
1 Nature and Classification of Crude Oil 3

2 Modern Characterization and Analysis Techniques for Crude Oil 67

161
Part II Regional Petroleum Industry
3 Petroleum Producing Countries: OPEC and Non-OPEC 163

4 International Petroleum Companies 184

203
Part III Main Processes in the Petroleum Refining Industry
5 Crude Oil Distillation 205

6 Processing of Light and Heavy Distillates 242

7 Environmental Issues Facing the Refining Industry 281

301
Part IV Heavy Oil Processing—Chemistry of Asphaltenes
8 Chemistry of Crude Oil Asphaltenes 303

9 Processing of Heavy Crude Oils and Crude Oil Residues 334

Appendix A: Conversion Factors Important for Crude Oil Chemists 370

Appendix B: Glossary 371
Index 376
 Part I
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 12 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 Egyptians 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 construction 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
waterresistant medium for the construction of most of the ancient dams on Ephrata 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 construction. 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 considerably 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 explosion 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 Arabian 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 elemental 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 sometimes 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 atoms. 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 branchedchain (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), hydrogen 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 (pressures ranging from 25
to 45 MPa), these high molecular weight compounds dissolve the gas. Initially during oil
production from gas condensate wells, pressure 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,
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 C1 to C78 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 C7 to C14. Lighter or heavier paraffins are present in crude oil in smaller amounts or
as trace compounds.
All types of paraffins (i.e. n-paraffins and iso-paraffins) are present in crude oil The
methyl-substituted paraffins were analytically proven to be present 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 C20H42 and pristane C19H40 (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 C5 till C17 are
liquids, and from C18 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 paraffinic 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 paraffinic 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 ( ) 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 geometrical 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 temperature; the higher the
temperature, the less the fraction of associated paraffins in crude oil.
Usually paraffins are less prone to most known industrial reactions. The most
important industrial reactions of paraffins are oxidation, catalytic isomerization 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 compounds in heavy oils.
The distribution of monocyclic naphthenes is well investigated at the moment in
comparison to polycyclic naphthenes. Monocyclic naphthenic compounds are distributed
mainly in the light fractions of crude oil. So, naphthenic hydrocarbons 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 tricyclic and
four tetra- 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 naphthenic crude
oil. The following bicyclic naphthenic compounds were observed in different crude oils:
bicyclo[3,3,0]octane, bicyclo[3,2,1]octane, bicyclo[2,2,2]octane, bicyclo[4,3,0]nonane,
bicyclo[2,2,1]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 analytically
identified.

Tetracyclic naphthenic compounds are mainly isomers and substituted

cyclopentanperhydrophenanthrene (C27–C30). Examples are presented as compounds d),
e) and f).

The most important compounds of the class of pentacyclic naphthenes are represented by
gopan (g), lupan (h) and phridelan (i).
There are no analytical proofs for the exact structure of polycyclic naphthenic 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 polycyclic 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 aromatics 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. Asphaltenes are the most
complicated known compounds in crude oil.
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 studies 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 hemoglobin 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.

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 compounds can be classified as alkaline (lye) nitrogen and neutral
nitrogen compounds.
Pyridines (a), hinolines (b) and acredines (c) belong to the strong alkaline (lye)
nitrogen, because of their free, non-compensated electron pair.

The substituted anilines (d), amides and/or imides belong to the weak alkaline (lye)
nitrogen compounds.

The non-substituted compounds such as indols (e) or carbozoles (f) are typical nitrogen
neutral compounds.

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 surfactants. 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 during the production of crude oil
from the oil well. For example, hinoline can prevent 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 compounds. 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 of the fraction. Over
20% of all oxygen compounds are concentrated in asphaltenes and resins.
Almost similar to nitrogen compounds, the oxygen compounds can be classified 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), thiophenes (d),
benzothiophenes (e), alkylbenzothiophenes (f), etc., or as elemental sulfur.
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 contributor to corrosion in
refinery processing units. Other corrosive sulfur materials are elemental sulfur and
mercaptans. Pyrophoric iron sulfide results from the corrosive action of sulfur
compounds on the iron and steel materials used in refinery process equipment, piping and
tanks. The combustion of petroleum products containing sulfur compounds results in the
production of undesirable by-products such as sulfuric acid and sulfur dioxide. Catalytic
hydrotreating processes such as hydrodesulfurization 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 fractions, 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 metals 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. However, these
compounds can be produced during the thermal or/and catalytic treatment of the crude
oil. These compounds differ from all crude oil compounds 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 compounds such as
compounds of iron, nickel and vanadium as well as various salts.
Petroleum is also characterized by physical properties such as density, viscosity,
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 connection 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 “eruptions” 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 underground with heat, prepared
from stone coal and brown coal, this black oily material 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 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 petroleum 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 nineteenth 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 experiments were performed by evaporation of
fish fat at 400°C and 1 bar. Oil, combustible 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 saturated hydrocarbons (ranging from pentane to nonane), paraffin,
lubricant oils as well as olefins and aromatic hydrocarbons. Later, a Russian scientist
(N.D.Zelinskiy) carried out a similar experiment in 1919. However, his initial material
was organic silt of mainly vegetative origin from Lake Balhash. The evaporation
products 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 inorganic 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 temperature and pressure according to the following:

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 planets showed that, there are hydrocarbon
compounds in the atmosphere of Jupiter and other large planets as well as in gas
environments of comets. If hydrocarbons 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, Kudryavzev 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 kilometers, 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. Nevertheless, 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 formation 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.
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 significant 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 quantities of organic material dissolved
per m3 of water are 2 g in the Atlantic and Pacific 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 structurally 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 gravity. Shallow conditions are the preferable places for accumulation of organic
material. 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 dispersed in the water due
to the activity of bacteria. Consequently, only 1% of organic 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”. Bitumoid 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 proportion 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 70–80×1012 ton.
This exceeds the established volume of hydrocarbons in oil fields (about 2.2×1012 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 reserves.
 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 water 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
minerals [3].

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.
 Fig. 1.3: Traps associated with a salt dome.

Fig. 1.4: Oil entrapment in a limestone reef.

Detailed discussions on oil and gas formation and modern methods of investigation 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, “lithosphere-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 of forces 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 failures or “rifts”. These were then transformed into the ocean.
Today, typical continental 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 lithosphereplates, the friction involved
generates a considerable amount of heat that results in increasing the temperature of the
zone by hundreds of degrees. This process promotes 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 Pacific Ocean and on the eastern part of the Indian Ocean.
These processes are accompanied 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
various 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
transformation 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 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 terrestrial 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 connected with postponing salt formation within the deep thermal water.
Normal sea minerals are collected during the process of rift formation as well as its
transformations 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 minerals 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 subduction, but the
result of these processes is the same: the acceleration of the transformation 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
rnaterial 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 geological 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 prospecting 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 density 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 different densities), another fraction of seismic waves continues
movement but refracted deeper through layers up to a new border between terrestrial
layers. Reflected 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 seismic crude oil
prospecting, other methods, including the method of controlled directed 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 obsolete for
geophysicists. Since the 1960s, first in the US and now worldwide, non-explosive
methods have been used for generating seismic waves. The most popular 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.
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 mountain 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 anomaly 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 gravitational 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 natural 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 minerals 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, lumenescic, 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 displaced from a source upwards of the layers.
The lumenescic method is based on an investigation of the bitumen dispersion 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 investigated using ultra-violet light.
The radioactive photography method is based on investigation of distribution of
radioactive elements (first of all uranium) above petroleum and gas deposits. 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 studied. A large
amount of hydrocarbons in the underground water shows a high possibility 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 principle. 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 borehole usually has a diameter of 10 to 70 cm.
The borehole begins with the largest diameter at the surface and then decreases with
depth.

Fig. 1.5: Example of drilling tower.

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.
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 (approximately between 2500 and 3500 meters).
3. Pumping extraction. Pumping is the most frequently used artificial extraction 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.
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 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 boreholes 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 petroleum) is carried out cyclically, with each cycle consisting of three
stages.
 Fig. 1.6 Example of pumping extraction.

In the first stage, the introduction of the heat-medium is conducted simultaneously

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 boreholes 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 borehole, 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 compared 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 observed 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 registered 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 problem 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 surface 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 character 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 epicenter 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.
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 earthquakes. 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 measure 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 oxygen whereas the content of carbon oxides has
increased by 12%. Annually, mankind 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 adverse
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 CO2 allow short wave
solar radiation to penetrate the atmosphere of the Earth and retain infrared radiation
which penetrates into the terrestrial surface. This gives rise to the so-called greenhouse
effect, resulting in an increase in the average temperature 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 atmosphere 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 released 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 radiation has fallen by 1.3% since 1964. This is
equivalent to the loss of approximately 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 atmosphere—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 hydrocarbons with oxygen. A high
concentration of ozone is more poisonous than charcoal 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, machines 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 worldwide total is already more than 500
million, pollute the atmosphere very significantly. 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 environment 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 aftermath 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.
Old monuments also suffer due specifically to atmospheric pollution. For example, the
Athenian Acropolis, which had already seen 2,500 destructive earthquakes and fires, is
today being threatened by another danger—atmospheric pollution. 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 plastic.
Atmospheric pollution resulting from the release of various harmful gases and solid
particulates has the result that the air in large cities has become unsuitable 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 registered 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 allowable 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 allowable 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 petroleum 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. Approximately 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 of ten 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” carrying 33
thousand tons of petroleum as it was navigating its way from Peru to Colombia. The
vessel sank and the petroleum content poured into the sea. The seamen 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 irreparable 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 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 petroleum 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 petroleum 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 William was declared “a zone of disaster”. The
US Navy was involved with the cleanup. Nevertheless, there was the “potential for
ecological disaster” with consequences 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 km2.
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 California, 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 impossibly 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
• 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 depending on the intended
application:
For further processing to fuel fractions:
• 350–500°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 fractions”. 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 (Canada) 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 following fractions:
• Gasoline and naphtha—2.8%
• Kerosene—0%
• Diesel—19.0%
• Light oil—4.3%
• Medium oil—8.5%
• Heavy oil fraction—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 paraffinic nature of the constituent
fractions whereas a high asphaltic content corresponds with the naphthenic properties of
the fractions. This could lead to the misconception that paraffin-base petroleum consists
mainly of paraffins and that asphalt-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-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
parafins and paraffinic if it contained more than 5%. A division according 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 compounds 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 described 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:

(1.2)

where T, in the case of a petroleum fraction, is the average boiling point, determined 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
Naphthemc 15–26 61–76 8–13 trace 0–6
–6'
Paraffinic-naphthenic- 27–35 36–47 26–33 0.5–1 0–10
aromatic
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 predominance of either
naphthenes or mixtures of paraffins, naphthenes, and aromatics; values above 50 indicate
a predominant aromatic character. Although the correlation 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 approximately 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 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 distillation.
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 boiling up to 145°C as
well as that of the asphaltene content, followed by more detailed 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 paraffin-
naphthene ratio.

1.2.4
Characterization by Viscosity-Gravity Constant (vgc)
This parameter, along with the Universal Oil Products (UOP) characterization 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

(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 lubricating 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

(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 originally 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 gasoline
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 paraffins. 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-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 processed 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 represented by fuel
fractions compounded from the products of many different processes.
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 distillate from petroleum. On the
other hand, automotive engines became vastly improved 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 hydrocracking), 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 decreased, octane number initially decreased as well, but vapor pressures
continued to increase while sulfur and olefins remained constant. The aromatic content
increased. 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 continue 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 countries 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 between 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 burn in air with a clean flame.
• The octane number depends on branching and number of carbon atoms. Generally
octane number is low for n-alkanes and high for the iso-alkanes (isooctane 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, naphthalene, 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 formation 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 gasoline 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 oxygenate’s octane
number and volatility properties. If the hydrocarbon fraction is not correctly modified,
oxygenates can even increase smog-forming and toxic emissions 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 hydrocarbons emissions during
combustion. Oxygenates cause engines without sophisticated 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, unfortunately, 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 oxygetiates
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 separate 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 octane numbers.
The main characteristics of gasoline are:
• Vapor pressure and distillation classes. There are six different classes according 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. Distillation 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 protection. 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.
• 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 actual 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 sample 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, tetra ethyl lead was added to the gasoline to improve the octane
number.
Tetra 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 C2H5. 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 impossible. 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, alkylhalogens 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.

15% 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% olefins
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

Adding tetra ethyl lead appeared to be quite an effective method to improve

antidetonating properties of gasoline. The additive added in a very small amount in
gasoline allows the increase of the octane number by about 5–10 units. Unfortunately
however, lead and tetra ethyl lead are very poisonous substances. If contacted with the
skin, they can filter into the blood. The lead compounds 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 alcohol 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 mention
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 pressure specifications. The higher boiling fractions of the
gasoline have significant effects on the emission levels of undesirable compounds
(hydrocarbons and oxygen containing compounds), and a reduction of 40°C in the end
boiling point will reduce the levels of benzene, butadiene, formaldehyde and
acetaldehyde by 25%, and will also reduce hydrocarbons emissions.
• Combustion Characteristics. Gasoline contains a wide variety of hydrocarbons. 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 temperature 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 affects the alkyl lead octane
response. Furthermore, it adversely affects the exhaust 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 sulfur present.
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 gasoline 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 A1), 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 A1), low freezing
point for high altitude flying ( 47°C for Jet A1), 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 substantial refining
and hydrotreatment Kerosene is a very stable product, and additives are not required to
improve the quality. Apart from the removal of excessive quantities of aromatics,
kerosene fractions may need only hydrotreatment if hydrogen sulfide is present. The
kerosene fraction from shale oil is like the gasoline fraction, which generally contains
high amounts of nitrogen and oxygen. However, 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 freezepoint
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 specifications.
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 additives but anti-
icing chemicals may be added.
• Jet-A1: 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 components. 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-A1 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 different 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. Normal alkanes
have a high cetane rating, (n-C16=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. Environmental legislation is reducing the amount of
aromatics and sulfur permitted in diesel. Their emission as well as those of small
particulates are considered as possible 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 highpressure 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.
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 distillation 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 mechanically 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 characteristics 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 accumulate 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 containing 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
bubbled 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 measured 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 become 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 according 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 injector clean.
The fuel injector is the heart of a diesel engine. These precision components meter fuel to
a high degree of accuracy. Correct engine behavior depends on the injector functioning
properly.
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 cylinder. 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 improver. 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. Excessive 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 deposit 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 10
ppm).
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 polymer-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 performance in engines.
Fuel stability additives prevent the formation of gums that can lead to injector 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-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 manufactured.
Antioxidants prevent the oxidation of the fuel. Antioxidants work by interrupting the
chain in free radical chain reaction by blocking the free radicals, Phenylenediamines 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 concentrations 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, hydrocarbons and
water separate rapidly and cleanly. But if the fuel contains polar compounds 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 surfactants 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 engines. 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 contaminated 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 concentrations of up to 15 ppm.
Modern 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 petroleum diesel, biodiesel can
operate in combustion-ignition engines. Essentially no engine modifications are required,
and also biodiesel maintains the payload capacity and range of diesel.
The use of biodiesel in a petroleum diesel engine results in substantial reduction of
unburned hydrocarbons, carbon monoxide, and formation of particulate 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 testing 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 heating and processing.
The two most critical specifications of residual fuels are viscosity and low sulfur content
for environmental control.
Furnace oil is one kind of residual fuel. These are blended with other suitable 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 material,
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 removed and usually lead to lower market
prices for fuel oils with high metal contents.
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 residual fuels are traded
internationally on the basis of viscosity measured in centistokes (one centistoke=1
mm2/sec). The value for viscosity should be given together with the temperature at
which it is determined. Accepted temperatures 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 recalculated to obtain viscosity at 100°C. Due to the variability of the
composition of residual fuels, calculations for viscosity at another temperature from
that measured at one temperature may not be accurate. Therefore, such calculated
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 pumping. 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 considered 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 encountered 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 temperatures 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 tem-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 combustion and exhaust spaces. Fuels
produced from thermal cracking residues show a higher carbon/hydrogen ratio and,
hence, high percentage carbon residue. Carbon residue can only be an indicator of
potential deposit-forming tendency 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 ashforming 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: vanadium, 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 residual 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 include 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 conditions 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 acids 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 addressed 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.

1.3.5
International Standards for Fuels
MS ISO 8216/0—8216/4 have been developed as standards for fuel classification 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 application, type,
properties and characteristics establishes the groups of products for each category and
these are provided by separate parts of ISO 8216. Thus, parts designated 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 petroleum
fuels (Class F). The Russian equivalent for this standard is GOST 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 GOST 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 petroleum 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 specifications 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 specification covering the
restrictive requirements of the basic specifications. These are used in the countries in
which consumption of the jet fuels is greatest. This document 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 physicalchemical
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 gasoline, 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 DEF 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 fusion of work piece
and tool. The main functions of lubricating oils and lubricants 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 application 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 friction).
• Ensuring leak tightness. Lubricants ensure leak tightness between the mechanical
components such as the cylinder and the piston, improving compression and producing
better engine performance.
• Removing impurities. Lubricants keep engine components clean by preventing 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 component that
lubricants have in common is that they are composed of a main ingredient 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 synthetic
hydrocarbons (in particular polyalphaolefins manufactured from ethylene). These
products have excellent physical properties and exceptional thermal 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 millions 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, Lubricating 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 relative 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 numerous phosphorus
derivatives.
• Antioxidants. These eliminate or slow down lubricant oxidation, increasing the time
between oil changes through improved resistance to high temperatures.
Dithiophosphates that are used as antiwear additives are also excellent antioxidants.
Other chemical families such as substituted phenols and aromatic 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 alkylsalicylate are used
as detergents.
• Dispersing agents. These maintain in suspension all the solid impurities formed during
engine operation. The solid impurities include unburned residue, 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 sulfonates. 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, neutral 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
polymethacrylates, maleate-styrene copolymers, naphthalene waxes and vinylacetate-
fumarate polyesters.
• Foaming inhibitors. Oil foaming can be caused by the presence of other additives. 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 lubricating 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 common 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 lubricating
properties of the lubricant and to make the lubricant as stable against adverse effects such
as oxidation, corrosion, etc. It is important to know the mechanisms 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.

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 modification 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 protecting film for film friction, but the
products of their decomposition during friction 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 radicals. 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:

Fig. 1.9: Formation of the film in film friction.

1. Antioxidants, which prevent oxidation by reaction with peroxide radicals. Such

additives often contain aromatic compounds in their structure with relatively weak O–
H and N–H bonds. Examples of such compounds are phenols, naphthols, aromatic
amines, aminephenols, and diamines. This type of additive has strong reducing
properties and reacts a quickly with peroxide radicals.
2. Antioxidants which prevent oxidation by reaction with alkyl radicals. The additives
react quickly with alkyl radicals. Examples of such additives are hynones,
iminehynones, methylhynones, stable nitrogen oxide radicals, and molecular iodine.
Alkyl radicals react quickly with oxy-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 reacts 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 former”, which forms with a metal complex that is rendered inactive
to hydroperoxide. Examples include diamines, hydroacids and other compounds 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 oxidation 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 thiophosphate 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 appropriate reaction. For example, phenolsulphide reacts
with hydroperoxide 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 antioxidant and
products of its transformation. Often the mixtures of additives have combined function.
For example, adding phenol and sulphide 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 antioxidants, antagonism results.
In the last type of antioxidants we learn that an important property of antioxidants is
synergy. It is to be understood that by synergy one can mix antioxidants 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 during the preparing of many industrial
additives. This is why it is especially important 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 encountered 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 association of
products that are not fully miscible in oil. In this case, the final stability 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 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 devices: 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 engines 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 countries 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 equipment 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 products.
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 Etectrical 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 accepted
worldwide.
Motor oils are classified according to their viscosity and operational properties.
Besides, motor oils are subdivided in terms of energy conservation and ability to reduce
fuel charge in comparison with a reference oil.
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)

Viscosity Viscosity at low temperature Viscosity at low

class temperature
pumpability, pumpability, Kjnematic Kinematic
Mpa’s, at the Mpa’s, at the viscosity, viscosity,
temperature (° temperature (° mm2/s, at mm2/s, at
C) ASTM D C) ASTM D 100°C 150°C
5293 4684 min max
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 15 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.l 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 1972)
SF Engines working at heavy conditions reformed gasoline
SG Engines released since 1989
SH Engines released since 1994
SJ Engines released since 1997
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 1990
CF-2 Improved characteristics of CD-II
CG-4 Engines released since 1994

Table 1.8: CCMC classification for motor oils by its operational properties and areas of
application.

Class Area of application

Oils for gasoline engines
G1 Engines, working in usual conditions
G2 Engines of modern cars working in hard conditions
G3 Engines of modern cars, with high viscous properties
G4 Engines of modern cars, used for driving with high-speed
G5 Engines of sports high-speed automobiles
Oils for diesel engines
D1 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

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 A1-96, A2-96, A3-96), diesel engines (classes B1-96, B2-96, B3-96) and
diesel trucks (classes E1-96, E2-96, E3-96). After the changes and additions, new classes
A1-98 and A3-98 for gasoline engines, B1-98, 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 collecting 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 formulated
requirements for motor oils for gasoline engines of cars. In ILSAC classification, 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 classification has the low
temperature properties of the viscosity class SAE 75W (i.e. dynamic 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 The maximum temperature of the Kinematic

class achievement of the dynamic viscosity of viscosity
150 Pa*s, °C Min Max
winter oils
75W 40 4.1
80W 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 limiting 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 application.

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 requirements that
are specified.
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 guaranteed 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 properties. 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 categories 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