Classification and Characterization of Crude Oil: Chapter 2)

Parti
CLASSIFICATION AND
CHARACTERIZATION OF CRUDE OIL
OVERVIEW
In this part of the book, fundamental chemical information of interest to

petroleum chemists is given. The first chapter deals with the main definitions as
well as the important properties of crude oil and petroleum products used by
petroleum specialists. A short history is given as to how crude oil became the most
important power source for our civilization for over thousands of years.
A short discussion is also given on the ecological consequences of crude oil
production and treatment as well as problems that generally arise in the petroleum
industry which crude oil chemists have to confront.
A detailed discussion on the properties of crude oil and crude oil products
and some methods for their improvement prepares the reader for the problems the
crude oil chemist faces daily. Some early traditional solutions for these problems,
which never became popular at the industrial scale, will show the reader that there
are many yet-to-be-researched ways to improve the methods for crude oil
treatment. This chapter also highlights the general chemistry of crude oil and crude
oil products.
The last chapter (i.e. chapter 2) of Part I deals with modern analytical
methods used in crude oil chemistry. Modern and classical methods of petroleum
and petroleum products characterization are explained. This chapter is an essential
chapter for present and potential crude oil chemists since analytical chemistry
constitutes an important part of crude oil chemistry. Besides, crude oil products
have so many special properties that are important for the industry. The need to
determine these properties gives rise to the very many analytical methods used in
petroleum chemistry.
Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved.

1
Nature and Classification of Crude Oil
1.1 HISTORY AND NATURE OF PETROLEUM
Petroleum or crude oil has been known for a long time. Archeologists have
shown that it had already been extracted and used for about 5-6 thousand years
before Christ. The most ancient known oil wells are those at Ephrata and the
Kerch coast in the Chinese province of Sychuan. The mention of petroleum has
been found in many ancient manuscripts and books. For example, the Bible writes
about "pitch wells in the vicinities of the Dead Sea".
In ancient times, petroleum had some applications in medicine as well as
civil works. For example, the ancient Greek scientist Hippocrates (IV-V century
B.C.) has described many recipes of medicines which included petroleum. In one
ancient manuscript is written: "we shall rub the patients with petroleum in such a
way that the illness is taken away. White petroleum takes away the illness (cough
in this case). Black petroleum takes away a reasoning of the cough". The Egyp-
tians used petroleum oils to manufacture preservation mixtures.
Petroleum was also widely applied during construction work. Petroleum
bitumen was added to cement and the resulting product used during the con-
struction of the tower of Babylon. In the Bible, there is a narration that goes:
"Also each other has told to each other: "we shall do bricks and heat it by fire".
And they used the bricks instead of stones, and earthen pitch instead of cement".
Modern chemical analyses show that "earthen pitch" is "asphalt", the viscous
resinous substance remaining after the natural evaporation of the light fractions
from petroleum. Asphalt was applied in the construction of the Great Chinese
Wall as well as the trailing gardens of Semiramida. It was used as a water-
resistant medium for the construction of most of the ancient dams on Ephrata

River. In the ruins of the ancient Indian city Mohengo-Daro was found a huge
pool constructed five thousand years ago. The walls of the pool were covered
with a layer of asphalt.
However, the greatest glory petroleum got was not for its use for construc-
tion. For more than two thousand years, petroleum was applied in military actions
and served as a source of military power. This was found in the discovery of the
antiquity based on the invention of "Greek fire". This new kind of weapon consid-
erably strengthened the military power of the countries that knew how to make
and operate them. It is still not proven scientifically who first invented the napalm.
Some people attribute the invention to the Byzantium alchemists, while others
think that the secret of its preparation was already known in ancient Greece. The
Greeks used to bind a vessel with a mysterious mixture to the end of a stick, and
threw it with the huge fire. Historians indicate that the fire flew with the speed of
light and with sound of thunder. When this vessel impinged on the wall, an explo-
sion occurred that gave rise to a huge cloud of smoke. The flame was distributed
in all directions. Water could not extinguish this fire.
Byzantium won a lot of fights using "Greek fire". The antic napalm was
especially of great service to Byzantium in the VII century during the attack by
the Arabs on Constantinople. The Arabian fleet had besieged the capital of
Byzantium. Besieged inhabitants of Constantinople had lost any hope of rescue
when the great idea came. During one of the attacks, they allowed most of the
Arabian fleet to come very close and unexpectedly unleashed a huge quantity of
"Greek fire" on the sea and burned it. The flame burned all the Arabian ships. It
seemed as if the sea was burning.
The composition of "Greek fire" was kept as a top secret. However Ara-
bian alchemists solved the secret of the "Greek fire" after almost four hundred
years after the fight at Constantinople. The main component of "Greek fire" was
petroleum with the addition of sulfur and saltpeter.
Up till now, petroleum has been used in many branches of construction
work or military service. It is thus hard to imagine what our life today would be
without crude oil. It brings power to all our machines and our houses. It is used
as a lubricant for various parts of machines. Hardly any modern device would
work without relying on various products derived from crude oil.
Even though the history of crude oil could be traced back by more than
two thousand years, real production of crude oil perhaps began in August 27,
1859, when the first industrial-scale crude oil well with a depth of 22 meters was
opened in Oil Creek, Pennsylvania. After this first industrial crude oil well was
opened, there was the commencement of a rapid development of crude oil
production and treatment. Probably, this day could be said to mark the birth of
modern crude oil chemistry. In 1878, the Swedish businessman Alfred B. Nobel
together with his brothers formed the Naphtha Company Brothers Nobel. The
company extracted the crude oil in Baku, Russia and transported it to the first
crude oil refineries via the pipelines built by Naphtha Co., which still exists
now.

It may sound strange but petroleum refers to a mountain mineral. It
usually exists together with sand, clay, stone, salt, etc. We normally think of a
mineral as a firm substance. However, there also exist minerals in the liquid
form and even in the gaseous form. One important property of petroleum is its
ability to burn. Other minerals that have this property are peat, brown and stone
coal, and anthracite. These combustible minerals form the special family of
minerals named "caustobolites" (derived from the Greek words causthos,
combustible; bios, life; cast, stone) meaning combustible organic stone [1].
There is a distinction between coal caustobolites and petroleum caustobolites.
All caustobolites, however, contain carbon, hydrogen and oxygen even
though in different proportions for different caustobolites. Specifically, petroleum
is a complex mixture of hydrocarbons and other carbon compounds. At the ele-
mental level, it consists of elements such as carbon (84-87%) and hydrogen (12-
14%) as well as oxygen, nitrogen and sulfur (1-2%). The sulfur content can some-
times be up to 3-5%. Overall, petroleum consists of hydrocarbons, asphaltenes and
resins, paraffins, sulfur and ash. There are three main groups of hydrocarbons in
petroleum—namely, paraffinic, naphthenic and aromatic hydrocarbons [2].
The paraffinic series of hydrocarbons have the general formula CnH(2n+2) and
can be either straight chains (normal) or branched chains (isomers) of carbon at-
oms. The lighter, straight-chain paraffins are found in gases and paraffin waxes.
Examples of straight-chain paraffinic hydrocarbons are methane, ethane, propane,
and butane (gases containing one to four carbon atoms, respectively), and pentane
and hexane (liquids with five and six carbon atoms, respectively). The branched-
chain (isomer) paraffins are usually found in the heavier fractions of crude oil.
They usually have higher octane numbers than the normal paraffins. Paraffinic
hydrocarbons are saturated compounds with all carbon bonds saturated (i.e., the
hydrocarbon chain carries the full complement of hydrogen atoms).
The amount of paraffins in different crude oils varies from 2 to 50%. The
light paraffins are mainly components of natural gas, which dissolve in the crude
oil in the oil wells. Depending on the composition and conditions in the oil well,
one can specify well classes such as gas wells, gas condensate wells and crude oil
wells. Gas wells contain mainly such light paraffins as methane, ethane, propane
and butane, all of which are gases at normal conditions (0.1 Mpa and 20 °C). Apart
from these hydrocarbon gases, gas wells also contain carbon dioxide (CO2), hy-
drogen sulfide (H2S) and inert gases such as nitrogen (N2), argon (Ar), helium
(He), neon (Ne) and xenon (Xe).
Often, gas condensate wells contain compounds with higher molecular
weights than compounds of gas wells. At natural conditions in the oil well (pres-
sures ranging from 25 to 45 MPa), these high molecular weight compounds
dissolve the gas. Initially during oil production from gas condensate wells, pres-
sure will decrease thereby releasing the low molecular weight compounds and
leaving the high molecular weight compounds behind. This high molecular
weight fraction is called condensate.

Crude oil wells contain crude oil as well as gas. The amount of gas in the
crude oil varies from very little to hundreds of cubic meters per ton of crude oil.
These gases, solved in crude oil, can be released from the crude oil at normal
pressures. After production, crude oil is stabilized by separating the gas from the
oil (see Part III). The crude oil coming to the refinery usually contains less than
1% of dissolved gas.
All paraffins from C, to C7g can be separated from crude oil. However, it
has been shown that the largest fraction of paraffins in the crude oil is composed
of molecules from €7 to CM- Lighter or heavier paraffins are present in crude oil
in smaller amounts or as trace compounds.
All types of paraffins (i.e. «-paraffins and wo-paraffins) are present in
crude oil. The methyl-substituted paraffins were analytically proven to be pre-
sent in crude oil in the 1960s. It has been shown that methyl groups in paraffins
are located in positions 2, 6, 10, 14, 18 and further. Over 20 such isomers have
been found. The most abundant compounds of this kind of isomer are phitane
C2oH42 and pristane Ci9H4o (each was found in different crude oils in amounts up
to 1.5%).
It is known that paraffins from methane to butane are gases, from €5 till
On are liquids, and from C!8 onwards are solid substances. The solid paraffins
are present in all crude oils in different amounts, often up to 5%, but in some
crude oils up to 7% or even 12% have been found. Solid fractions of crude oils
do not only contain paraffins, but indeed these solids are complicated mixtures
of paraffins, naphthenes, aromatics and other compounds. It has been shown that
some heavy fractions from paraffmic oils can contain up to 50% paraffins, 47%
naphthenes and up to 3% aromatic compounds. It is known that the higher the
boiling temperatures of the crude oil fraction, the less the amount of paraffmic
compounds present in the fraction. However, paraffins are present in smaller or
higher amounts in all crude oils, crude oil fractions and products. The kind and
how the paraffins are present in oil (i.e. gas, solved or dispersed) depend on the
properties of the crude oil and the chemical conditions of paraffins.
The carbon atoms in the paraffin molecule are connected by a covalent
sigma (a) bond. The length of these bonds for the free isolated molecule in the
gas phase is 0.154 nm. The covalent angle between these C-C bonds is 112°.
The length and the valent angle can be different from the numbers shown for the
liquids and real gas paraffins. This difference can be explained on the basis of
the formation of hydrogen bonds between paraffin molecules. Through these
bonds, the conditions for intermolecular equilibrium in the paraffin will be
changed. However, it is well known that the power of the crystal field can
strongly influence the geometrical parameters of molecules by the formation of
hydrogen bonds. At the moment, there are very limited studies on the geometri-
cal differences between free isolated molecules and condensed molecules.
Paraffins can be present in crude oil as molecular paraffins as well as
associated molecules. The fraction of associated or molecular paraffins in crude
oil depends on many factors. However, one of the more important factors is

temperature; the higher the temperature, the less the fraction of associated paraf-
fins in crude oil.
Usually paraffins are less prone to most known industrial reactions. The
most important industrial reactions of paraffins are oxidation, catalytic isomeri-
zation and sulfurization.
Naphthenic hydrocarbons have the formula CnH2n. All bonds of carbon with
hydrogen are saturated. As such, naphthenic hydrocarbons in petroleum are also
relatively stable compounds.
Naphthenic hydrocarbons are the most abundant class of hydrocarbons in
most crude oils. Their composition in oil can vary from 25 to 75%. Usually, the
amount of naphthenes in crude oil fractions increases as the boiling point of the
fraction also increases. However there is an exception: The amount of naphthenic
hydrocarbons decreases with an increasing boiling temperature for heavy oils.
This can be explained on the basis of the increasing amounts of aromatic com-
pounds in heavy oils.
The distribution of monocyclic naphthenes is well investigated at the mo-
ment in comparison to polycyclic naphthenes. Monocyclic naphthenic compounds
are distributed mainly in the light fractions of crude oil. So, naphthenic hydrocar-
bons in the gasoline fraction are mainly present as substituted cyclopentanes and
cyclohexanes. The amount of these compounds in gasoline fractions varies from
10 to 85%. The polycyclic naphthenes can be found mainly in the heavy fractions
of crude oil (with boiling temperatures over 350°C).
At the moment, chemical analysis has identified only 25 dicyclic, five tricy-
clic and four terra- and pentacyclic naphthenic compounds in crude oil. In cases
where there are over one naphthenic ring in one molecule, a part of the molecule
normally consists of a polycondensed ring.
Bicyclic naphthenes (C7 - C9) are usually used as an indication of a naph-
thenic crude oil. The following bicyclic naphthenic compounds were observed in
different crude oils: bicyclo[3,3,0]octane, bicyclo[3,2,l]octane, bicy-
clo[2,2,2]octane, bicyclo[4,3,0]nonane, bicyclo[2,2,l]heptane and their isomers or
substituted compounds.
The tricyclic naphthenes are mainly present by alkylperyhydrophenantrens.
The following compounds of this class, a), b) and c), have already been analyti-
cally identified.
a) b) c)

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

represented by gopan (g), lupan (h) and phridelan (i).
g) h)

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

Special properties of asphaltenes include the tendency to associate, high
molecular weight and paramagnetism. All these properties make asphaltenes very
difficult to analyze or investigate. This is why approximately since the 1970s,
asphaltenes chemistry exists as a separate science independent from crude oil
chemistry. In part four of this book, some problems that arise in asphaltenes stud-
ies will be discussed.
Porphyrins, special nitrogen compounds of organic origin, are also present
in petroleum. They are believed to be formed from chlorophyll of plants and he-
moglobin of animals. Porphyrins can be cracked at temperatures ranging from 200
to 250°C. The basic structural unit of porphyrins is given in Fig. 1.1.
.R'
R
\ \
N N
R"
R'"' R
Fig. 1.1: The structure of porphine basic structural unit of porphyrins.
The amount of nitrogen in different crude oils varies from 0.02 to 1.5%.
There are many types of nitrogen compounds in crude oil. The example shown in
Figure 1.1 is only one of them.
Studies of nitrogen compounds present in crude oil are made possible in two
ways. First, these compounds can be analyzed directly in crude oil. The biggest
advantage of such an analysis is the possibility to investigate these compounds
both in their natural form and natural environment. However, the concentration of
nitrogen compounds in crude oil is relatively small, and this makes the analysis
not only difficult but results in a rather wide divergence of the measurements. The
second method is that the nitrogen compounds can be separated before analysis.
The disadvantage of this method is the possibility that during separation, the native
structure could be destroyed. However, despite the difficulties in investigating

nitrogen compounds, analysis has shown that, at the moment, nitrogen compounds
are present in crude oil mainly as cyclic compounds. Nowadays, nitrogen com-
pounds can be classified as alkaline (lye) nitrogen and neutral nitrogen com-
pounds.
Pyridines (a), hinolines (b) and acredines (c) belong to the strong alkaline
(lye) nitrogen, because of their free, non-compensated electron pair.
a) b) c)
The substituted anilines (d), amides and/or imides belong to the weak alka-
line (lye) nitrogen compounds.
d)
NH
LJ*
The non-substituted compounds such as indols (e) or carbozoles (f) are
typical nitrogen neutral compounds.
f)
NH
The above are some examples of nitrogen compounds in crude oil. It is

however difficult to show all the possible nitrogen compounds present in crude oil.
Recent investigations have shown that compounds with two nitrogen atoms or one
nitrogen atom and one sulfur atom in one molecule can be found in crude oil.
The nitrogen compounds are very important in their role as natural surfac-
tants. The concentration of these compounds in crude oil has a great influence on
the chemical and physical activities of the crude oil, on metal/crude oil interface
and ground/crude oil interface. This property of nitrogen compounds is used dur-
ing the production of crude oil from the oil well. For example, hinoline can pre-
vent the corrosion of metal parts; this is very important for the continuous working
of many oil production plants.
The next class of heteroatom compounds in crude oil is the oxygen com-
pounds. The amount of oxygen in crude oil can vary from 0.1 to 3% or even 4%.
The amount of oxygen in crude oil fractions increases with the boiling temperature

of the fraction. Over 20% of all oxygen compounds are concentrated in asphalte-
nes and resins.
Almost similar to nitrogen compounds, the oxygen compounds can be clas-
sified as neutral oxygen and acidic oxygen compounds. The cyclic and aromatic
compounds, ethers, anhydrides, furans and so on usually belong to the neutral
oxygen compound class.
The acidic oxygen compounds are usually represented by carbon acids. The
presence of these compounds in crude oil has been known for a very long time. It
was noticed during the production of light kerosene. In the production of high
quality light kerosene, it was necessary to clean the kerosene with lye. Compounds
with strong emulsifying properties were produced during this process. At the end
of the nineteenth century, it was shown that these compounds were sodium salts of
carbon acids.
Sulfur may be present in crude oil either as hydrogen sulfide (H2S), or as
compounds such as mercaptans (a), thiophenols (b), cycloalkanethiols (c), thio-
phenes (d), benzothiophenes (e), alkylbenzothiophenes (f), etc., or as elemental
sulfur.
a) b) c) d)
CH2
CH2
i ;s
R
e)
Each crude oil has its own types and proportions of sulfur compounds. As a
general rule, however, the proportion, stability, and complexity of the compounds
are greater in the heavier crude oil fractions. Hydrogen sulfide is a primary con-
tributor to corrosion in refinery processing units. Other corrosive sulfur materials
are elemental sulfur and mercaptans. Pyrophoric iron sulfide results from the cor-
rosive action of sulfur compounds on the iron and steel materials used in refinery
process equipment, piping and tanks. The combustion of petroleum products con-
taining sulfur compounds results in the production of undesirable by-products such
as sulfuric acid and sulfur dioxide. Catalytic hydrotreating processes such as hy-
drodesulfurization remove sulfur compounds from refinery product streams.
Sweetening processes either remove obnoxious sulfur compounds (example, mer-

captans) or convert them to odorless disulfides. The amount of sulfur in petroleum
of different origins ranges from 0.1 to 5% [2].
Sulfur compounds in crude oil sharply decreases the quality of fuels and
oils produced from the crude oil. They cause corrosion of equipment during
treatment, reduce activity of antidetonation additives and antioxidizing stability
of gasoline, raise the propensity to form hard residues in cracking gasoline frac-
tions, and result an environment pollution.
Metals (including heavy metals) have been found in all crude oils. Their
composition varies from 0.01 to 0.04% of crude oil. About thirty different met-
als are found in different crude oils. The most common are vanadium, nickel,
iron, zinc, mercury, boron, sodium, potassium, calcium and magnesium.
Unsaturated compounds like alkenes are not presented in crude oil. How-
ever, these compounds can be produced during the thermal or/and catalytic
treatment of the crude oil. These compounds differ from all crude oil com-
pounds by their high chemical activity. Based on the high chemical activity of
unsaturated compounds, it is clear why this class of compounds does not exist in
crude oils.
Ash forms the balance in petroleum. It is the noncombustible portion that is
left behind after petroleum is burned. Ash is composed of various metallic com-
pounds such as compounds of iron, nickel and vanadium as well as various salts.
Petroleum is also characterized by physical properties such as density, vis-
cosity, temperature of hardening, boiling temperature and solubility as well as
electrical and optical properties [4].
1.1.1 Origin of Petroleum
The first attempt to explain the origin of petroleum dates back to antiquity.
For example, the Greek scientist Strabon, who lived about 2000 years ago wrote:
"At the place named Nymphey, there is a rock spiting fire, and under it are the
sources of warm water and asphalts... ". Strabon united two facts: the eruption of
volcanoes and the formation of asphalts (the way he named petroleum). This con-
nection between the two facts was a mistake. In the places mentioned by his work,
there were no erupting volcanos. The events which Strabon described as "erup-
tions" were actually "emissions", i.e. breaking out of underground waters (so-
called geysers), accompanied by outputs of petroleum and gas on the surface.
M.V. Lomonosov was one of the first scientists to introduce a reasonable
scientific concept of the origin of petroleum. In his mid-eighteenth century work
on "terrestrial layers", this Russian scientist wrote: "It is expelled from under-
ground with heat, prepared from stone coal and brown coal, this black oily mate-
rial... And this is a birth of a different grade of combustible liquid and dry hard
matter. This is the essence of stone oil, liquid pitch, petroleum, and similar materi-

als which are different by cleanliness, but occur from the same origin" [5]. It can
therefore be stated that the idea of the organic origin of petroleum from stone coal
was conceived more than 200 years ago. The initial substance was an organic
material transformed at first into coal and then into petroleum.
Lomonosov was not the only one who addressed the question of the origin
of petroleum in the eighteenth century. However, some of the other hypotheses
formed at this time were less than scientific. For example, a hypothesis credited to
a Warsaw priest was that the Earth was very fertile in the paradise period. The
core of the earth contained a fatty impurity. After the paradise period, this fat was
partially evaporated, and the vapor partially condensed on the ground where it
mixed up with a variety of materials. This was later transformed to petroleum by
the world flood.
There are many other less scientific hypotheses about the origin of petro-
leum even by scientists. At the end of the nineteenth century, the authoritative
German geologist H. Hefer reported of an American petroleum industrialist who
considered petroleum to have resulted from wet whales that existed at the bottom
of polar seas. This petroleum penetrated into Pennsylvania by seeping through
underground channels [5].
In any case, the most widespread ideas among the scientists in the nine-
teenth century centered on the organic origin of petroleum. Disputes were mainly
around the initial material for petroleum formation: animals or plants? German
scientists H. Hefer and K. Engler carried out experiments in 1888 in which they
sought to prove that petroleum formation was from animal origin. The experi-
ments were performed by evaporation of fish fat at 400°C and 1 bar. Oil, combus-
tible gases, water, fats and different acids were formed from the 492 kg of fat
used. The largest fraction of evaporated material was oil (299 kg, or 61%) with a
density of 0.8105 g/cm3. Subsequent evaporation of the oil product yielded satu-
rated hydrocarbons (ranging from pentane to nonane), paraffin, lubricant oils as
well as olefms and aromatic hydrocarbons. Later, a Russian scientist (N.D. Ze-
linskiy) carried out a similar experiment in 1919. However, his initial material was
organic silt of mainly vegetative origin from Lake Balhash. The evaporation prod-
ucts in this case were: crude pitch - 63.2%, coke - 16.0%, and gases (methane,
carbon oxides, hydrogen, hydrogen sulfide) - 20.8% [5]. Subsequent processing of
the pitch yielded gasoline, jet oil and heavy oil.
By the end of the nineteenth century, two different hypotheses of petroleum
origin had emerged: organic and inorganic hypothesis. The main concept of inor-
ganic petroleum origin was illustrated by the experiments of Berthelot. In 1866,
Berthelot considered that acetylene was the basic material. Large quantities of
acetylene were assumed to be produced by the reaction of water with carbides
which, themselves, were formed by the reaction of alkali metals with carbonates.
The conversion of acetylene to petroleum was accomplished at an elevated tem-
perature and pressure according to the following:

CaCO3 -> CaC2 + H2O -» C2H2
petroleum
Indeed, the idea of the inorganic origin of crude oil did not initially have
any success with geologists, who considered that experiments carried out in the
laboratory considerably were different from processes that occur in a nature.
However, the inorganic theory of crude oil formation unexpectedly received
support due to new evidence from astrophysics. Research on the spectra of plan-
ets showed that, there are hydrocarbon compounds in the atmosphere of Jupiter
and other large planets as well as in gas environments of comets. If hydrocar-
bons are widespread in space, it means natural processes of synthesis of organic
substances from inorganic substances are possible.
In the 1950s, the Russian scientist N.A. Kudryavzev collected a lot of
geological material involving petroleum and gas deposits in the world. First of
all, Kudryavzev noticed that many gas and petroleum deposits were found in
zones of deep cracks of the terrestrial core. This knowledge was not new at this
time since other scientists had noticed this fact much earlier. However, Ku-
dryavzev extended the application of such ideas to a great extent. For example,
in the north of Siberia, near the area of the so-called Marhiinskij shaft, there are
frequent outbursts of petroleum onto the surface. At a depth of about two kilo-
meters, the mountain layers are literally impregnated with petroleum. At the
same time, it has been shown that the amount of carbon formed simultaneously
with mountain layers is extremely small (only 0.02 to 0.4%). But further from
the shaft, the amount of organic compounds in the layers increases. Neverthe-
less, the quantity of petroleum sharply decreases. Based on these extra data,
Kudryavzev suggests that crude oil formation in the Marhiinskij shaft can most
likely be explained not on the basis of formation from organic substance, but by
an inorganic theory of oil formation in the deep layers (or shells) of the planet.
Similar oil wells have been found in other regions of the world as well. A long
time ago in Wyoming (USA), the inhabitants heated their houses using pieces of
asphalt, which they collected from the cracks in mountain layers in the Copper
Mountains. But the minerals, of which these mountains consisted, could not
accumulate petroleum and gas. This means that the asphalt (similar to oil) could
only be formed according to the inorganic theory.
The space hypothesis of the origin of oil deserves mention as well. In 1892,
Sokolov stated that the dust cloud from which the Earth and other planets of the
solar system were formed consisted of hydrocarbons. In the process of the forma-
tion of the Earth, hydrocarbon substances were buried in the core of the earth.
Further, during the cooling of the planet, the hydrocarbons were pushed out. As a
result, they penetrated into cracks of friable minerals. This hypothesis is also one
of the representations of petroleum synthesis from minerals.

However, the origin and formation of petroleum are very difficult questions
and it is almost impossible to answer them using only one theory. A more detailed
discussion concerning the origin of crude oil formation can be found in references
[6-9].
1.1.2 Oil Formation in the World's Oceans
All seas and oceans are populated with biomass which are essentially a wide
variety of animals and plants. Of all sea biomass, the ones with the most signifi-
cant role in petroleum formation are microorganisms, typically plankton, 90% of
which is microscopic seaweed (phytoplankton). Plankton is the basic source of
organic material in the sea. Plankton is contained not only in the silts at the bottom
of seas or lakes but also dispersed or dissolved in the water. Approximate quanti-
ties of organic material dissolved per m3 of water are 2 g in the Atlantic and Pa-
cific oceans, 5-6 g in the Baltic and Caspian sea, and 10 g in the Azov sea. It is
interesting that the dissolved organic material is like greasy acids that is structur-
ally similar to plankton fats. The concentration of organic material is highest at the
bottom of the oceans. This is obvious because, for the most part, these organisms
are denser than the liquid medium. As such, they fall down to the bottom by grav-
ity. Shallow conditions are the preferable places for accumulation of organic mate-
rial. Generally, the process of mineral (clay, sandy minerals, etc.) accumulation
promotes fast trapping or collection of organic material as well as its protection
from decomposition. On the other hand, for organic material found deep in the
ocean water, there is sufficient time for it to be substantially dissolved and dis-
persed in the water due to the activity of bacteria. Consequently, only 1% of or-
ganic material is usually collected annually per m2 of ocean bottom in the world's
oceans out of 150 g that is formed.
Now, let us consider what occurs when organic material is collected on the
sea bottom. Organisms that are either brought from different continents or are
formed directly in the sea are collected rapidly in clay or sandy minerals. Although
organic materials contain various substances, the one with the greatest interest for
subsequent petroleum formation is "bitumoid". Birumoid can be extracted from
organic material using various solvents such as chloroform, benzene or ether. The
main source of bitumoides are lipoid (i.e., fat or a similar compound). The propor-
tion of bitumoides in the sea bottom deposits ranges from 2 to 20% of all organic
material. Apart from bitumoides, materials such as hydrocarbons (from 0.1 to 3%)
are also available in organic material. Approximately 300 g (and in some cases up
to 15 kg) of hydrocarbons are contained in 1 m3 of minerals formed. The average
quantity of dispersed hydrocarbons in minerals is 70-80xl012 ton. This exceeds the
established volume of hydrocarbons in oil fields (about 2.2xl012 ton) by about
tenfold. It is therefore evident that the organic material collected as described

earlier in this section is sufficient to form the established world petroleum re-
serves.
Dispersed hydrocarbons in solid minerals and silts in the seas are similar to
petroleum hydrocarbons. They are called dispersed petroleum or micro-petroleum.
Mountain minerals are hydrofill, meaning that they are moistened with wa-
ter instead of petroleum. Thus, in addition to mountain pressure, capillary forces
enhance the displacement of petroleum in the solid minerals.
The process of petroleum displacement in the native minerals (i.e. from
which it is formed) is referred to as primary migration or emigration. By getting
into loose solid minerals (collectors or traps), petroleum begins a new life.
Petroleum migration through collectors proceeds as long as it does not encounter
a trap (i.e. a layer that is capable of keeping the petroleum as a trapped deposit).
Examples of these traps are anticline traps, traps associated salt domes and oil
entrapment in a limestone reef. These are shown in Figures 1.2-1.4. Thus, the
pre-history of petroleum begins in live organisms from which are synthesized
initial biochemical compounds. On the other hand, the history of petroleum
begins with the collecting of biological and organic substances in the solid min-
erals [3].
oil
Fig. 1.2: Anticline traps.
Traps associated with salt intrusions are of many types (example: Fig. 1.2-
1.3); limestone reefs (Fig. 1.4) can also serve as reservoir rocks and give rise to
overlying traps of anticlinal form as a result of different compaction. Examples are
also known in which the reservoir rock extends to the surface of the earth but oil
and gas are sealed in it by clogging of the pores by bitumen or by natural cements
[3]. Many reservoirs can display more than one of the factors that contribute to the
entrapment of hydrocarbons.

water
oil
water
salt dome
Fig. 1.3: Traps associated with a salt dome.
oil
water
Fig. 1.4: Oil entrapment in a limestone reef.
Detailed discussions on oil and gas formation and modern methods of inves-
tigation in this area can be found in references 10-33.
1.1.3 Modern Concept of Formation of Petroleum
The characteristic feature of the modern concept of petroleum formation is

based on a new geological idea. Here, there is the representation that there occurs
a horizontal movement of separate blocks of the lithosphere, the so-called, "litho-
sphere-plates". Deep down our planet is a circulation of material according to the

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

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

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

The gravimetric method is based on investigating the distribution of the
gravitational force on the Earth's surface. The acceleration of an object (for
example in a mountain area) in a free fall depends on the density of the moun-
tain layers. If the underground is the layer of stone salt having a relatively low
density, the acceleration due to free fall decreases, indicating a negative anom-
aly in the gravitational field. In the case where the layers are composed of a
more dense material (granite for example), a positive anomaly in the gravita-
tional field is indicated.
Usually, the gravimetric method is applied in combination with magnetic
prospecting. Our planet is a huge magnet. That means the Earth has a magnetic
field. The characteristics of the field are influenced by the compositions of the
mountain layers constituting the terrestrial core. For example, magma layers are
more magnetically active than sands. A magnetic anomaly arises above a place
of layer location.
Usually, gravimetric and magnetic methods are carried out before seismic
prospecting. Seismic prospecting is carried out based on what information on the
gravimetrical and magnetic anomalies is obtained. After detecting anticline traps
or any other kind of traps, a detailed seismic investigation of the area is carried
out to establish both the exact contours of the trap and the depth of its location.
After that, drilling is possible.
There is one more geophysical method. This is the electrical prospecting
method developed in France in 1923. This method is based on investigating the
Earth's core by measuring the electromagnetic fields either of an artificial or natu-
ral origin on a ground. The main idea of the method is that the mountain layers
have various electrical properties. For example, petroleum is dielectric, the miner-
als rich in iron are good electric conductors. Geophysicists investigate the Earth's
core by creating an artificial electrical field and studying the electrical resistance
of mountain layers. By tracing high-resistance layers, it is possible to identify deep
relief anticline traps.
The geological and geophysical methods of crude oil prospecting do not
always give the correct answer to the question whether there is an oil or gas
deposit in the Earth. As a matter of fact, the presence of traps or collectors is
necessary, but it is not a sufficient condition for the accumulation of crude oil
deposits. Frequently, it has been observed that after drilling in the prospected
area, neither petroleum nor gas is present. This is why it is recommended to
carry out geochemical and hydrogeological prospecting after geological and
geophysical investigation of the area. Based on results of the geochemical and
hydrogeological prospecting, it is possible to confirm the presence of petroleum
or gas in traps based on the microconcentration of the hydrocarbons on the
Earth's surface in a researched area. Geochemical methods include gas, lume-
nescic, radioactive, photography and hydrochemical methods.
The gas photography method was first used in Russia in 1929. The main
principle of the method is that there is filtration and diffusion of gases through the
pores and cracks in the mountain layers of dispersed hydrocarbon gases around

any crude oil deposit. Such an anomaly is usually a direct attribute of the crude oil
or gas deposits. The disadvantage of the method is that the anomaly can be dis-
placed from a source upwards of the layers.
The lumenescic method is based on an investigation of the bitumen dis-
persion area. The bitumen content in a layer rises above the crude oil or gas
deposits. Samples from the layer are selected from shallow depths, and investi-
gated using ultra-violet light.
The radioactive photography method is based on investigation of distribu-
tion of radioactive elements (first of all uranium) above petroleum and gas depos-
its. The radioactivity above the crude oil deposits is lower than around the deposit.
However, radioactive anomalies in surface layers can be due to changed lithologic
structure of layers. That is why this method is applied rarely.
With the hydrochemical method, the chemical composition of underground
water together with its contents of dissolved gases and organic substances is stud-
ied. A large amount of hydrocarbons in the underground water shows a high pos-
sibility of the presence of petroleum deposit in this area.
More about oil and gas prospecting and modern investigation in this area
can be found in references 38-46.
1.1.3.2 Drilling and crude oil extraction
Practically all the drilling today is carried out according to the rotary prin-
ciple. A drilling tool screwed in at the lower end of the hollow linkage (either
roller chisels or diamond chisels) is shifted in a rotary motion by a turntable
installed in the drilling tower. The chisel drills into the Earth's layers. The bore-
hole usually has a diameter of 10 to 70 cm. The borehole begins with the largest
diameter at the surface and then decreases with depth.
Heavy bars are installed to increase the load pushing on the chisel and to
improve the drilling capacities. The individual parts are lined with steel tubes
and sealed against the mountain layers with cement. The layers of material
drilled out must be removed from the borehole. The scavenge pump is used to
ensure this removal as it maintains a liquid circulation in the drilling borehole.
Water is constantly supplied to the chisel as coolant. It ascends the pipe system
with constant pressure and thereby carries all detached rock particles forward.
During the drilling process, particles that are constantly brought by the flushing
water are examined in order to obtain information on the characteristics of the
drilled layers. The first pipe system (so-called "preventers") is now installed for
protection against uncontrolled oil or gas release. A simplified example of a
drilling tower is shown in Figure 1.5.

Fig. 1.5: Example of drilling tower.
Crude oil extraction begins after successful drilling. The three most popular
extraction methods are:

1. Eruptive extraction. Each crude oil deposit has a natural layer pressure,
which increases by up to one bar for every 10 meters of depth. Dissolved
gas also flows together with the crude oil from the oil well, the combined
flow resulting in pressure depletion in the well. Consequently, the gas
begins to exit from the oil accompanied by volume enlargement. The exit
of crude oil from the oil well in this case can be compared with the exit
of soda water from the bottle when it is opened.
2. Gas elevator extraction. After eruptive extraction has ended naturally,
one then sets the oil well under sufficient pressure that will force the oil
out, and so extend the period of free flowing out of the oil. Gas elevator
extraction has a distinct area of application. Frequently, one prefers to
pump to gas elevators during extraction of oil from larger depths (ap-
proximately between 2500 and 3500 meters).
3. Pumping extraction. Pumping is the most frequently used artificial ex-
traction method. The most important feature of this extraction method is
the use of a pump. The pump consists of three sections: the deep pump,
the pump linkage and finally the drive unit, which is represented by the
pump support (so-called horse head) with the driving motor. The usual
stroke rate for this pump varies from a few strokes up to 20 strokes per
minute. An example of such a pump is shown in Figure 1.6.
Fig. 1.6 Example of pumping extraction.
A special problem in crude oil extraction arises if high viscous petroleum or

bituminous petroleum is being extracted. There is a significant number of oil
wells in some places in the world, especially in Canada, with viscous and paraf-

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

any prime consideration. The key was to extract as much petroleum as possible.
However, about fourteen years into the twentieth century, some indications of
these adverse effects had already appeared.
It happened in the oil well in Wilmington (California, USA). This oil well is
located between the southwest areas of Los Angeles and a gulf where Long Beach
reaches the coastal quarters of the same resort city. The area of this petroleum pool
is 54 km2. The oil well was drilled in 1936. In 1938, it became the center of oil
extraction in California. By 1968, almost 160 million tons of petroleum and 24
billion m3 of gas were extracted from this oil well.
The location of the oil well at the center of industrial and densely populated
areas of southern California, and also its proximity to the large oil refineries in Los
Angeles, was considered very crucial to the economic development of the whole
of California. As a result, a very high level of extraction from this well (as com-
pared with other petroleum wells in North America) was constantly supported
from the beginning of the operation of the oil well till 1966.

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

An earthquake was registered in April, 1989 in Tataria with an intensity up
to 6 M. In the opinion of the local experts, there was a direct connection between
amplification of petroleum extraction from oil wells and activation of weak earth-
quakes. Cases of breakage of oil well trunks and columns are on record in the
Tataria example. Earthquakes in this area are especially dangerous since Tataria
nuclear power station is located in this area. In all these cases, one effective meas-
ure to mitigate the problem is water flooding. Forcing water into the productive
layer compensates for the extracted petroleum.
1.1.4.1 Dangerous fogs
Another danger in petroleum lies in the use of petroleum and gas as a fuel.
During the combustion of these materials, enormous amounts of carbon oxides
(such as carbon dioxide (CO2)), various sulfur compounds (such as sulfur dioxide
(SO2)), nitrogen oxides (such as nitric oxide (NO) and nitrogen dioxide (NO2)),
etc. are released into the atmosphere. In the last half of the twentieth century, the
contents of CO2 in the atmosphere has increased by almost 288 billion tons, and
more than 300 billion tons of oxygen has been used up for combustion processes
involving various kinds of fuel, including stone coal. Thus, starting from the first
fires of primitive man to the present, the atmosphere has lost about 0.02% of oxy-
gen whereas the content of carbon oxides has increased by 12%. Annually, man-
kind burns 7 billion tons of fuel, for which more than 10 billion tons of oxygen is
used up, and up to 14 billion tons of CO2 is released into the atmosphere. In the
future, these values will grow because of the general increase in the production
and combustion of combustible minerals. It is predicted that in 2020, about 12,000
billion tons of oxygen (0.77%) will disappear from the atmosphere as a result of
being used up for combustion processes. This means that in the next 100 years, the
composition of the atmosphere will be essentially changed, probably, in an ad-
verse direction.
It is feared that reduction in the quantity of oxygen and the growth in the
content of CO2 will cause adverse changes in the climate. The molecules of C02
allow short wave solar radiation to penetrate the atmosphere of the Earth and re-
tain infrared radiation which penetrates into the terrestrial surface. This gives rise
to the so-called greenhouse effect, resulting in an increase in the average tempera-
ture of the planet. It is indicated that the change in climate from 1880 till 1940 is
substantially related to this effect. It seems that the climate will progressively
change due to the greenhouse effect. However, other human influences on the
atmosphere may help to neutralize the greenhouse effect.
Mankind contributes huge quantities of dust and other microparticles into
the atmosphere. These particles shield solar beams and reduce the heating action
of CO2. According to the American expert K. Frazer, the turbidity of the atmos-
phere above Washington in the period from 1905 to 1964 has increased by 57%.

The transparency of the atmosphere above the Pacific Ocean was decreased by
30% from 1957 till 1967.
Atmospheric pollution by itself introduces another problem: it reduces the
quantity of solar radiation that reaches the Earth's surface. According to data re-
leased from studies of the oceans and the atmosphere above the US by a US health
agency, solar radiation in the period from 1950 to 1972 decreased by 8% during
the fall season, and increased by only 3% in the spring. On the average, solar ra-
diation has fallen by 1.3% since 1964. This is equivalent to the loss of approxi-
mately 10 minutes of daylight per day. This apparent triviality can have serious
consequences on the Earth's climate.
In 1975, the atmospheric pollution above the United States resulted in an
absolutely unexpected phenomenon. In the area of Boston (Massachusetts), it was
established that there was a large increase in the quantity of ozone in the atmos-
phere - 0.127 ppm, whereas the established USA EPA safety limit is 0.08 ppm. It
is known that ozone is formed in the atmosphere during the interaction of hydro-
carbons with oxygen. A high concentration of ozone is more poisonous than char-
coal gas. On August 10, 1975, the Department of Public Health Services of the
state issued an "ozone-alarm", which lasted till August 14, 1975. This was already
the second alarm for one year.
Other notable contributors to atmospheric pollution include jet planes, ma-
chines and factories. For example, modern jets need to use 35 tons of oxygen to
enable them to cross the Atlantic Ocean. Also, the process of flying leaves "traces"
behind thereby increasing the cloudiness of the atmosphere. Cars, whose world-
wide total is already more than 500 million, pollute the atmosphere very signifi-
cantly. They use fossil fuel and emit CO2, SOX, NOX, etc. into the atmosphere. In
the US, automobiles contribute up to half of the air pollution. This type of statistic
led a US senator, E. Muskie, to declare in 1976 that 15 thousand men and women
die each year in the US because of diseases caused by air pollution. There are
strong efforts to seek to design automobile engines that can work with other types
of fuel. For example, electric cars are no longer dreams of the past. There are
demonstrations of various types of electric cars in many countries of the world.
However, their commercial application worldwide has been hampered by the low
capacity of the accumulators.
Petroleum fueled electrical power plants are also a major contributor to air
pollution. Such power plants emit about 500 tons per day of sulfur into the envi-
ronment in the form of sulfuric anhydride. This reacts with water resulting in the
immediate formation of sulfuric acid. A French journalist, M. Ruze, has presented
data to show that a French thermal power plant belonging to Electricite de France
emits about 33 tons of sulfuric anhydride into the atmosphere on a daily basis.
This can result in a daily production of about 50 tons of sulfuric acid. The after-
math of acid production is acid rain, the adverse effect of which covers the power
plant and surrounding territory up to a radius of 5 km. Such rains have high
chemical activity. They corrode even cement and marble.

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

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

ocean. One liter of petroleum deprives about 40 thousand liters of sea water of the
oxygen that is used to sustain living inhabitants such as fish. Also, one ton of pe-
troleum can pollute about 12 km2 surface of the ocean.
There are many sources of petroleum pollution in the seas and oceans. These
include failures of tankers and drilling platforms as well as dumping of ballast and
clearing waters.
Perhaps, the first catastrophe that stirred worldwide interest in this issue was
the one that took place in 1967. The supertanker "Tory Canyon" sank at the coast
of Western Europe, and 120 thousand tons of petroleum poured into the sea. A
huge petroleum slick painted the coastal waters of France and England. Approxi-
mately fifty thousand birds died (i.e. almost 90% of the see bird population in
these areas).
In 1974 there was the failure of the American tanker "Transheron", which
had on board 25,000 tons of petroleum. About 3,500 tons of petroleum flowed out
from the holes in the tanker in only the first week. A huge petroleum slick covered
the area often square kilometers and moved slowly towards the coastal city of the
South Indian State of Kerala.
450 tons of petroleum poured from the Gulf Oil tanker "Afran Zodiac" into
the Gulf of Bantry (Ireland) in January of 1976. The whole northern part of the
gulf was under its cover.
In February of 1976, there was a fire onboard the tanker "San-Peter" carry-
ing 33 thousand tons of petroleum as it was navigating its way from Peru to Co-
lombia. The vessel sank and the petroleum content poured into the sea. The sea-
men from Colombia tried unsuccessfully for ten days to clean the waters in the
area of the disaster.
The supertanker "Olympic Bravery", property of the company owned by the
Greek magnate A. Onassis, sank at the coast of Great Britain in 1976. A mixture
of petroleum and sand flooded the coast. The British government was compelled
to involve naval forces in clearing the coast. However, it was not before irrepara-
ble damage was done to vegetation and animals.
About 20 million liters of petroleum was released into the waters in the area
of the Hawaiian Islands in 1977 as a result of the disaster with the tanker "Irins
Challenger". In the same year, 90 thousand tons of petroleum was released into the

waters of the northern part of the Pacific Ocean as a result of the fire on board the
tanker "Hawaiian Patriot".
The year 1978 was marked by the largest tanker disaster on the coast of
Great Britain. The American supertanker "Amoko Cadiz" sank on the reefs, and
about 230 thousand tons of petroleum poured into the sea.
The collision of tankers "Atlantic Empress" and "Idgen Captain" in the
Caribbean Gulf was the largest disaster in 1979. About 300 thousand tons of petro-
leum poured into the sea.
In the November storm of 1981, the Greek tanker "Globe Asini" had a
disaster on the wave protector off the Port of Klaipeda. About 10 thousand tons of
petroleum poured into the sea.
In August of 1983, the tanker "Castillo de Believer" had a disaster near the
European Atlantic coast. The vessel sank, and about 250 thousand tons of petro-
leum was released into the ocean.
The tanker "Baia Paraiso" with one thousand tons of diesel oil on board
sank at the coast of the Antarctic continent in January of 1989. Another tragedy
happened in the Arctic waters of Alaska two months later. The tanker "Exxon
Valdez" sank at the reef because of the fault of the captain. More than 40 thousand
tons of petroleum flowed out from the hole into the waters. A petroleum slick
covering an area up to 800 km2 was formed. The area in the Strait of Prince Wil-
liam was declared "a zone of disaster". The US Navy was involved with the
cleanup. Nevertheless, there was the "potential for ecological disaster" with con-
sequences that are difficult to foresee, according to the Washington Post.
At the end of March of 1989, the Dutch River tanker ran aground in the area
of Bad-Honnefa. Approximately one thousand tons of petroleum poured into the
river. Petroleum film covered the river up to an area of 7 km .
In April of 1989, the Indian tanker "Kanchendgunga" ran aground at the reef
in the Red Sea in the territorial waters of Saudi Arabia 5 km from the port of Jeda.
More than 10 thousand tons of petroleum flowed out into the sea.
The sad list of tanker failures could go on, but their share in petroleum
pollution of seas and oceans is not big. Three times more petroleum is released
due to dumping of the water used in washing tanker tanks into the sea or oceans.
Also, four times more pollution comes from the waste water of petrochemical
factories; and almost the same amount of petroleum is released by the disasters
that occur at sea platforms.
Now, the question arises: How can the ocean be rescued?
Fortunately, there are good methods. Some of these methods involve the
application of dispersing additives - special substances - that adsorb petroleum;
another is the treatment of petroleum slicks with iron powder and the subsequent
collection of iron particles with a magnet. A promising method, however, lies in
biological protection: the use microbes. These micro-organisms (already designed
in the US and elsewhere for this purpose) are capable of splitting molecules of
hydrocarbons.

Russian scientists have established that any bio-organisms that inhabit the
sea are not affected by petroleum pollution. An example is cardium. This plays an
important role in clearing sea water of petroleum by extracting for itself both food
and oxygen from the pollutant. Nature has already designed for the clearing of
seas and oceans following natural penetration of petroleum in the ocean. The
penetration of oil from underground is seen, for example, on the coasts of Califor-
nia, Australia, Canada, Mexico and Venezuela as well as in the Persian Gulf. In
one part of the bottom of the Californian Gulf, in the Strait of Santa Barbara, there
is a natural outflow of petroleum from underground. It is supposed that this oil
penetration had been taking place for the past ten thousand years. However, it was
noticed for the first time in 1793 by the English seafarer D. Vancouver. According
to US scientists, the annual penetration of petroleum into the world oceans from
natural infiltration is approximately 200 thousand tons. This is about 6% from the
total volume of petroleum that penetrates into the seas and oceans on the planet
from anthropogeneous sources. Suffice it to say that during the disaster of the
tanker "Tory Canyon", as much petroleum that will penetrate into water from the
Californian oil wells for 28 years poured into the ocean. This was too large an
amount of petroleum pollution to be mitigated by natural cleaning alone.
1.2 GENERAL PROPERTIES AND CLASSIFICATION OF

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

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

• 140-180°C - heavy naphtha

• 180-240°C - kerosene fraction
• 240-350°C - diesel fraction
The residue after atmospheric distillation is called "atmospheric residue".

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

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

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

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

• carbon (83 - 87%)
• hydrogen (11.5-14%)
• hetero-atoms (1-5.5%)
Table 1.1 shows the chemical composition of oils from the US, Canada, and
Russia.
Even though the chemical composition of petroleum varies, almost all the
hydrocarbons found in petroleum do not include alkenes. On the other hand, many
oils with high amounts of paraffinic or naphthenic compounds or arenes are
known.
It is necessary to make a chemical classification of petroleum since chemical
properties are very crucial in selecting the right method for processing the oil.
There are many classifications with regard to fractions and chemical compositions
of petroleum. In this chapter we will present the basis for these classification
methods.
Table 1.1: Ultimate analysis for crude oils.

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

paraffin base from those of an asphaltene base was introduced into petroleum
chemistry to distinguish the oils that separate paraffin on cooling from those that
separate asphaltenes. The presence of paraffins is usually reflected in the paraf-
finic nature of the constituent fractions whereas a high asphaltic content corre-
sponds with the naphthenic properties of the fractions. This could lead to the mis-
conception that paraffin-base petroleum consists mainly of paraffins and that as-
phalt-base petroleum consists mainly of cyclic (or naphthenic) hydrocarbons. In
order to avoid confusion, a mixed base has been introduced for those oils that
leave a mixture of asphaltic petroleum and paraffins as residue from nondestruc-

tive distillation. A fourth class has also been suggested, the hybrid base; it includes
asphaltic oils that contain a small amount of paraffins. A simplified scheme has
been proposed by Speight [3] with paraffinic, naphthenic, aromatic, and asphaltic
petroleums as extremes (Fig. 1.7). It is indeed possible to characterize petroleum
semi-quantitatively in this manner.
An attempt to give the classification system a quantitative basis suggested
that petroleum should be called asphaltic if the distillation residue contained less
than 2% of parafms and paraffinic if it contained more than 5%. A division ac-
cording to the chemical composition of the 250 to 300°C fraction has also been
suggested (Table 1.2), but the difficulty in using such a classification is that in the
fractions boiling above 200°C, the molecules can no longer be placed in one group
because most of them are typically of a mixed nature.
Fig.1.7: Composition diagram for petroleum.
Purely naphthenic or aromatic molecules occur very seldom; cyclic com-

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

CI=473.7d - 456.8 + 48.640/T (1.2)
where T, in the case of a petroleum fraction, is the average boiling point, deter-
mined by the standard Bureau of Mines distillation method
d is the specific gravity.
Table 1.2: Petroleum classification according to chemical composition.

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

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

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

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

v is the Saybolt viscosity at 99°C
The viscosity-gravity constant is of particular value in indicating petroleum
of a predominantly paraffinic or cyclic composition. The lower the index number,
the more paraffinic the stock; for example, naphthenic lubricating oil distillates

have a vgc of 0.876 while the raffinate obtained by solvent extraction of lubricat-
ing oil distillate has a vgc of 0.840.
The UOP characterization factor is perhaps one of the more widely used of
the derived characterization or classification factors and is defined by the formula
K=TB"3/d (1.3)
where TB is the average boiling point in degrees Rankine (degrees Fahrenheit +

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

as:
• low sulfur oil containing not more than 0.5% of the sulfur, whereby the gaso-
line fraction contains less than 0.1% sulfur and diesel fraction less than 0.2%.
• sulfur petroleum containing over 0.5% but under 2% of the sulfur, whereby
the gasoline fraction contains less than 0.1 % sulfur and the diesel fraction
less than 1.0%.
• high sulfur petroleum containing over 2% of sulfur.
• low paraffinic petroleum containing under 1.5% of paraffins. This type of oil
can be used for production of jet and winter diesel fuels without
deparaffinization.
• medium paraffinic petroleum containing over 1.5% and under 6% of paraf-
fins. This type of oil can be used for production of jet and summer diesel fuels
without deparaffinization.
• high paraffinic petroleum containing over 6% of paraffins. This type of oil
can be used for production of diesel and jet fuels only after deparaffinization.
1.3 PRODUCTS FROM CRUDE OIL [2-4]
The list of products from petroleum is endless. Oil products fuel planes,
trains, cars, trucks, buses, and so on. Oil is also used to heat homes. Chemicals
made from oil are used to make products that range from makeup, toys, fabrics,
sneakers and football helmets to aspirin, toothpaste, deodorant, clothes, hair dryers
and lipstick to name just a few. Plastics made from oil are widely used in every-

thing from compact discs and video cassette recorders, to computers, television
sets, and telephones. In this chapter we will focus on petroleum fuels since it is
presently the most important power source.
Crude oil contains a wide range of hydrocarbons and other compounds
containing sulfur, nitrogen, etc. In the refinery, petroleum is distilled into various
fractions. Depending on the desired final products, these fractions are further proc-
essed and then blended to yield a wide variety of products.
Typical final products are:
• gases for chemical synthesis and fuel, liquified gases
• aviation and automotive gasoline
• aviation (jet) and lighting kerosene
• diesel fuel
• distillate and residual fuel oils
• lubricating oil base grades
• paraffin oils and waxes
Many of the common processes in the refinery are intended to increase the
yield of blending feedstocks for gasoline. As such, most modern fuels are repre-
sented by fuel fractions compounded from the products of many different proc-
esses.
Typical modern refinery processes for gasoline components include:
• Catalytic cracking
• Hydrocracking
• Isomerization
• Reforming
• Alkylation
1.3.1 Gasoline
In the late 19th century, the most suitable fuels for automobile use were coal
tar distillates and the lighter fractions from the distillation of crude oil. During the
early 20th Century, the oil companies were producing gasoline as a simple distil-
late from petroleum. On the other hand, automotive engines became vastly im-
proved and these required a more suitable fuel. Typical gasoline products in the
1920s had octane numbers (ratings) in the range 40-60. Tetraethyl lead was often
used to enhance the octane number.
Because sulfur in gasoline inhibited the octane-enhancing effect of the alkyl
lead, there was a restriction on the sulfur content of thermally cracked refinery
streams for gasoline. By the 1930s, it was determined that larger hydrocarbon
molecules had major adverse effects on the octane number of the gasoline, and
specifications consistent with the desired properties were developed.

The increase in the compression ratios of cars started in the 1950s. The
consequence was that such car engines required fuels with higher octane numbers.
Thus, octane number, lead levels, and vapour pressure increased whereas sulfur
and olefin contents decreased. Some new refining processes (such as hydrocrack-
ing), designed to provide hydrocarbon components with good lead response and
octane number, were introduced. Minor improvements were made to gasoline
formulations to improve yields and octane number until the 1970s, when unleaded
fuels were introduced to protect the catalysts that were also being introduced for
environmental reasons. From 1970 until 1990, there was a slow but progressive
change in the gasoline produced. Lead was being phased out. Lead levels de-
creased, octane number initially decreased as well, but vapor pressures continued
to increase while sulfur and olefins remained constant. The aromatic content in-
creased. In 1990, the US Clean Air Act started to force the implementation of
major compositional changes in gasoline. This resulted in the plummeting of the
vapor pressure and the increase in the oxygenate levels. These changes will con-
tinue into the 21st century as a way to minimize the polluting effect of the use of
gasoline as fuel in automobile engines.
The move to unleaded fuels continues worldwide. However, several coun-
tries have increased the aromatics content (by up to 50%) to replace alkyl lead.
These highly aromatic gasolines can lead to damage of elastomers and increased
levels of toxic aromatic emissions if is used without catalysts.
Gasoline as a fuel is composed of a mixture of various hydrocarbons, which
can be burnt to form water (H2O) and CO2. If combustion is not complete, carbon
monoxide (CO) is also formed.
The following main groups of hydrocarbons are contained in gasoline:
• saturated hydrocarbons or alkanes
• unsaturated hydrocarbons or olefins
• naphthene or cyclic hydrocarbons
• aromatics
• oxygenates
• other hetero-atom compounds
Gasoline contains over five hundred types of hydrocarbons that have be-
tween 3 to 12 carbon atoms in their structure. Gasoline has a boiling range from 30
to 180°C at atmospheric pressure. The boiling range is narrowing as the initial
boiling point is increasing, and the final boiling point is decreasing. Both these
changes are for environmental reasons.
Saturated hydrocarbons have the following major properties:
• Are thermally and chemically stable, it is the major component of leaded
gasolines.
• Tend to bum in air with a clean flame.

The octane number depends on branching and number of carbon atoms. Gen-
erally octane number is low for n-alkanes and high for the iso-alkanes (iso-
octane is assigned the octane number of 100).
The cyclic hydrocarbons all have the positive properties of the alkanes with
regard to thermal and chemical stability as well as good environmental properties.
In addition, they have a higher octane number in comparison to alkanes.
Alkenes or unsaturated hydrocarbons have the following major properties:
• Are chemically unstable.
• Tend to be reactive and toxic, but have high octane numbers.
Arenes or aromatics are characterized as follows:

• Gradually being reduced to less than 20% in the US.
• Tend to be more toxic than other hydrocarbons, but have the highest octane
ratings.
• Some countries are increasing the aromatic content (up to 50% in some super
unleaded fuels) to replace the alkyl lead octane enhancing additive.
Polynuclear aromatics are high boiling compounds, and are only present in
small amounts in gasoline. The simplest and least toxic polynuclear arene, naph-
thalene, is present in only trace amounts in traditional gasoline, and in even lower
levels in reformulated gasoline. The larger multi-ringed polynuclear arenes are
highly toxic, and are not present in gasoline.
Oxygenates contain oxygen that does not contribute to the energy content,
but because of their structure, provides a reasonable antiknock value. Thus, they
are good substitutes for aromatics. They also reduce the tendencies of the forma-
tion of toxic gases. Most oxygenates used in gasoline are either alcohols or ethers
that contain 2 to 6 carbon atoms per molecule. Alcohols have been used in gaso-
line since the 1930s whereas ether (such as methyl tertiary butyl ether (MTBE))
was first used in commercial gasoline in Italy in 1973 and in the US in 1979.
Oxygenates can be produced from fossil fuels or from biomass. MTBE is
produced by reaction of methanol with iso-butylene in the liquid phase over an
acidic ion-exchanger resin catalyst at 100°C. MTBE production has increased at
the rate of 10 to 20% per year.
Oxygenates are added to gasoline to reduce emissions. However, they can
only be effective if the hydrocarbon fractions are modified to utilize the oxygen-
ate's octane number and volatility properties. If the hydrocarbon fraction is not
correctly modified, oxygenates can even increase smog-forming and toxic emis-
sions both of which are undesirable. It should also be noted that oxygenates do not
necessarily reduce all toxins.
Initially, oxygenates were added to hydrocarbon fractions that were just
slightly modified unleaded gasoline fractions. These were known as "oxygenated"

gasolines. Since 1995, the hydrocarbon fraction has been significantly modified
resulting in "reformulated gasoline".
Oxygenates added to gasoline function in two ways. First, they have a high
blending octane number, and so can replace high octane aromatics in the fuel.
These aromatics are responsible for disproportionate amounts of CO and hydro-
carbons emissions during combustion. Oxygenates cause engines without sophisti-
cated engine management systems to move to the lean side of stoichiometry, thus
reducing emissions of CO (2% oxygen can reduce CO by 16%) and hydrocarbons
(2% oxygen can reduce hydrocarbons emissions by 10%). Other researchers have
observed that similar reductions occur when oxygenates are added to reformulated
gasoline and used on older and newer vehicles. They have also shown that, unfor-
tunately, NOx levels may increase, as may some regulated toxins.
On the other hand, on vehicles with engine management systems, the fuel
volume will be increased to bring the stoichiometric combustion to the preferred
optimum setting. It is to be noted that oxygen in the fuel cannot contribute energy.
Consequently, the fuel has less energy content. Thus, for the same efficiency and
power output, more fuel has to be burned. Therefore, the slight improvements in
combustion efficiency that oxygenates provide on some engines usually do not
completely compensate for the energy loss due to the presence of oxygen.
There are some other properties of oxygenates that have to be considered if
they are to be used as fuels. These relate particularly to (i) their ability to form
very volatile azeotropes that cause the fuel's vapor pressure to increase, (ii) the
chemical nature of the emissions, and (iii) their tendency to separate into a sepa-
rate water-oxygenate phase when water is present. These problems are solved
more successfully in the reformulated gasoline than in the original oxygenated
gasoline.
Table 1.3 shows some hydrocarbons in gasoline and their corresponding oc-
tane numbers.
The main characteristics of gasoline are:
• Vapor pressure and distillation classes. There are six different classes accord-
ing to location and/or season. As gasoline is distilled, the temperatures at
which various fractions are evaporated are recorded. Specifications define the
temperatures at which various percentages of the fuel are evaporated. Distilla-
tion limits include maximum temperatures at which 10% is evaporated (50-
70°C), 50% is evaporated (110-121°C), 90% is evaporated (185-190°C), and
the final boiling point (225°C). A minimum temperature for 50% evaporated
(77°C), and a maximum amount of residue (2%) after distillation. Vapor
pressure limits for each class (54, 62, 69, 79, 93, 103 kPa, respectively) are
also specified.
• Vapor lock protection classes. There are five classes for vapor lock protec-
tion. This classification depends on location and/or season. The limit for each
class is a maximum vapor-liquid ratio of 20 at one of the specified testing
temperatures of 41,47, 51, 56, or 60°C.

• Antiknock index. Limits are not specified, but changes in engine requirements
according season and location are discussed.
• Lead content
• Copper strip corrosion. This determines the ability to tarnish clean copper,
indicating the presence of any corrosive sulfur compounds.
• Maximum sulfur content. Sulfur adversely affects catalysts and fuel hydro-
carbon lead response. Sulfur may also be emitted as polluting sulfur oxides.
• Maximum solvent washed gum limits the amount of gums present in fuel at
the time of testing to 5 mg/100 mLs. The results do not correlate well with ac-
tual engine deposits caused by fuel vaporization.
• Minimum oxidation stability. This ensures that the fuel remains chemically
stable, and does not form additional gums during periods in the distribution
systems (can be up to 3-6 months). The test is conducted by heating the sam-
ple with oxygen inside a pressure vessel. The time required for a significant
oxygen uptake is measured to indicate minimum oxygen stability.
• Water tolerance. This is the highest temperature that causes phase separation
of oxygenated fuels. The limits vary according to location and month.
An understanding of the reasons for detonation makes it obvious that there
are two ways to improve the octane number of gasoline. It is possible to change
the composition of gasoline. However, this is a difficult and expensive method.
It is also possible to add additives that destroy peroxides. However, any "knock"
caused by the fuel will rapidly mechanically destroy the engine. The problem is
to identify economic additives which could be added to gasoline to prevent
knock effects. Originally, iodine was the best antiknock additive available, but
was not a practical gasoline additive, and was used as the benchmark. Later,
terra ethyl lead was added to the gasoline to improve the octane number.
Terra ethyl lead (C2H5)4Pb is an organometallic compound, which is well
soluble in hydrocarbons in the gasoline. At the temperatures of 200-250°C, this
substance is cracked to lead and four ethyl radicals CiHs'. All the compounds
formed prevent the formation of explosive compounds in gasoline, or promote
their fast destruction. However, the application of pure tetra ethyl lead was im-
possible. The formed lead deposits as a residue on the walls of the cylinder, and
further makes the working of the engine impossible. This is why, in practice,
tetra ethyl lead is mixed with various alkyl-halogens. At high temperature, alkyl-
halogens are cracked and react with lead to form volatile salts, which leave the
engine together with the exhaust gases.

Table 1.3: The average gasoline composition.
1 5% n-paraffins RON MON
n-pentane 62 66
n-hexane 19 22
n-heptane 0 0
n-octane -18 -16
n-decane -41 -38
n-dodecane -88 -90
n-tetradecane -90 -99
30% iso-paraffins
2-methylpropane 122 120
2-methylbutane 100 104
2-methylpentane 82 78
3-methylpentane 86 80
2-methylhexane 40 42
3-methylhexane 56 57
2,2-dimethylpentane 89 93
2,2,3-trimethylbutane 112 112
2 ,2 ,4-trimethylpentane 100 100
12% cycloparaffins
Cyclopentane 141 141
Methylcyclopentane 107 99
Cyclohexane 110 97
Methylcyclohexane 104 84
35% aromatics
Benzene 98 91
Toluene 124 112
ethyl benzene 124 107
meta-xylene 162 124
para-xylene 155 126
ortho-xylene 126 102
3-ethyltoluene 162 138
1 ,3,5-trimethylbenzene 170 136
1 ,2,4-trimethylbenzene 148 124
8% olefms
2-pentene 154 138
2-methylbutene-2 176 140
2-methylpentene-2 159 148
cyclopentene 171 126
1 -methylcyclopentene 184 146
1,3 cyclopentadiene 218 149
dicyclopentadiene 229 167
Oxygenates
methanol 133 105
ethanol 129 102
iso-propyl alcohol 118 98

Adding tetra ethyl lead appeared to be quite an effective method to im-
prove antidetonating properties of gasoline. The additive added in a very small
amount in gasoline allows the increase of the octane number by about 5 - 1 0
units. Unfortunately however, lead and tetra ethyl lead are very poisonous sub-
stances. If contacted with the skin, they can filter into the blood. The lead com-
pounds formed in engines falls on the ground and near vegetation. This can
produce tragic consequences for the ecology.
The alkyl leads rapidly became the most cost-effective method of enhancing
octane. Up until the late 1960s, alkyl leads were added to gasoline in increasing
concentrations to improve octane number. However, in later years, the use of tetra
ethyl lead was not encouraged. Presently in most countries of the world, the use of
tetra ethyl lead as an additive to gasoline is prohibited by law.
However, the need for gasoline with high octane number is ever increasing.
The next possible way to improve the octane number of gasoline is to mix it with
other compounds having high octane numbers. In the table above is shown that
oxygenates have very high octane number (over 100). It is known that in the US,
the so-called gasohol, a mixture of gasoline and alcohol, was used. In Europe
syntin was produced from CO2 and hydrogen. The product of this process includes
a mixture of different types of alcohol.
However, the most effective and ecologically sound additive to gasoline
nowadays is methyl tetra butyl ether ((CH3)3COCH3). This additive is well known
as MTBE. The octane number of MTBE is 135. The use of methyl tetra butyl
ether as the additive fortunately solved a problem that resulted from using alcohols
as the additive. In contrast to alcohols, MTBE is not soluble in water. It is known
that water in different amounts can be found in industrial reservoirs. Even gasoline
contains small traces of water. All alcohols are well soluble in water such that
alcohol can stay in water at the bottom of the reservoir during storage. MTBE is
insoluble in water and so this problem does not arise. Another problem with alco-
hol is that light alcohols (for example methanol) have a much lower heat of
combustion than gasoline. It means that the need of fuel in tanks of the cars
should be increased. MTBE has approximately the same fuel characteristics as
gasoline. Moreover the presence of oxygen in its structure essentially improves
the combustion process of gasoline in cylinders and reduces the contents of
products of incomplete combustion in the exhaust gas.
There is only one disadvantage of using MTBE. There is a shortage in the
production of MTBE in comparison to the need for high quality fuel for modern
cars. One more method to improve the antidetonating properties of gasoline was
introduced in the 1970s. In this method, the properties of gasoline were not
changed. Instead the working mechanism of the engine was changed. It was
introduced to make the engine capable of working with two different gasolines.
Because the highest danger of detonation in engine occurs only during the
forced working regime, it is rational to use two different gasolines in one engine:
the high quality gasoline for the forced regime of the engine and the gasoline
with low octane number for the stable working regime. It was shown that nor-

mally the engine works about 20% of the general working time in forced regime.
This means that by using two tanks in a car, one can save up to 80% of the high
quality gasoline by partly using low quality fuel. However, this method did not
become popular and therefore did not result in industrial production of cars with
dual tanks.
It is useful at this stage, close to the end of the chapter on gasoline, to men-
tion additional properties of gasoline of importance:
• Volatility. This affects evaporative emissions and derivability. It is a property
that is changed with location and season. For example, fuel for mid-summer
Arizona would be difficult to use in mid-winter Alaska. For this reason, the
US is divided into zones, according to altitude and seasonal temperatures. The
fuel volatility is adjusted accordingly. Incorrect fuel may result in difficult
starting in cold weather, carburetor icing, vapor lock in hot weather, and
crankcase oil dilution. Volatility is controlled by distillation and vapor pres-
sure specifications. The higher boiling fractions of the gasoline have signifi-
cant effects on the emission levels of undesirable compounds (hydrocarbons
and oxygen containing compounds), and a reduction of 40°C in the end boil-
ing point will reduce the levels of benzene, butadiene, formaldehyde and ac-
etaldehyde by 25%, and will also reduce hydrocarbons emissions.
• Combustion Characteristics. Gasoline contains a wide variety of hydrocar-
bons. Thus, the only significant variable that characterizes different gasoline
grades is the octane number. Most other properties are similar. There are only
slight differences in combustion temperatures (most are around 2000°C in
isobaric adiabatic combustion). It should also be noted that the actual tem-
perature in the combustion chamber is also determined by other factors, such
as load and engine design. The addition of oxygenates changes the pre-flame
reaction pathways and also reduces the energy content of the fuel. The level
of oxygen in the fuel is regulated according to regional air quality standards.
• Stability. Motor gasoline may be stored up to six months. As such, they must
not form gums during storage. Gums formed may precipitate. Gums are
formed due to oxidation and polymerization reactions involving unsaturated
hydrocarbons. Antioxidants and metal deactivators are added to prevent gum
formation due to these reactions.
• Corrosiveness. Sulfur in the fuel facilitates corrosion. The combustion of
sulfur containing fuels results in the formation of corrosive gases that attack
the engine, the exhaust as well as the environment. Sulfur also adversely af-
fects the alkyl lead octane response. Furthermore, it adversely affects the ex-
haust catalysts. However, the monolithic catalysts usually recover when the
sulfur content of the fuel is reduced. In this case, sulfur is considered to be an
inhibitor rather than a catalyst poison. The copper strip corrosion test and the
sulfur content specification are used to ensure fuel quality. The copper strip
test measures the active sulfur whereas the sulfur content reports the total sul-
fur present.

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

(for narrow kerosene fraction or Jet Al), 100-250°C (for wide kerosene fraction or
JP-4), or 170-315°C (for heavy kerosene, Russian standards). It contains about
20% aromatics. However, the aromatic content is usually reduced for high quality
lighting kerosene, as the aromatics reduce the smoke point. The other constituents
include 20 to 60% aliphatic compounds, 20 to 60% naphthenes and up to 1%
unsaturated compounds. The major use for kerosene today is as aviation turbine jet
fuels. Special properties are required for this application, including high flash
point for safe refueling (38°C for Jet Al), low freezing point for high altitude
flying (-47°C for Jet Al), and good water separation characteristics.
The quantity and quality of kerosene vary with the type of crude oil; some
crude oils yield excellent kerosene, but others produce kerosene that requires sub-
stantial refining and hydrotreatment. Kerosene is a very stable product, and addi-
tives are not required to improve the quality. Apart from the removal of excessive
quantities of aromatics, kerosene fractions may need only hydrotreatment if hy-
drogen sulfide is present. The kerosene fraction from shale oil is like the gasoline
fraction, which generally contains high amounts of nitrogen and oxygen. How-
ever, hydrotreatment will remove most of the nitrogen, but catalyst degeneration
can be quite severe.
Jet fuels must burn cleanly and remain fluid and free from wax particles at
the low temperatures experienced in high-altitude flight. The conventional freeze-
point specification for commercial jet fuel is -50°C. The fuel must also be free of
any suspended water particles that might cause blockage of the fuel system with
ice particles. Special-purpose military jet fuels have even more stringent specifica-
tions.
The quality of this fuel varies widely. This is why there is no universal jet
fuel. Instead, there very many different types of jet fuels. The main types for North
America and Russia are:
• Jet-A: This is a narrow cut kerosene product. This is the standard commercial
and general jet fuel available in the United States. It usually contains no addi-
tives but anti-icing chemicals may be added.
• Jet-Al: This is identical to Jet-A with the exception of its freezing point. It is
used outside of the US and is the fuel of choice for long haul flights where the

fuel temperature may fall to near the freezing point. It often contains a static
dissipator additive.
• Jet-B: This is a wide cut kerosene with lighter gasoline type naphtha compo-
nents. It is used widely in Canada. It contains a static dissipator and has a very
low flash point;
• JP-4: This is a military designation for a fuel like Jet-B but contains a full
additive package including corrosion inhibitor, anti-icing and static dissipator.
• JP-5: This is another military fuel. It has a higher flash point than JP-4 and
was designed for use by the US Navy on board aircraft carriers. It contains
anti-ice and corrosion inhibitors.
• JP-8: This is like Jet-Al with a full additive package.
• T-5: This is a Russian heavy jet fuel without any additives and had been used
for civil aviation. It has not been used any more since 1971.
• RT: This is a Russian hydroteated jet fuel with antioxidation additive ionol;
• T6: This is a Russian thermo-stabilized jet fuel made from the east sulfuric
petroleums with antioxidation additive ionol.
• T7: This is the same as the RT jet fuel without any additives.
• T8W: This is a Russian hydrotreated jet fuel without any additives.
1.3.3 Diesel
Diesel fuel is derived from petroleum. Diesel, gasoline and jet fuel are dif-
ferent cuts from the refining of petroleum. The difference is that diesel contains
heavier hydrocarbons with a higher boiling point than gasoline and jet fuel. The
term diesel fuel is therefore generic; it refers to any fuel mixture developed to run
a diesel-powered vehicle, i.e. engines with compression ignition engines.
Diesel is a hydrocarbon fraction that typically boils between 250-380°C.
Diesel engines use the cetane (n-hexadecane) rating to assess ignition delay. Nor-
mal alkanes have a high cetane rating, (n-Ci6=100) representing short ignition
delays. On the other hand, aromatics (alpha-methylnaphthalene = 0) and iso-
alkanes have low ratings representing long ignition delays. Because of the size of
the hydrocarbons, the low temperature flow properties control the composition of
diesel. Consequently, additives are usually added to prevent filter blocking in
cooler temperatures. There are usually summer and winter diesel grades. Envi-
ronmental legislation is reducing the amount of aromatics and sulfur permitted in
diesel. Their emission as well as those of small particulates are considered as pos-
sible carcinogens and are also known to cause other adverse health effects.
Cetane number is one of the most widely known quality characteristics of
diesel fuel. It is important to not confuse cetane number with cetane index.
The fuel in a diesel engine is ignited by the high-temperature and high-
pressure air created in the cylinder as the piston nears the end of the compression
stroke. In contrast, fuel in gasoline engines is ignited by a spark plug.

Cetane number is therefore a measure of the power with which diesel fuel is
ignited during the compression stroke. The number is determined using a specified
laboratory test engine. Cetane index is calculated using an equation involving the
density and the distillation curve of the fuel. Consequently cetane index cannot be
increased and improved by cetane-improving additives because the equation does
not account for the type and amount of cetane-improving additive in the fuel.
However, cetane index can be modified through changes in the density or distilla-
tion curve of the fuel.
The time between the beginning of fuel injection and the start of combustion
is called "ignition delay". As stated earlier, higher cetane number fuels result in
shorter ignition delays, providing improved combustion, lower combustion noise,
easier cold starting, faster warm-up, less smoke, and in many engines, reduction of
emissions.
In most diesel engines, the ignition delay is shorter than the duration of
injection. Under these circumstances, the total combustion period can be divided
into the following four stages:
• Ignition delay
• Rapid pressure rise
• Constant pressure or controlled pressure rise
• Burning on the expansion stroke
Rapid pressure rise results from the large number of ignition points and the
accumulation of fuel during the ignition delay period. Following this stage, the
rate of combustion can be controlled to a much greater degree by controlling the
injection rate since the fuel is being injected into the flame. Because the rapid
pressure rise represents uncontrolled and inefficient combustion, it is necessary to
limit the ignition delay to a minimum. This limitation can be accomplished me-
chanically by the selection of a spray pattern configuration properly tailored to the
combustion chamber.
The nature of the fuel is also an important factor in reducing ignition delay.
Physical characteristics such as viscosity, density, and medium boiling point are
influencing parameters. Hydrocarbon composition is also important as it affects
both the physical and combustion characteristics of the fuel. Ignition delay charac-
teristics of diesel fuel are of primary importance since they directly influence the
interval of uncontrolled combustion during the injection and, as such, the overall
engine performance.
The next important parameter of diesel fuel is stability or storage stability.
As fuel ages, it can become unstable and form insoluble particulates that accumu-
late and eventually end up on the fuel filter. For the most part, instability involves
the chemical conversion of precursors to compounds of higher molecular weight
with limited fuel solubility. The precursors are certain nitrogen and/or sulfur con-
taining compounds, organic acids, and reactive olefins. The conversion process
often involves oxidation of the precursors. Certain dissolved metals, especially

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

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

members of this class are used to improve engine performance in different time
frames. Any benefit that is provided by a cetane number improver is immediate,
whereas that provided by detergent additives or lubricity additives is typically seen
over the long term.
Cetane number improvers or diesel ignition improvers reduce combustion
noise and smoke. The magnitude of the benefit varies among engine designs and
operating modes, ranging from no effect to readily perceptible improvement.
2-Ethylhexyl nitrate (EHN) is the most widely used cetane number im-
prover. It is also sometimes called, "octyl nitrate". EHN is thermally unstable and
decomposes rapidly at the high temperatures in the combustion chamber. The
products of decomposition help initiate fuel combustion and, thus, shorten the
ignition delay period as compared with that of the fuel without the additive.
The increase in cetane number from a given concentration of EHN varies
from one fuel to another. It is greater for a fuel whose natural cetane number is
already relatively high. The incremental increase gets smaller as more EHN is
added. Thus, there is little benefit to exceed a certain concentration. EHN typically
is used in the concentration range of 0.05 to 0.4 mass % and this may yield a 3 to 8
cetane number benefit. A disadvantage of EHN is that it decreases the thermal
stability of the fuels.
Other alkyl nitrates as well as ether nitrates and some nitroso compounds,
have also been found to be effective cetane number improvers. However, they are
not currently used commercially. Di-tertiary butyl peroxide has recently been
introduced as a commercial cetane number improver.
Injector cleanliness additives and crankcase lubricant can form deposits in
the nozzle area of injectors. The extent of deposit formation varies with engine
design, fuel composition, lubricant composition, and operating conditions. Exces-
sive deposits upset the injector spray patterns and these hinder the fuel-air mixing
process. In some engines, this leads to increased emissions and fuel utilization.
Ashless polymeric detergent additives can clean the fuel injector from deposits.

These additives are composed of a polar group that bonds to deposits and deposit
precursors and a non-polar group that dissolves in the fuel. Thus, the additive can
redissolve deposits that already have formed and reduce the opportunity for de-
posit precursors to form deposits.
Lubricity additives are used to compensate for the poor lubricity of severely
hydrotreated diesel fuels. They contain a polar group that is attracted to metal
surfaces, causing the additive to form a thin surface film. The film acts as a
boundary lubricant when two metal surfaces come in contact. Two additive
chemicals, fatty acids and esters, are typically used for this purpose.
Smoke suppressants are combustion catalysts. This class of additives is
usually composed of organometallic compounds. Adding these compounds to fuel
can reduce the emissions of pollutants that result from incomplete combustion.
Smoke suppressants that are based on organometallic compounds of iron, cerium,
platinum are in common use.
The following additives belong to the fuel handling additives:
Antifoam additives prevent formation of foam. Diesel fuels tend to be prone
to foam formation when they are pumped into the tanks. Most antifoam additives
are organosilicone compounds and are typically used at very low concentrations
(about lOppm).
De-icing additives prevent ice formation from the free water in diesel fuel. If
free water in diesel freezes, the resulting ice crystals can plug fuel lines and filters.
Low molecular weight alcohols or glycols can be added to diesel fuel to prevent
ice formation. The alcohols/glycols preferentially dissolve in the free water, giving
the resulting mixture a lower freezing point than that of pure water.
Low temperature operability additives lower a diesel fuel's pour point and
improve its cold flow properties. Most of these additives are polymers that interact
with the wax crystals that form in diesel fuel when it is cooled below the pour
point. The added polymers mitigate the adverse effect of wax crystal formation on
fuel flow by modifying their size, shape, and degree of agglomeration. The poly-
mer-wax interactions are fairly specific. As such, a particular additive generally
will not perform equally well in all fuels. Unfortunately, the best additive for a
particular fuel cannot be predicted; it must be determined experimentally.
Drag reducing additives are used by pipeline companies to increase the
volume of product they deliver. These high molecular weight polymers reduce
turbulence in fluids flowing in a pipeline. This can increase the maximum flow
rate by up to 40%. When the additive modified product passes through a pump,
the additive is broken into smaller molecules that have no effect on product per-
formance in engines.
Fuel stability additives prevent the formation of gums that can lead to injec-
tor deposits or particulates that can plug fuel filters and the fuel injection system.
The need for a stability additive varies widely from one fuel to another. Stability
additives typically work by blocking one step in a multi-step reaction pathway of
gum formation. Because of the complex chemistry involved, an additive that is
effective in one fuel may not work as well in another. If a fuel needs to be stabi-

lized, it should be tested to select an effective additive and treatment rate. The best
results are obtained when the additive is added immediately after the fuel is manu-
factured.
Antioxidants prevent the oxidation of the fuel. Antioxidants work by inter-
rupting the chain in free radical chain reaction by blocking the free radicals. Phen-
ylenediamines are the most commonly used antioxidants.
Stabilizers prevent acid-base reactions in the diesel fuel. Basic amines are
usually used as stabilizers. They react with weakly acidic compounds with the
formation of products that remain dissolved in the fuel and do not react further.
Metal deactivators prevent the catalytic influence of the metals on reactions
that can lead to its instability in diesel fuel. They are typically used in concentra-
tions of up to 15 ppm.
Dispersants disperse the formed insoluble products in diesel fuel, preventing
them from clustering into aggregates large enough to plug fuel filters or injectors.
Dispersants are typically used in concentrations of up to 100 ppm.
Biocides prevent the growth of bio-organisms. The best choice is an additive
that dissolves in both the fuel and the water such that it can attack the microbes in
both phases. Biocides are typically used in concentrations of up to 600 ppm. A
biocide may not work if a heavy biofilm has accumulated on the surface of the
tank or other equipment, because then it does not reach the organisms living deep
within the film.
Demulsifiers aid in the separation of fuel from water. Normally, hydrocar-
bons and water separate rapidly and cleanly. But if the fuel contains polar com-
pounds that behave like surfactants and if free water is present, the fuel and water
can form a stable emulsion. Any operation that subjects the mixture to high shear
forces, like pumping the fuel, can stabilize the emulsion. Demulsifiers are surfac-
tants which can destabilize the emulsions and allow the fuel and water phases to
separate. Demulsifiers are used in concentrations of up to 30 ppm.
Corrosion inhibitors prevent the oxidation of the metal pieces in diesel en-
gines. Since most petroleum pipes and tanks are made of steel, the most common
corrosion is the formation of rust in the presence of water. The fuel is thus con-
taminated with rust particles, and these can plug fuel filters as well as increase fuel
pump and injector wear. Corrosion inhibitors attach to metal surfaces and form a
film that prevents attack by corrosive agents. They typically are used in concentra-
tions of up to 15 ppm.
Modem diesel fuel can be produced from sources other than petroleum.
Recently, attention has been focused on biodiesel. This is a cleaner-burning fuel
made from natural and renewable sources such as vegetable oils. Just like petro-
leum diesel, biodiesel can operate in combustion-ignition engines. Essentially no
engine modifications are required, and also biodiesel maintains the payload capac-
ity and range of diesel.
The use of biodiesel in a petroleum diesel engine results in substantial re-
duction of unburned hydrocarbons, carbon monoxide, and formation of participate
matter, i.e. in reduction of emission of pollutants. Emissions of nitrogen oxides are

either slightly reduced or slightly increased depending on the duty cycle and test-
ing methods. The use of biodiesel decreases the solid carbon fraction of particulate
matter (since the oxygen in biodiesel enables more complete combustion to CO2)
and eliminates sulfate fraction (as there is no sulfur in the fuel), while the soluble
and hydrocarbon fraction stay the same or are increased. Therefore, biodiesel
works well with new technologies such as catalysts (which reduce the soluble
fraction of diesel particulate but not the solid carbon fraction), particulate traps,
and exhaust gas recirculation (leads potentially to longer engine life due to less
carbon).
Biodiesel has physical properties that are very similar to those of petroleum
diesel. As mentioned earlier, emission properties, however, are better for biodiesel
than for petroleum diesel.
Biodiesel is produced by a process called "trans-esterification". Vegetable
oil or animal fat is first filtered, then pre-processed with alkali to remove free fatty
acids. It is then mixed with an alcohol and a catalyst. The oil's triglycerides react
to form esters and glycerol, which are then separated from each other and purified.
Much of the current interest in biodiesel production comes from vegetable
oil sources such as soybean (in the USA), canola oil (in Canada) and rapeseed oil
(in Europe) because the vegetable oil producers are faced with excess production
capacity, product surpluses, and declining prices.
Waste animal fats and used frying oils (known as 'Fellow grease') are also
potential feedstocks. These are cheaper than soybean oil and are being considered
as a way to reduce feedstock costs.
1.3.4 Residual Fuel
Many marine vessels, power plants, commercial buildings and industrial

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

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

perature of around 10°C above the pour point if wax deposition is to be
avoided. Some waxy residual fuels have pour points between 40 and 45°C.
• Carbon residue varies from 10 to 22% depending on the residual fuel. The
carbon residue provides information on the coke or carbonaceous deposits
which result from combustion of the fuel. Fuels which are rich in carbon
prove more difficult to burn fully, resulting in increased deposits in the com-
bustion and exhaust spaces. Fuels produced from thermal cracking residues
show a higher carbon/hydrogen ratio and, hence, high percentage carbon resi-
due. Carbon residue can only be an indicator of potential deposit-forming ten-
dency of the fuel. Thus, operating experience with different fuels at different
engine loadings and conditions should be recorded to determine individual
engine tolerance levels to high carbon fuels.
• Ash ranges from 0.1 to 0.2%. The ash content of a fuel is a measure of the
amount of inorganic noncombustible material it contains. Some of the ash-
forming constituents occur naturally in crude oil; others are present as a result
of refining or contamination during storage or distribution. For instance, it
could be due to the presence of compounds of the following elements: vana-
dium, sodium, calcium, magnesium, zinc, lead, iron, nickel.
• Water content varies from 0.5 to 1%. Water is introduced into residual fuels
by poor storage. The standards allow water up to a maximum of 1% in resid-
ual fuels. However, the majority of fuel deliveries have water contents below
0.5%. The problems with high water levels in fuel can be complex and in-
clude sludging of fuel tanks, filter blockage, corrosion of fuel injection
equipment, exhaust valve corrosion, etc.
• Sulfur ranges from 3.5 to 5%. The main problem resulting from the use of
high sulfur fuels is corrosion. During the combustion process, sulfur dioxide
(SO2) and sulfur trioxide (SO3) are produced. Depending upon engine condi-
tions such as excess air, temperature and pressures, these gases will convert to
sulfurous acid (H2SO3) and sulfuric acid H2SO4), to some extent. These acids
are formed when the gases exist below their dew points. For the formation of
sulfurous acid, the favorable temperature should range between 50 and 60°C
whereas for sulfuric acid, it should range between 110 and 150°C. These ac-
ids cause corrosion in the low temperature zones of engines and boilers.
Hence, their effect is often referred to as "cold end corrosion".
• Vanadium content ranges from 150 to 600 mg/kg. The vanadium content of
fuels from different countries varies considerably and is directly related to the
crude oil source. Problems associated with high vanadium have been ad-
dressed under ash, sodium and sulfur. These problems are largely overcome
by good engine design, and correct fuel treatment. To prevent these problems
additives are widely used.

1.3.5 International Standards for Fuels
MS ISO 8216/0 — 8216/4 have been developed as standards for fuel classi-
fication in the framework of international standardization.
MS ISO 8216/0 establishes the general classification of petroleum fuels
(fuels of class F). There are five categories of products which are included in class
F. These categories depend on the type of fuel.
A detailed classification of fuel groups with regard to conditions of applica-
tion, type, properties and characteristics establishes the groups of products for each
category and these are provided by separate parts of ISO 8216. Thus, parts desig-
nated as ISO 8216/1, ISO 8216/2, ISO 8216/4 which have been developed are
based on these standards. The Russian standards are included in the international
standards system:
• ISO 8216/0-86 - Classification. Part 0. This is a general classification of pe-
troleum fuels (Class F). The Russian equivalent for this standard is COST
28577.0-90.
• ISO 8216/1-86 - Classification. Part 1. This covers the categories of fuels for
sea engines. The Russian equivalent for this standard is COST 28577.1-90.
• ISO 8216/2-86 - Classification. Part 2. This covers the categories of fuels for
gas turbines for applications in industry and for sea engines. The Russian
equivalent for this standard is GOST 28577.2-90.
• ISO 8216/4-86 - Classification. Part 3. Group 1. This covers liquefied petro-
leum gases. The Russian equivalent for this standard is GOST 28577.3-90.
Table 1.4 shows the international classification of petroleum fuels.

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

Table 1.4: Classification of petroleum fuels (class F).
Category Characterization
G Gas.
Gas of petroleum origin consisting basically of methane and ethane
L Liquefied Gas.
Liquefied gas of petroleum origin consisting basically of propane, propene and both
butane and butene
P Liquid Fuels.
Fuels of petroleum origin excluding liquefied petroleum gases. They include gaso-
line, jet fuels, gas oil and diesel fuel.
Heavy distillates can contain small quantities of residues
R Residual Fuels.
Petroleum fuels containing residual fractions of a distillation process
C Petroleum Coke.
Hard fuels of petroleum origin produced in cracking processes, and consisting
basically of only carbon
The requirements for British jet fuels for civil aircraft are established by the
specification D, Eng. RD (DERD) 2494. Previously, it was developed for military
aircraft. This is fuel of the kerosene type with a freezing temperature of-47°C.
The list of control operations (AFQRJOS) is a basis for the international
requirements for jet fuels.
Fuel for turbines that are made and delivered according to AFQRJOS should
correspond to the most rigid requirements of the following specifications:
• The standard of the British Defense Ministry DBF STAN 91-91/ Editions 2
(DERD 2494) from May, 1996
• The standard specification ASTM D 1655
• The managing material of the international association of air transport (IATA)
from December, 1994
The jet fuel that corresponds to the requirements of AFQR-JOS in the

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

the cooling agent of the forging parts, support the filing of parts and prevent the

fusion of work piece and tool. The main functions of lubricating oils and lubri-
cants are:
• Reducing friction. Putting lubricating oil between moving metal surfaces
decreases friction. This results in energy conservation and significantly less
wear.
• Reducing wear. Lubricating oils reduce mechanical wear (caused by abrasion
and erosion) and chemical wear (corrosion caused by combustion acids and
water). Wear is influenced by various factors which can be divided into the
fields of tool, rough part, forming machine, lubricant and actual contact area.
Possible ways to reduce wear lie in the increase of annealing durability as
well as in the hardness of the surface, for example through nitriding, and ap-
plication of mostly ceramic wear resistant layers on the tool surface. Also,
massive wear reduction can be achieved by lowering the tool temperature.
• Cooling. Lubricating oil cools the mechanical components by helping to
remove heat and decreasing the amount of heat produced (by reducing fric-
tion).
• Ensuring leak tightness. Lubricants ensure leak tightness between the me-
chanical components such as the cylinder and the piston, improving compres-
sion and producing better engine performance.
• Removing impurities. Lubricants keep engine components clean by prevent-
ing the formation of deposits and suspended impurities (dust, combustion
residue, engine wear particles) that then build up on the oil filter.
Properties differ from one lubricant to another. However, the one compo-
nent that lubricants have in common is that they are composed of a main ingredi-
ent called the lubricating base. The lubricating base may be petroleum derived or
synthetic. The lubricating base accounts for 75 to 85% of the lubricant. There are
three different classes of lubricating bases that are used in modern oil industry:
• Mineral bases are manufactured from petroleum that has undergone a variety
of complex separation processes. They are the most commonly used for both
automotive and industrial applications.
• Synthetic bases or synthetics are products created by the chemical reaction of
several ingredients. Two main classes are used for lubricants: esters and syn-
thetic hydrocarbons (in particular polyalphaolefms manufactured from ethyl-
ene). These products have excellent physical properties and exceptional ther-
mal stability.
• Semi-synthetic oils are obtained from mixing both types of bases (generally
70 to 80% of mineral oil and 20 to 30% of synthetic oil).
The development of modern lubricants and their correct use are especially
important as these have substantial economic consequence on the use of these
devices. Optimally chosen lubricant brings saving of energy needed for machine
work, conserves the parts of these devices, reduces wear and tear, reduces the

maintenance time and shortens the overhaul intervals, which can take away mil-
lions of dollars from industry. The characteristics of lubricants are improved by
special substances called additives. In the current industrialized society, the use of
lubricants without these enhanced characteristics is no longer conceivable. Lubri-
cating oil additives are synthetic active substances, which are added to the basic
oils in order to give the products the desired characteristics or properties. This is
why, additives are the next main compounds of the oils (15 to 25%).
The following main classes of additives are available:
• Viscosity index improvers. These make the oil a sufficiently low viscous fluid
when cold (to facilitate starting) by lowering the pour point to between -45
and -45 °C (depending on the oil), and to viscous fluid when hot (to prevent
the contact between moving mechanical components). This class of additives
are polymers which are introduced into a lubricating base to produce a rela-
tive greater increase in viscosity when hot than when cold.
• Antiwear additives. These reinforce the antiwear action of the lubricant. The
main family of antiwear additives are alkyl-zinc dithiophosphates and numer-
ous phosphorus derivatives.
• Antioxidants. These eliminate or slow down lubricant oxidation, increasing
the time between oil changes through improved resistance to high tempera-
tures. Dithiophosphates that are used as antiwear additives are also excellent
antioxidants. Other chemical families such as substituted phenols and aro-
matic amines are also used.
• Detergents. These prevent the formation of deposits and varnish on the hottest
areas of the engines (such as ring grooves). Calcium or magnesium metal salts
from main chemical families such as alkylaryl-sulfonate, alkylphenate and al-
kylsalicylate are used as detergents.
• Dispersing agents. These maintain in suspension all the solid impurities
formed during engine operation. The solid impurities include unburned resi-
due, gums, sludge, diesel soot, deposits cleaned by detergents. Usually polar
compounds from the alkenylsuccinimides, succinic esters or their derivatives
are used as dispersing additives.
• Alkalinity additives. Those that neutralize combustion acid residue from fuels
are made primarily for diesel engines. The main compounds of this class of
additives are phenols and salicylates (which are natural alkaline), and sul-
fonates. In the case of sulfonates, their neutralizing property can be reinforced
by adding basic salts such as carbonates or hydroxides.
• Corrosion inhibitors. These prevent the corrosion of ferrous metals under the
combined effects of water, atmospheric oxygen and a number of oxides
formed during combustion. Mainly alkaline or alkaline-earth sulfonates, neu-
tral or alkaline (Na, Mg, Ca) salts, fatty acids or amines, alkenylsuccinic acids
and their derivatives are used as corrosion inhibitors.
• Antifreeze agents. These enable lubricating oils to retain good fluidity at low
temperatures (from -15 to -45°C). The main classes of this type of additive are

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

wear and tear is minimal in this type of friction. However, there is still very high
need for lubricants for fluid friction, even though it is economically unjustifiable
to use this type of friction in big industrial devices. The most popular types of
friction in industrial devices are mixed and film friction. Mixed friction is present
as a combination of fluid friction and hard surface friction. The tear by mixed
friction is obviously higher than by fluid friction, because there is contact between
surfaces at some points. The optimal for the industry is the so-called film friction.
In this kind of friction, a thin film of surface-active substance is formed. This film
protects the surfaces from direct contact and high wear and tear.

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

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

cals. Such additives often contain aromatic compounds in their struc-
ture with relatively weak O-H and N-H bonds. Examples of such com-
pounds are phenols, naphthols, aromatic amines, aminephenols, and di-
amines. This type of additive has strong reducing properties and reacts
quickly with peroxide radicals.
2. Antioxidants which prevent oxidation by reaction with alkyl radicals.
The additives react quickly with alkyl radicals. Examples of such addi-
tives are hynones, iminehynones, methylhynones, stable nitrogen oxide
radicals, and molecular iodine. Alkyl radicals react quickly with oxy-

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

the action of a mixture is less than the sum of the actions of each anti-
oxidants, antagonism results.
In the last type of antioxidants we learn that an important property of anti-

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

carrying out the following specific tests:
• Oxidation tests. The combined effects of ambient oxygen and temperature
affect lubricant aging; this phenomenon is known as oxidation. In laboratory
oxidation tests, temperatures are selected in accordance with those encoun-
tered during equipment operation.
• Corrosion tests. One of the lubricant's main functions is protection against
corrosion. Accordingly, the reactions between the lubricant and various metal
surfaces need to be determined and, where appropriate, modified.
• Chemical compatibility tests. These tests are used to determine the behavior
of various materials when they are in contact with oil. For example, specific
tests are conducted to ensure the compatibility of a lubricant with seals.
• Storage stability tests. Some lubricant combinations are formed by the asso-
ciation of products that are not fully miscible in oil. In this case, the final sta-
bility that represents changes during storage needs to be verified.
• Dispersion tests. The purpose of these tests is to determine the ability of an oil
to maintain in suspension solids that are likely to form during operation. For
example, combustion engines produce carbon residues, some of which are
found in the oil. The latter must be able to maintain the soot in suspension and
prevent deposits that could result in fouling or even clogging.
• Shear tests. These tests determine how well lubricants withstand mechanical
loads that can cause the molecules of some components to break up.
• Pressure tests. There is currently no device available that can directly measure
the ability of an oil film to withstand pressure. Various properties (film

strength, high pressure, extreme pressure) can only be assessed using bench
tests in the laboratory to determine their effects on other oil properties. The
same types of tests are carried out for greases as for oils, using special de-
vices: four-ball machine, Timken, etc.
• Laboratory tests are supplemented by bench tests on machines very similar to
real ones and which operate under controlled conditions.
• Engine tests are designed to determine the behavior of oils on either gasoline
or diesel engines. Each test is performed in such a way as to highlight one or
more lubricant properties. No single engine test is available that enables all
properties to be tested simultaneously.
• Bench tests are carried out either on standard automotive multi-cylinder en-
gines or on single-cylinder engines.
• Gear tests check the internal cohesion and pressure withstanding properties of
lubricants on real gears. Various methods are used depending on the type of
gear and test conditions.
1.4.1 International Standards for Lubricating Oils
1.4.1.1 Industrial oils
The most fully developed standards system of classifications of industrial

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

Table 1.5: Classification of lubricant materials, industrial oils and related prod-
ucts. Division into groups according to area of application.
Group Application
A Open systems
B Formless systems
C Gear wheels
D Compressors (including cooling)
E Engines of internal combustion
F Spindles, bearings and couplings connected to spindles

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

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

Table 1.7: API classification for motor oils by its operational properties and
areas of application.
Class Application area

Category S (Oils for gasoline engines)
SA Engines working at light conditions
SB Engines working at moderate conditions
SC Engines working with high loadings (models released before 1964)
SD Engines working at heavy conditions (models released before 1968)
SE Engines working at heavy conditions (models released before 1 972)
SF Engines working at heavy conditions reformed gasoline
SG Engines released since 1989
SH Engines released since 1 994
SJ Engines released since 1 997
Category C (Oils for diesel engines)
CA Engines working at moderate loadings with low sulfuric fuel
CB Engines working at high loadings with sulfuric fuel
CC Engines working in heavy conditions
CD Engines working in heavy conditions with high sulfuric fuel
CD-II The same for old diesel engines
CE Engines working in heavy conditions
CF-4 Engines released since 1 990
CF-2 Improved characteristics of CD-II
CG-4 Engines released since 1 994
Table 1.8: CCMC classification for motor oils by its operational properties and
areas of application.
Class | Area of application
Oils for gasoline engines
Gl Engines, working in usual conditions
G2 Engines of modern cars working in hard conditions
G3 Engines of modern cars, with high viscous properties
04 Engines of modern cars, used for driving with high-speed
G5 Engines of sports high-speed automobiles
Oils for diesel engines
Dl Engines working under usual conditions
D2 Engines working under heavy conditions
D3 Engines working under especially heavy conditions
PD-1 Diesel engines of the cars
D4 Engines working in heavy conditions
D5 Engines working in especially heavy conditions
PD-2 Engines with turbo-pressurization for cars

Since January of 1996, the ACEA classification has practically replaced the
CCMC classification. The ACEA classification was developed as an integration of
standards of European organizations: CEC, ATC and ATIEL. It was adopted in
1998.
The ACEA classification is applicable to different oil products for different
gasoline engines (classes Al-96, A2-96, A3-96), diesel engines (classes Bl-96,
B2-96, B3-96) and diesel trucks (classes El-96, E2-96, E3-96). After the changes
and additions, new classes Al-98 and A3-98 for gasoline engines, Bl-98, B2-98,
B3-98 and B4-98 for diesel engines of cars and E4-98 for diesel engines of trucks
have been included.
A new system known as the European monitoring system of the qualities of
motor oils (EELQMS) has been developed to cover the requirements for European
motor oils. EELQMS includes the requirements of registration of tests, data col-
lecting and change of compositions. All tests should be registered in the European
registration center (an independent organization, possessing experience in the
control of the order of the performance of tests) before they are performed.
The car firms in the USA and Japan cooperating with ILSAC have formu-
lated requirements for motor oils for gasoline engines of cars. In ILSAC classifica-
tion, there are two classes which are designated as GF-1 and GF-2. They are close
to API classes SH and SJ, respectively.
1.4.1.3 Transmission oils
The requirements for quality of transmission oils intended for various tasks
are numerous. This is why there is the need for classification.
Similar to motor oils, there are two systems of classification: SAE with
regard to viscosity and API with regard to operational properties.
According to SAE classification, tractor transmission oils are divided into 6
classes (Table 1.9) with regard to viscosity.
A hyphenated viscosity class implies that the oil is suitable for all seasons
for the specific climatic zone. For example, the oil with SAE 75W-90 classifica-
tion has the low temperature properties of the viscosity class SAE 75W (i.e. dy-
namic viscosity of the oil does not exceed 150 Pa*s at the temperature of -40°C).
At a positive temperature, the kinematic viscosity corresponds to the viscosity of
the class SAE-90, (i.e. at 100°C the kinematic viscosity is 13.5-24 mm2/s).
The distinctions in designs of transmission units and conditions of their
operation create distinctions in the requirements for operational properties of the
oil.
The development of API classification was based on this principle. As such,
the oils are divided according to the type and loading degree of the gears where the
oil is applied (Table 1.10).

Table 1.9: The SAE classification for transmission oils with regard to viscosity.
Viscosity class The maximum temperature Kinematic viscosity
of the achievement of the Min Max
dynamic viscosity of 150
Pa*s, °C
winter oils
75W ^0 4.1
SOW -26 7.1
85W -12 22.1
summer oils
90 13.5 24
140 24 41
250 41
The SAE and API classifications give only the general characteristic of oils
without consideration of all parameters of quality. The complete requirements for
physical, chemical and operational properties of the oils and their allowable limit-
ing values are given in the specifications. In the countries of Western Europe and
the USA, transmission oils are produced with two types of specifications:
• Specifications of firms making automobiles
• Military specifications for oils for supply to the armed forces of both the USA
and NATO are made
Both specifications include the requirements for physical, chemical and

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

kinds of oils from GL-1 up to GL-6. On the other hand, military specifications are
only applied to GL-4 and GL-5.
These specifications provide the check for all parameters of quality require-
ments that are specified.

In the USA and the countries of Western Europe, the widest application has
been achieved by the military specifications from the USA:
• MIL-L-2105 (1959 is replaced by MIL-L-2105B)
• MIL-L-2105B (1973 is replaced by MIL-L - 2105C)
• MIL-L-2105C (1987 is replaced by MIL-L-2105D)
• MIL-L-2105D (since 1987)
In USA in 1995, a new military specification MIL-PRP-2105E that unites

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

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

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Parti

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

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1.1 HISTORY AND NATURE OF PETROLEUM

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The most important compounds of the class of pentacyclic naphthenes are

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

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

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1.1.1 Origin of Petroleum

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1.1.2 Oil Formation in the World's Oceans

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Fig. 1.2: Anticline traps.

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Fig. 1.4: Oil entrapment in a limestone reef.

1.1.3 Modern Concept of Formation of Petroleum

The characteristic feature of the modern concept of petroleum formation is

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1.1.3.1 Crude oil prospecting

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1.1.3.2 Drilling and crude oil extraction

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Fig. 1.6 Example of pumping extraction.

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

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

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

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1.1.4.1 Dangerous fogs

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1.1.4.2 Black oceans

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

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1.2 GENERAL PROPERTIES AND CLASSIFICATION OF

1.2.1 Fractions and Chemical Composition of Petroleum

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

• Boiling begins -140°C - gasoline fraction

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The residue after atmospheric distillation is called "atmospheric residue".

For further processing to fuel fractions: