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Chapter - 1
INTRODUCTION
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1.1. Petroleum (Crude Oil)
The word petroleum derived from the Latin petra and oleum, means literaf
oil and refers to hydrocarbon that occurs widely in the sedimentary rocks in the
form of gases and liquids. Petroleum is often called crude oil. It is also called a
fossil fuel because it was formed from the remains of tiny sea plants and animals
that died millions of years ago. Petroleum is perhaps the most important substance
consumed in modern society. It provides not only raw materials for ubiquitous
plastics and other products but also fuel for energy, industry, heating and
transportation. Crude oil is one of the world’s treasures because of its importance
in our lives.
Crude oil is naturally occurring, toxic, flammable liquid consisting complex

mixture of hydrocarbons of various molecular weights and other organic
compounds that are found in geological formation beneath the earth’s surface. It is
recovered mostly through oil drilling. It is refined and separated, most easily by
boiling point, into a large number of consumer products, from petrol and kerosene
to asphalt and chemical reagents used to make plastics and pharmaceuticals.
Petroleum plays a significant, even critical role in the modern industrial world.
Petroleum products and petrochemicals affect almost every aspect of our
civilization and the quality of our lives as individuals, including transportation,
food, clothing, shelter and recreation.
The supply, production and consumption of petroleum influence national

economy and security issues and have a bearing on global politics and
international relationship-nations even fight war over petroleum. The amount of
time required for oil and gas to form is not known precisely. Since virtually no
petroleum is found in rocks younger than one to two million years old, geologist
infer that the process is comparatively slow. Even if it took only a few tens of
thousands of years, the world’s oil and gas resources are being used up much faster
1
Chapter -1 Introduction
than significant new supplies can be produced by geologic processes. Therefore, oil
and natural gas are considered as non-renewable energy sources.
The production and use of fossil fuels raise environmental concerns. A global
movement toward the generation of renewable energy is therefore under way to
help meet increased energy needs. Currently, petroleum is among our most
important natural resources. We use gasoline, jet fuel, and diesel fuel to run cars,
trucks, aircraft, ships and other vehicles. Home heat sources include oil, natural
gas, and electricity, which in many areas are generated by burning natural gas.
Petroleum and petroleum-based chemicals are important in manufacturing plastic,
wax, fertilizers, lubricants, and many other goods. Different types of petroleum
can be used in different ways. Refineries separate different petroleum products by
heating petroleum to the point where heavy hydrocarbon molecules separate from
lighter hydrocarbons. As a result, each product can be isolated and used for a
specific purpose without waste. Thus, tar or asphalt, the dense, nearly solid
hydrocarbons, can be used for road surfaces and roofing materials. Waxy
substances called paraffin can be used to make candles and other similar products.
And less dense, liquid hydrocarbons can be used for engine fuels. Fossil fuels are of
great importance because they can be burned (oxidized to carbon dioxide and
water), producing significant amounts of energy. The use of coal as a fuel predates
recorded history. Coal was used to run furnaces for the melting of metal ore. Semi
solid hydrocarbons from seeps were also burned in ancient times, but these
materials were mostly used for waterproofing and embalming. Commercial
exploitation of petroleum, largely as a replacement for oils from animal sources
(notably whale oil) for use in oil lamps began in the nineteenth century. Natural
gas, once flared-off as an un-needed by-product of petroleum production, is now
considered a very valuable resource. Heavy crude oil, which is much more viscous
than conventional crude oil, and tar sands, where bitumen is found mixed with
sand and clay, is becoming more important as sources of fossil fuel. Oil shale and
similar materials are sedimentary rocks containing keroên, a complex mixture of
2
high-molecular weight organic compounds, which yield synthetic crude oil when
heated (pyrolyzed). These materials have yet to be exploited commercially. These
fuels are employed in internal combustion engines, fossil fuel power stations and
other uses. Prior to the latter half of the eighteenth century, windmills or
watermills provided the energy needed for industry such as milling flour, sawing
wood or pumping water, and burning wood or peat provided domestic heat. The
wide-scale use of fossil fuels, coal at first and petroleum later, to fire steam
engines, enabled the industrial revolution. At the same time, gas lights using
natural gas or coal gas were coming into wide use. The invention of the internal
combustion engine and its use in automobiles and trucks greatly increased the
demand for gasoline and diesel oil, both made from fossil fuels. Other forms of
transportation, railways and aircraft also required fossil fuels. The other major use
for fossil fuels is in generating electricity and the petrochemical industry.
1.2. Petroleum Formation
Petroleum, also called crude oil, is a thick, flammable, yellow-to-black coloured

liquid. Petroleum was first found oozing out of rocks on Earth's surface. Today,
most scientists agree that oil was formed from the remains of plants and tiny
animals that settled to the bottom of ancient oceans. These remains or sediments
were buried by layers of mud and sand. Gradually, over millions of years, the
weight of these accumulating layers built up great pressure and heat. The
sediments packed together and became rock. The organic (once living) remains
were changed into kerofen, a waxy substance that forms oil and natural gas. Most
of the world's petroleum is more than 100 million years old, and is thus called a
fossil fuel.
Fossil fuels formed from ancient organisms that died and were buried under layers
of accumulating sediment. The additional sediment layers built up over organic
deposits and most organic debris is destroyed at the Earth's surface by oxidation or
by consumption by microorganisms. Organic material that survives to become
3
buried under sediments or deposited in other oxygen-poor environments begins a

series of chemical and biological transformations that may ultimately result in
petroleum, natural gas, or coal [1, 2f Many such deposits occur in sedimentary
basins and along continental shelves. Sediments may accumulate to the depths of
several thousand feet in a basin, exerting pressures up to one hundred million
pascal (tens of thousands of pounds per square inch) and temperatures of several
hundred degrees on the organic material. Over millions of years, these conditions
can chemically transform the organic material into petroleum, natural gas, coal, or
other types of fossil fuels [3].
Unlike coal, which stays in one spot unless moved by Earth's shifting crust, oil
slowly migrates upward through cracks and pores, or tiny holes, in nearby rocks.
Eventually the oil reaches a solid layer of rock and becomes trapped underneath in
a reservoir (pool). Natural gas often occurs in association with oil. Most of the
world's petroleum reservoirs lie deep underground in structures called anticlines-
gently folded layers of rock that form an arch above the deposit. Petroleum can
also be trapped by fractured layers (or faults), salt formations, and stratigraphic
(rock) traps. Some oil is also contained in clay and sands.
1.3. Petroleum Composition

Petroleum is not a uniform material, its chemical and physical composition can
vary not only with the location and age of the oil field but also with the depth of
the individual well. Indeed, two adjacent wells may produce petroleum with
markedly different characteristics. On a molecular basis, petroleum is a complex
mixture of hydrocarbons with small amounts of organic compounds containing
sulphur, oxygen and nitrogen as well as compounds containing metallic
constituents, particularly vanadium, nickel, iron and copper [3_7].
Crude oil varies greatly in appearance depending on its composition. It is usually

black or dark brown. Petroleum is a mixture of a large number of different
4
hydrocarbons; the most commonly found molecules are paraffin or wax,
naphthenes, aromatics and more complicated chemical like asphaltene. Each
petroleum variety has a unique mix of molecules, which defines its physical and
chemical properties, like colour and viscosity.
Table 1.1: Elementary composition of crude oil
Element %by wt.
Carbon 83.0-87.0%
Hydrogen 10.0-14.0 %
Nitrogen 0.1-2.0%
Oxygen 0.05-1.5%
Sulphur 0.05-6.0%
Metals <1000 ppm
The alkanes, also known as paraffin or wax, are saturated hydrocarbons with
straight or branched chains which contain only carbon and hydrogen and have
the general formula CnH2n+2. They generally have from 5 to 40 carbon atoms per
molecule, although trace amounts of shorter or longer molecules may be present
in the mixture.
The alkanes from pentane (C5H12) to octane (CsHis) are refined into petrol, the ones
from nonane (C9H20) to hexadecane (C16H34) into diesel fuel and kerosene (primary
component of many types of jet fuel), and the ones from hexadecane upwards
into fuel oil and lubricating oil. At the heavier end of the range, paraffin wax is an
alkane with approximately 25 carbon atoms, while asphalt has 35 and up, although
these are usually cracked by modem refineries into more valuable products. The
shortest molecules, those with four or fewer carbon atoms, are in a gaseous state at
room temperature. They are the petroleum gases. Depending on demand and the
cost of recovery, these gases are flared off, sold as liquefied petroleum gas under
pressure, or used to power the refinery's own burners. During the winter, butane
5
(C4H10) is blended into the petrol pool at high rates, because butane's high vapour
pressure assists with cold starts. Liquefied under pressure slightly above
atmospheric, it is best known for powering cigarette lighters, but it is also a main
fuel source for many developing countries. Propane can be liquefied under modest
pressure, and is consumed for just about every application relying on petroleum
for energy, from cooking to heating to transportation.
The cycloalkanes, also known as naphthenes, are saturated hydrocarbons which
have one or more carbon rings to which hydrogen atoms are attached according to
the formula CnELn. Cycloalkanes have similar properties to alkane but have higher
boiling points.
The aromatic hydrocarbons are unsaturated hydrocarbons which have one or
more planar six-carbon rings called benzene rings, to which hydrogen atoms are
attached with the formula CnHn. They tend to bum with a sooty flame, and many
have a sweet aroma. Some are carcinogenic.
Asphaltenes are operationally defined as the non-volatile and polar fraction of
petroleum that is insoluble in n-alkanes (i.e. pentane or heptane). As a result,
asphaltenes constitute a solubility class of crude oil components, rather than a

chemical class. The molecular weight, polarity and aromaticity of precipitated
asphaltene generally increase -with increasing carbon number of n-alkane
precipitant. Asphaltene are characterized by fused ring aromaticity, small aliphatic
side chains, and other elements including sulphur, oxygen, nitrogen and metals
such as vanadium and nickel. The heteroatom accounts for a variety of polar
groups such as aldehydes, carbonyl, carboxylic acid and amide, which are found in
the asphaltene molecules. The aromatic carbon content of asphaltene is typically
in the range of 40 to 60%, with a corresponding H/C atomic ratio of 1.0-1.2. A
large percentage of these aromatic carbon rings are interconnected in the
molecular structure and, consequently, the asphaltene molecules appears flat or
6
Chapter - 1 Introduction
planar. Yen and co-workers [8' 91 proposed a macrostructure model, where the
asphaltene was depicted as stacks of flat sheets of condensed aromatic systems,
which was interconnected by sulphide, ether and aliphatic chains. Espinat et al. !10]
suggested the asphaltene molecules to be disc-like with polyaromatic fused ring
cores containing polar functional groups. It is currently accepted that asphaltene
consist of aromatic compounds with tt-tt interactions, which undergo acid-base
interactions and self associate hydrogen bonding t11- 12f Figure 1.1 shows a
suggested asphaltene structure [13).
Figure 1.1: Hypothetical asphaltene molecules
Several major problems associate with the recovery and refining of petroleum [2' 14~
181 are related to the aggregation and precipitation of asphaltene. Investigations
have shown that asphaltene particles may self-associate, and form aggregates in
the presence of aromatic hydrocarbons [19).
Resins are defined as the non-volatile and polar fraction of crude oil that is soluble
in n-alkanes (i.e. pentane) and aromatic solvents (i.e. toluene) and insoluble in
liquid propane. They are structurally similar to asphaltene; on the other hand,
molar mass is lower, H/C ratio higher, and the heteroatom content lower. Long et
al. [201 showed that once resins were removed from the crude by adsorption
chromatography, the remaining oil phase could no longer stabilize the asphaltene.
7
Chapter-1 Introduction
1.4. General Properties of Crude Petroleum

1.4.1. Density, Specific Gravity and API (American Petroleum Institute) gravity
In early days of the petroleum refineries, density and specific gravity were used to:
1. Indicate crude oil quality and

2. Correlate with aromatic character, naphthenic character and paraffinic
character.
The specific gravity is highest for aromatics and lowest for paraffin. The API
gravity reverses this relationship. Thus the density and specific gravity of crude oil
are two properties that have found wide use in the industry for preliminary
assessment of the character of the crude oil.
In the early years of the petroleum industry, density was the principal
specification for petroleum and refinery products; it was used to give a very
approximate estimation of the gasoline and the kerosene present in the crude .oil.
However, the derived relationship between the density of petroleum and its
fractional composition were valid only if they were applied to a certain type of
petroleum and lost some of their significance when applied to different types of
petroleum. Nevertheless, density is still used to give a rough estimation of the
nature of petroleum and petroleum products.
The use of density or specific gravity has largely been replaced by the API gravity
as the preferred property. It is one criterion that is used in setting prices for
petroleum. The API gravity is related to specific gravity by following formula.
Degree API = (141.5/Specific gravity at 15 °C) - 131.5
ASTM D70, ASTM D71, ASTM D287, ASTM D941, ASTM D1217, ASTM D1298,
ASTM D1480, ASTM D1481, ASTM D1555, ASTM D1657, ASTM D4052, IP 235,
IP 160, IP 249 and IP 365 methods were used to determine density, specific
gravity and API gravity C21’22^.
8
1.4.2. Distillation
It gives the idea about the distillation behaviour of the crude oil. A measured
amount of the sample is distilled under atmospheric condition up to 300 °C. The
various fractions or cuts (at each multiple of 25 °C) are collected and subjected to
series of lab tests. The obtained results used for further processing of the crude
(blending of fractions, chemical treatment) for the finished products [23l
1.4.3. Pour point

Pour point is defined as the temperature at which the crude oil sample will no
longer flow when held at a horizontal position in a test jar for about 5 seconds, due
to formation of a wax gel network. Pour point is an indicator of the gelling
potential of the crude sample. Its measurement is believed to be affected by factors
such as wax content, wax crystal size and number, pressure and solution gas, as
well as the thermal history of the crude oil [24l Fast cooling rates tend to raise the
pour point, while slow cooling rates yield lower pour point values. Pour point is
measured primarily to determine the flow characteristics of crude oil. It is a
temperature expressed in a multiple of 3 °C, under which the oil is no longer move
when the plane of its surface is held vertical for 5 seconds. The pour point is then
taken as 3 °C above the temperature of cessation of flow. It may however be
pointed out that this test is carried under static conditions p5].
1.4.4. Cloud point

The point defining when paraffin separates into solid phase from the bulk oil
liquid phase is a very important thermodynamic parameter in wax deposition
studies. It is a very important parameter that affects wax precipitation and is basic
to the wax deposition problem. It has been reported that Theologically, crude oil is
a low-viscosity Newtonian fluid but exhibit non-Newtonian behaviour at low
temperature, a phenomenon attributed to paraffin wax solid-phase separation.
This point of separation, defined by temperature, happens to be unique for a
particular pressure as well as oil composition, and is interchangeably referred to as
9
Chapter -1 Intrpduction
wax appearance temperature or cloud point[26-27> 28l Cloud point is of importance
since it defines the temperature at which a cloud or haze of crystals appears in the
oil under prescribed conditions. Cloud point is an indicator of the tendency of the
oil to plug filters or small orifices at cold operating temperatures. ASTM D2500,
test method is used for determining cloud point of petroleum oils.
1.4.5. Bottom sediment and water content

The water and sediment content of crude oil, results principally from production
and transportation practices. Water, with its dissolved salts, may occur as easily
removable suspended droplets or as an emulsion. The sediment dispersed in crude
oil may be comprised of inorganic minerals from the production horizon or from
drilling fluids, as well as from scale and rust from pipelines and tanks used for oil
transportation and storage. Usually water is present in far greater amounts than
sediment, but collectively, it is unusual for them to exceed 1 % of the crude oil on
a delivered basis [28l Water and sediment can foul heaters, stills and exchangers
and can contribute to corrosion and to deleterious product quality. Also, water and
sediments are principal components of the sludge that accumulates in storage
tanks and must be disposed of periodically in an environmentally acceptable
manner. Knowledge of water and sediment content is also important in
determining net volumes of crude oil in sales, exchanges and taxation and custody
transfers. A number of test methods exist for the determination of water and
sediment. They are ASTM D4007, ASTM D473, ASTM D4807, ASTM D4006,
ASTM D4377 and ASTM D4928.
1.4.6. Water content by Dean and Stark method
The centrifuge method (ASTM D4007) does not measure the water content
accurately. However, it can be determined accurately by Dean and Stark method
[29). A measured volume of sample is refluxed with an equal volume of liquid
carrier, preferably toluene. The carrier liquid distils into a graduated receiver
carrying with the water. The separated water is measured for water content.
10
1.4.7, Salt content
Crude oil contain small amount of chlorides of sodium, calcium and magnesium
due to contact of crude oil with oil field brines paI. The salt content of crude oil is
highly variable and results principally from production practices used in the field
and, to a lesser extent, from its handling aboard tankers bringing it to terminals.
The bulk of the salt present will he dissolved in the crude oil itself. Salt may be
derived from reservoir or formation waters or from other waters used in secondary
recovery operations. Aboard tankers, ballast water of varying salinity may also he
a source of salt contamination. Salt in crude oil may be deleterious in several ways.
Even in small concentrations, salts will accumulate in stills, heaters and
exchangers, leading to fouling that requires expensive cleanup. More importantly,
during flash vaporization of crude oil, certain metallic salts can be hydrolyzed to
hydrochloric acid. The hydrochloric acid evolved is extremely corrosive,
necessitating the injection of a basic compound, such as ammonia, into the
overhead lines to minimize corrosion damage. Salts and evolved acids can also
contaminate both overhead and residual products, and certain metallic salts can
deactivate catalysts. The salt content in the crude is determined by using ASTM
D3230 and ASTM D6470 methods.
1.4.8. Wax content
To study rheology, measurement of solid wax content of crude oil is necessary.

High content of wax in crude oil affects the fluidity of oil. The wax content in the
crude oil is determined by M ethyl ethyl ketone (MEK) or acetone precipitation
technique. In this method, oily fraction of crude oil separated (by dissolving
asphaltene and resin by acid treatment) and precipitating the wax with the help of
ethyl alcohol and MEK, and cooling the mixture at -20 °C. The precipitated wax is
filtered out, washed thoroughly, dried and weight accurately[30].
The wax content is also determined by filtration. The oil is crystallized at given
temperature and treated with a dewaxing solvent (MEK, elichloroethylene,
11
Butanol) for ease of the filtration. The wax residue is repeatedly washed with
solvent (maintained at same temperature) until any colour in the wax has been
removed. A low temperature is chosen (-21 °C) for getting maximum amount of
wax lightly to crystallize under operating conditions and to minimize the
dissolution of the wax by the washing solvent however no solvent completely
rejects wax and hence each method would give different wax content result
depending on temperature, solvent and degree of washing.
1.4.9. Asphaltene content
Asphaltene are the organic molecules of highest molecular mass and carbon-
hydrogen ratio normally occurring in crude petroleum and petroleum products
containing residual material. They may give problems during storage and handling
if the suspension of asphaltene molecules is disturbed through excess stress or
incompatibility. They are also the last molecules in a product to combust
completely, and thus may be one indicator of black smoke propensity. Their
composition normally includes a disproportionately high quantity of the sulphur,
nitrogen and metals present in crude petroleum or petroleum products. ASTM
D6560 method is used for determination of asphaltene content in crude petroleum
and petroleum products (31].
1.4.10. Viscosity
Viscosity is the measure of a fluid resistance to flow. The viscosity of oil is a
measure of the oil’s resistance to shear [32). A high viscosity implies a high
resistance to flow while a low viscosity indicates a low resistance to flow. Viscosity
varies inversely with temperature. Viscosity is also affected by pressure; higher
pressure causes the viscosity to increase. With increasing temperature the viscosity
decreases. There are two types of viscosity: kinematic viscosity and dynamic
(absolute) viscosity. The more common is kinematic viscosity, which is the
absolute viscosity, divided by the density of the oil being tested. Kinematic
viscosity is expressed in centistokes (cSt), which is measured by the time taken for
12
fixed volume of oil to flow through a capillary tube. When viscosity is determined
by directly measuring shear stress and shear rate, it is expressed in centipoises (cP)
and is referred to as the absolute or dynamic viscosity. Viscosity is very important
property of oil because it affects the rate at which spilled oil will spread, the
degree to which it will penetrate shoreline substrates, and the selection of
mechanical spill countermeasures equipment. ASTM D445, ASTM D4486, ASTM
D2161, ASTM D2170 and ASTM D88 methods used for the determination of
viscosity of crude oils.
1.5. Rheology and Flow Behaviour of Crude Oil

Rheology is the science which focuses on the deformation of matter resulting from
the application of a force [33). The force can be applied in various ways: as a
tension, a compression, a shearing process, or some combination of three. An
understanding of rheology and ability to measure rheological properties, is
necessary before rheology can be controlled, and rheology control is essential for
the manufacture and handling of many materials e.g. foods, cosmetics, plastics,
paints, drilling fluid, crude oil etc.
The terms and descriptors associated with rheology are explained below in detail.
Deformation is the relative displacement of points of a body. It can be divided into
two types: Flow and Elasticity. Flow is irreversible deformation; when the stress is
removed, the material does not revert to its original position. This means that
work is converted into heat. Elasticity is reversible deformation, the deformed
body recovers its original shape and the applied work is largely recoverable. A
liquid is a material that continuous to deform as long as it is subjected to a shear
stress. The shear stress is a force applied tangentially to the material. To make an
incompressible fluid flow, a shear stress must be applied. Fluids include both gases
and liquids. Here the focus on the liquid. In a liquid, shear stress produces a sliding
of one layer over another, resulting in a stack-of-card type flow.
13
Consider a liquid placed between two parallel plates with area A as shown in
Figure 1.2. The top plate is moved with constant velocity V, by the action of a
shearing force F, while the bottom plate is fixed. Within this context, shear stress
T, is defined as the force per unit area F/A. If the variation in velocity between the
plates is constant, the shear rate y is the velocity difference between the plates
divided by the distance between them, h.
Figure 1.2: Shearing motion in a fluid between two parallel plates
For a liquid under shear the rate of deformation or shear rate is a function of the
shearing stress. The original exposition of this relationship is Newton’s law, which
states the ratio of shear stress to the shear rate is constant, i.e. the viscosity. For a
Newtonian fluid the viscosity is defined by Newton’s law of viscosity.
t=FY --------------------- (1)

The fluid viscosity p represents the resistance of the fluid to shearing force, and is
called the dynamic viscosity.
The kinematic viscosity is defined as,
K=p/p -------------—.-(2)
Where p = density of fluid in kg/m3
14
Chapter -1_______ Introduction
1.5.1. Classification of fluids
Fluids are normally classified into four categories, according to the relationship
between the shear stress and shear rate.
1) Newtonian Fluids
2) Time-independent non-Newtonian Fluids
3) Time-dependent non-Newtonian Fluids
4) Viscoelastic Fluids
Shear Mate
Figure 1.3: Rheological behaviour of various types of non-Newtonian fluids
1) Newtonian fluids.
Newtonian fluids follow the simple rheological equation known as Newton’s law
of viscosity (Eq. 1). The magnitude of the viscosity is not dependent on shear rate
or time. Its rheological behaviour (shear stress versus shear rate) is shown in
Figure 1.3. It shows a linear relationship and passes through the origin. Water and
mineral oils are common Newtonian liquids.
2) Time-independent non-Newtonian fluids
Non-Newtonian fluids are only type of fluid which does not obey Newton’s law of
viscosity (Eq. 1). The shear stress is a non-linear function of the shear rate. Figure
15
Chapter -1_____________________________________ Introduction
1.3 shows the rheological behaviour of several types of fluids. The viscosity of a
time-independent non-Newtonian fluid is dependent on the shear rate I34].
Depending on how the apparent viscosity changes with shear rate the flow
behaviour is characterized as follows:
• Shear thinning
The apparent viscosity of the fluid decreases with increasing shear rate. This
type of behaviour is also referred to as “pseudo plastic” and no initial stress
(yield stress) is required to initiate shearing. A number of non-Newtonian
materials are in this category, including grease, molasses, paint, starch and
many dilute polymer solutions.
• Shear thickening
The apparent viscosity of this fluid increases with increasing shear rate and no
initial stress is required to initiate shearing. This type of behaviour is also
referred to as “dilatant”. Beach sand mixed with water and peanut butter are
examples of dilatants liquids. Dilatants liquids are not as common as pseudo
plastic liquids. Dilatant rheological behaviour is also shown in Figure 1.3.
• Viscoplastic Quids
Viscoplastic materials are fluid that exhibits a yield stress. Below a certain
critical shear stress there is no permanent deformation of the fluid and it
behaves like a rigid solid. When that shear stress value is exceeded, the material
flows like a fluid. Bingham plastics are a special class of viscoplastic fluids that
exhibit a linear behaviour of shear stress versus shear rate once the fluid begins
to flow. An example of a plastic fluid is toothpaste, which will not flow out of
the tube until a finite stress is applied by squeezing.
3) Time-dependent non-Newtonian fluids
For these kinds of fluids, their present behaviour is influenced by what happened
to them the recent past. These fluids seem to exhibit a “memory” which fades with
16
time. The apparent viscosity of the fluid depends on a number of properties

including shear rate and the history of the shearing process. Depending on how
the apparent viscosity changes with time the flow behaviour is characterized as:
• Thixotropic
A thixotropic liquid will exhibit a decrease in apparent viscosity over time at a

constant shear rate. Once the shear stress is removed, the apparent viscosity
gradually increases and returns to its original value. When subjected to varying
rates of shear, a thixotropic fluid will demonstrate a “hysteresis loop”. Drilling
mud and cement slurries are among the many materials which can exhibit
thixotropic behaviour.
• Rheopectic
A rheopectic liquid exhibit a behaviour opposite to that of a thixotropic liquid,

i.e. the apparent viscosity of the liquid will increase over time at a constant
shear, rate. Once the shear stress is removed, the apparent viscosity gradually
decreases and returns to its original value. Rheopectic fluids are rare. Examples
include specific gypsum paste and printers inks.
4) Viscoelastic fluids
These materials exhibit both viscous and elastic properties. The rheological
properties of such a substance at any instant of time will be a function of the
recent history of the material and cannot be described by simple relationship
between shear stress and shear rate alone, but will also depend on the time
derivatives of both of these quantities. Typical examples of viscoelastic material
are bread dough, polymer melts and egg white.
1.5.2. Viscoplastic materials and yield stress concept

A viscoplastic material possesses a yield stress which must be exceeded before
significant deformation can occur. In limiting cases, a viscoplastic material may
flow and deform throughout the domain it occupies if the stress is everywhere
17
above the yield stress in the control volume of interest; on the other hand, it may
not flow at all if the stress is everywhere below this value. Such materials include
suspension and fine particle slurries including paint, pastes and foodstuffs.
A number of empirical relations have been proposed to account for the behaviour
of viscoplastic materials. The three most widely used are the Bingham, Casson and
Herschel-Buckley equations. The simplest and most widely used model is the two-
parameter model proposed by Bingham [35].
T=Ty + pPy | r\> Ty --------------------- (3)
y= 0 | rj^Ty --------------------- (4)
The Bingham model takes into account two parameters, the yield stress, Ty, and the
plastic viscosity, pPto fully characterize the material rheology. Note that once the
fluid flows, the plastic viscosity defines the rate of change of the excess shear stress
T- Ty with the shear rate y, shear stress with shear rate. In contrast, the apparent
viscosity is the ratio of the shear stress to the shear rate, and in this case it
approaches the plastic viscosity at very high shear rates. Figure 1.4 shows how two
Bingham materials could have one identical parameter and a very different second
parameter. These materials would consequently exhibit different flow behaviours.
18
• Apparent viscosity
Strictly speaking, only Newtonian fluid possesses the properties of viscosity and
that the consistency of the various non-Newtonian fluids is only defined by
their unit shear stress Vs shear rate curves. Notwithstanding this, the term
“Apparent viscosity” is frequently applied to non-Newtonians. The concept of
apparent viscosity has been adopted to describe the viscous properties of non-
Newtonians. Apparent viscosity is the ratio of shear stress to shear rate at a
specified shear rate (or shear stress). The apparent viscosity of Newtonian fluid
is the same as its viscosity: the apparent viscosity of Bingham plastic and
pseuodoplastic decrease with increasing rate of shear (to the limiting value).
The apparent viscosity gives very little information of the rheological nature of
the fluid or the way in which consistency may change with rate of shear.
• Plastic viscosity
Plastic viscosity is usually described as that part of resistant to flow caused by
mechanical friction. Particularly, it is affected by:
1) Solid concentration
2) Size and shape of solids
3) Viscosity of the fluid phase
An increase in plastic viscosity generally means an increase in percent volume
of solids, a reduction in the size of solid particles or a combination of these. Any
increase in the total surface area of the solid exposed will be reflected in an
increase on plastic viscosity.
• Yield value
When waxy crude is allowed to cool, paraffin will crystallize out causing the
entire mass of crude oil to gel. To initiate the flow again, a finite pressure is
required. This pressure is known as yield value or yield stress. Thus, yield value
19
is a shear stress required for setting solidified oil in motion. The pressure Po at
which the first flow is observed may be used for calculating yield stress, to.
to = PoD/4L ---------------------- (5)
Where,
to= Yield stress (Dyne/cm2)
Po= Pressure at which the first flow is observed (Dyne/cm2)
D= Diameter of the tube (cm) L= Length of the tube (cm)
The yield value of a gel of waxy crude oil in a given pipeline is one of the most
important factors influencing the restart of pipelines. For waxy crude oil yield
stress is inverse function of temperature. With the application of yield stress to the
crude below its pour point, the wax gel structure in oil starts to breakdown as flow
begins. The value of this yield stress depends on a large extent whether the oil is
cooled under static condition or dynamic condition. The value of yield stress is
higher for statically cooled oil. Thus, yield value gives the important information
about the flow of crude oil below its pour point and restarting of pipelines after
the shutdown.
1.6.Transportation of Crude Oil
For the storage of crude oil producing from the well with naturally occurring
ingredients like water and natural gas huge storage tanks are installed near the oil
fields. Different plants have to be prepared to separate water, sediments and
natural gas from crude oilt36]. The crude oil from here has to be transported to the
refinery. We can’t use crude oil as it comes out of the ground because petroleum is
a complex mixture of hydrocarbons of various molecular weights and other
organic compounds. We must change it into fuels that we can use. The first stop
for crude oil is at an oil refinery. A refinery is a factory that processes oil. The
refinery cleans and separates the crude oil into many fuels and products. The most
20
Chapter -1
important one is gasoline. Other petroleum products are diesel
rn&tfrn
1 pr^^^ ,
and jet fuel. Industry uses petroleum to make plastics and many otêt
\ V
-
p.
1.6.1. Transportation
Crude oil produced from the field through oil well has to be transported to the
refinery to convert it into the valuable products. Crude oil is transported by any of
the following means t37'38!.
1) Pipeline transportation
2) Tanker transportation
Figure 1.5: Pipeline transportation of crude oil
Crude oil production is done on a large scale and the oil fields are scattered via a
huge area. The oil produced is stored in storage tanks and demulsified to decant
the water produced with the oil. From this end the crude is sent to refinery mainly
by tankers and pipeline. As production is mostly in high quantity it is difficult to
store it and transport it by tankers so the known best way to transport crude oil is
through pipeline (Figure 1.5). Though the installation of pipeline is highly
expensive procedure but once it is layer down it becomejcheaper with time and is
21
safe method. It is the best protected system against environmental conditions.
Transportation by pipeline is used through the world as it has got its own
advantages. It is most suitable and secures way to transport the oil from field to the
refinery at a long distance. Further maintenance cost is very low than the
transportation by tankers. Moreover the transportation of the huge quantity of oil
is not possible for long distance by tankers. So preference is given to transport
crude oil through pipeline.
1.6.2. Problems during transportation
Crude oil is a complex mixture of saturates (paraffin/waxes), aromatics,
naphthenes, asphaltenes and resins. Among these components, high molecular
weight paraffins (interchangeably referred to as waxes) and asphaltenes are
typically responsible for production and transportation problems in pipeline
systems. At reservoir temperatures (70-150 °C) and pressures (50-100 mPa), wax
molecules are dissolved in the crude oil. However, as the temperature decreases,
the temperature of crude oil flows through a pipeline eventually decreases below
its cloud point or wax appearance temperature because of the heat loses to the
surroundings. The solubility of wax decreases drastically as the temperature
decreases and wax molecules start to precipitate out of the crude oil. Wax
problems will become more severe and extensive in winter season.
The flow assurance problems incurred by the precipitation of wax molecules
during the production and transportation in the field pipelines are:
1) Wax deposition in flow conditions and
2) Wax gelation and restart problem after shut down
1.6.2.1. Wax deposition in Sow conditions
Wax deposition occurs when paraffin components in crude oil (alkanes with
carbon number >20) precipitate and deposit on the cold pipeline wall when the
inner wall temperature falls below the cloud point temperature (solubility limit).
22
If preventive methods for wax deposition e.g. insulation of pipeline, injection of
wax inhibitor, or combination of both are not successful, a wax gel layer grows
rapidly in thickness and impedes the flow of oil due to the flow restriction as
shown in Figure 1.6.
Figure 1.6: Deposition of wax in pipeline
Once the wax deposition start to impede the production and transportation due to
the flow restriction, corrective methods to remediate the wax deposition are
generally necessitate. One of the most commonly corrective method used in the
field is pigging. In pigging, a pig (a solid object with diameter smaller than the
inner diameter of the pipe) passes through the pipeline to scrape off the wax
deposit as shown in Figure 1.7 [39l However, the pigging method cannot efficiently
be utilized without a proper wax deposition prediction.
Figure 1.7: Pigging method to remove wax deposits from pipelines
23
Another notable remediation technique is to use a fused chemical reaction with
controlled heat emission [39_431 to remove the wax deposit as shown in Figure 1.8
[39l However, in order to successfully use this technique, it is critical to know the
thickness profile and the wax fraction of the deposit as a function of axial location
and time. If this technique is to be used on inaccurate information on the location
of wax deposit and its wax fraction, there could be unwanted local high
temperature in the pipeline due to the failure of re-dissolving wax deposit.
Figure 1.8: Use of a fused chemical reaction to remediate the paraffin plugging in
pipelines
1.6.2.2. Wax gelation and restart problem after shut down
Whereas wax precipitation during oil flow results in wax deposition and flow
restriction, wax precipitation during a production shutdown results in problems
when attempting to restart the flow. If the transportation in pipeline is stopped
due to a planned maintenance or an emergency situation such as severe weather
conditions on the off-shore platforms t44’45!, the temperature and solubility of wax
decrease and wax molecules precipitate out of liquid phase in a static condition. In
the absence of flow, the precipitation of wax molecules leads to the formation of a
wax-oil gel as shown in a cross-polarized microscope photo in Figure 1.9 that
could encompass the entire cross-section of the pipe. In order to restart flow and
to recover the steady state flow, this wax-oil gel in the pipeline must be broken.
24
This restart flow problem is especially challenging when the ambient temperature
is below the pour point temperature or the gelation temperature [461. In order to
prevent this risk and to enhance the restart ability after shut down, chemical
agents which can depress the pour point temperature and/or weaken the strength
of the wax-oil gel can be used. When assessing the restart ability, it is necessary to
estimate the pressure required to break the plug of wax-oil gel. The pressure
required to break and to restart flow is proportional to the strength of the gel
(yield stress) and the aspect ratio of pipeline.
1.7. Mechanism of Wax Deposition

The mechanism of wax deposition is considered here with respect to the lateral
transport of waxy residue. Wax deposition is believed to occur as a result of lateral
transport by diffusion, shear dispersion, and Brownian diffusion [47] Gravity
settling is believed to be a possible transport mechanism also [47l
• Molecular diffusion
For all flow conditions, oil will be in laminar flow either throughout the pipe or
at least in a thin laminar sub layer adjacent to the pipe wall. When the oil is
25
being cooled, there will be a temperature gradient across the laminar sub layer.
If temperatures are below the level where solid waxy crystals can be
precipitated, then the flowing elements of oil will contain precipitated solid
particles, and the liquid phase will be in equilibrium with the solid phase; that
is, the liquid will be saturated with dissolved wax crystals. The temperature
profile near the wall will lead to a concentration gradient of dissolved wax, and
this dissolved material will be transported toward the wall by molecular
diffusion. When this diffusing material reaches the solid/liquid interface, it will
be precipitated out of solution.
9
• Brownian diffusion
Small, solid wax crystals, when suspended in oil, will be bombarded continually
by thermally agitated oil molecules. These collisions will lead to small random
Brownian movements of the suspended particles. If there is a concentration
gradient of these particles, Brownian motion will lead to a net transport, which
in nature and mathematical description is similar to nature.
• Shear dispersion
When small particles are suspended in a fluid that is in laminar motion, the
particles tend to move to the mean speed and in the direction of surrounding
fluid. The particle speed is that of streamline at its centre, and the particle
rotates with an angular velocity which is half the fluid shear rate. If the
particles approach a solid boundary, both linear and angular velocities will be
reduced. Because of fluid viscosity, rotating particles will impart a circulatory
motion to a layer of fluid adjacent to the particle. This rotating fluid region
exerts a drag force on neighbouring particles. In a shear field, each particle
passes and interacts with nearby particles in slower or faster moving
streamlines. When only two particles are present, far from a wall and at very
low Reynolds number, these passing encounters results in large temporary
displacements. As the particles pass, their trajectories are such that the particles
26
curve around one another and return to their original streamline. Thus, there is
no net lateral displacement. If the particle concentration is high, however, then
a significant number of multiparticle interactions will occur. These
- multiparticle collisions results in net lateral transport and a dispersing of
particles.
• Gravity settling
Precipitated waxy crystals are denser than the surrounding liquid oil phase.
Hence, if particles were non-interacting, they would settle in a gravity field
and could be deposited on the bottom of pipes or tanks. For an initially
uniform mixture in a vessel, there would be a beginning rate of settling
followed by a diminishing rate of deposition, which asymptotically would
approach zero at complete settling.
1.7.1. Factors leading to wax precipitation and deposition

Wax precipitation occurs when the wax molecules in the crude oil reach their
solubility limit due to change in equilibrium conditions in the crude, resulting in
loss of paraffin solubility. The solubility limit is directly dependent on temperature
and, as such, is defined by temperature, given other specified conditions. There are
other factors that affect the precipitation of wax and thus wax deposition. While
some of these factors influence wax precipitation by shifting the solubility limit in
terms of temperature upwards/downwards, other provide a favourable
environment for deposition to occur. Such factors include oil composition plus
available solution gas, and pressure of the oil which affects the amount of gas in
solution [47]. Others are flow rate, completion, and pipe or deposition surface
roughness.
• Temperature
Temperature seems to be the predominant and most critical factor in wax

precipitation and deposition due to its relationship with the solubility of
27
paraffin. Temperature and amount of light constituent are the two most
important factors affecting wax prepipitation and deposition [48]. Paraffin
solubility increases with increasing temperature and decreases with decreasing
temperature. Singh et al. showed the relationship between wax solubility and
temperature [49l Wax precipitates from crude oil when the operating
temperature is at or below the cloud point temperature. Wax deposition will
not occur until the operating temperature falls to or below WAT (Wax
Appearance Temperature) I50l All other factors actually lead to wax deposition
when the temperature is already at or below the cloud point. The ambient
temperature around the pipe is generally less than the oil temperature in the
pipe. Thus, there is loss of heat through the pipe wall to the surroundings
because a temperature gradient exists between the bulk oil and colder pipe wall.
This temperature gradient leads to wax deposition when the pipe wall
temperature falls below the cloud point. The rate of wax deposition is in direct
proportion to the temperature difference between the bulk oil and the pipe wall
[51J when bulk oil temperature is fixed. However, Haq et al. showed that keeping
the temperature constant at a value below the cloud point of the oil and varying
the bulk oil temperature reduce the amount of wax deposited as the
temperature difference between the bulk oil and pipe wall increasesI52].
The temperature gradient between the cold tubing/pipe wall and the bulk oil
initiates a concentration gradient in the paraffin molecule distribution. Paraffin
molecules near the pipe wall crystallize out of the oil as wall temperature falls
below cloud point, leading to a reduction in the number of dissolved paraffin
molecules around the wall including a radial concentration gradient. The
simple law of diffusion is obeyed then as dissolved paraffin molecules in the oil
diffuse towards the wall, causing additional precipitation and further
deposition. This leads to increasing wax deposit thickness with time. Cole and
Jessen et al. opined that it is the difference between the cloud point
28
temperature and the temperature of the pipe wall that most importantly
determines the rate of wax deposition[53].
• Crude oil composition

Crude oil is composed of Saturates, .aromatics, Resins, and Asphaltenes (SARA),
the distribution of which in a particular crude oil system is shown by the SARA
analysis. SARA determines the susceptibility of the crude to deposition of wax
solids, and thus the stability of the crude oil. Saturates are flexible in nature, the
flexibility being highest in normal paraffins because they are straight chain
compounds. The very high flexibility of normal paraffins makes it possible for
them to easily cluster and crystallize. The iso-paraffin equally enjoys a high
level of flexibility, but form a more unstable wax. Cycloparaffins (naphthenes)
are least flexible due to their cyclic nature and do not contribute much to wax
deposition. These components are in thermodynamic equilibrium at initial
reservoir conditions. It is known that aromatics serve as solvents for high
molecular weight saturates, which are the source of paraffin waxes in crude oil
while the polar components, especially asphaltenes, induce wax nucleation 1541.
The solubility of paraffins in aromatic, naphthenic, and other organic solvents
becomes low at room temperature [55!. Light ends of saturates equally help to
keep the high molecular weight heavy ends in solution. The onset of
production results in the loss of these light ends, as they are first to leave the
reservoir. This alerts the original composition of the oil system, resulting in
decreased solubility of the paraffin waxes. This loss of solubility could lead to
precipitation and deposition of wax. In a model study, Huanquan et al. reported
that increasing the percentage of light end (Cs) in a synthetic oil system
decreased the cloud point temperature, reducing the chance of wax deposition.
Generally, the weight percent of the saturates in the crude oil, the structural
distribution of the paraffin components, and the occurrence of other solids like
formation fines, corrosion materials, and presence of asphaltenes which could
29
form nucleating sites-all contribute to wax precipitation and deposition. Oils

containing high C3o+ concentrations exhibit high cloud temperatures [56].
Therefore, knowledge of the oil composition (SARA) gives a fair idea of the wax
deposit potential of the crude and, hence, the oil stability. Oil stability has been
reported to depend on its solids content and the balance between aromatics and
saturates. By SARA analysis, the distribution by weight percent of saturates,
aromatics, resins and asphaltenes components, for stable and unstable crude oil,
is as follows:
Unstable crude: Saturates > Aromatics > Resins > Asphaltenes

Stable crude: Aromatics > Saturates > Resins > Asphaltenes
This distribution is to be expected since the aromatics keep the heavy paraffin
wax in solution, while a crude oil system that displays a large amount of
saturates (paraffin) is likely to be unstable and thus precipitate and deposit wax
!57l
• Pressure
Pressure, as an important parameter in the exploration of reservoir fluids, plays

a significant role in wax precipitation and deposition. The pressure profile
during oil production is such that the reservoir pressure declines with
production, and the pressure of the flow stream drops all the way from the
reservoir to the surface. The lighter components of the reservoir fluid tend to
be the first to leave the reservoir as pressure depletes. This causes an increase in
the solute solvent ratio, since the light ends serve as solvent to the wax
components. Hence, the solubility of wax is reduced with the loss of these light
ends. The wax appearance temperature increases with increase in pressure
above the bubble point, at constant composition. This phenomenon implies that
increase in pressure in the one-phase liquid region will favour wax deposition.
The situation is different below the bubble point where there is two-phase
30
existence. Here wax appearance decreases with increase in pressure up to

bubble point pressure due to dissolution of light ends back into liquid phase [58l
• Other contributing factors

Though temperature, composition, and pressure of oil play the most significant
role in wax deposition, other factors that have been identified as contributing to
wax deposition include flow rate, gas-oil ratio, and pipe/tubing wall roughness.
Laboratory investigations have revealed that wax deposition is influenced more
by laminar flow than when flow is in the turbulent regime. Increasing flow rate
from laminar to turbulent reduces maximum deposition rate and at the same
time lowers the temperature at which maximum deposition rate occurs [59]. Low
flow rates offer the moving oil stream longer residence time in flow channel.
This increased residence time allows more heat loss to the surroundings,
leading to a higher chance of the bulk oil temperature falling below the WAT
and enough time for wax precipitation and final deposition. Jessen et al.
believed that when flow is in the laminar regime, wax deposition increases with
increase in flow rate [60]. Increase in flow rate in the laminar regime makes more
fluid available for wax deposition. However, wax deposition decreases as flow
moves to the turbulent regime. Turbulent flow stream exerts a kind of viscous
force, which tends to drag or slough the wax deposits from the pipe wall. When
this viscous drag exceeds the resistance to shear in the deposits, the wax then
sloughs and is lodged back into the liquid. This removal mechanism has a
significant impact on the wax deposition rate [59]. There is a difference in texture
between wax deposited at high flow rates and wax deposited at low flow rates
[52,59. si] Paraffin wax deposited at high flow rates appears harder, being more
compact and more firmly attached to the deposition surface, the molecules
having good cohesion among them.
In study of the effect of deposition surface roughness on paraffin deposition,

Hunt et al. concluded that deposits do not adhere to metals themselves, but are
31
held in place by surface roughness which acts as nucleating sites t62]. Jorda et al.
observed that paraffin deposition increases with greater surface roughness [63J.
In their wax deposition study with pipes of different materials, Jessen et al.
concluded that the amount of wax deposited on a smooth surface is less than
that deposited on steel [60]. However, Patton et al. could not see any relation
between wax deposition and surface roughness, but opined that adhesion bond
at a surface should be proportional to the total contact area and therefore
related to surface roughness t64L
Gas/Oil ratio influences wax deposition in a manner that depends on the
pressure regime. Above the bubble point, where all gases remain in solution,
solution gas helps to keep wax in solution. Luo et al. reported that WAT will
be high with low gas/oil ratio (GOR) [65], while Singh et al. observed that
injection of lift gas in a closed loop reduced wax deposition by causing a
depression in WAT as a function of pressure [66l. High GOR would result in
more expansion by causing a depression in wax expansion and subsequent
cooling as pressure of the oil system depletes a situation that can aggravate the
wax deposition problem. In a study to reduce WAT by injection of diluents lift
gas Singh et al. noted that good results were not obtained in high GOR wells [66l
1.8. Nature of Crude Oil Wax
Waxes are complex mixture of high molecular weight alkanes of three structural
types as straight chain, branched chain and cyclic. The physical properties of wax
depend upon the composition of waxes, molecular weight distribution and the
relative proportion of n-alkanes, iso-alkanes and cyclic alkanes [67]. The physical
strength of waxes increases by decrease in low molecular weight n-alkanes and
increase in the proportion of iso-alkanes and cyclic alkanes. The wax present in
petroleum crudes primarily consists of paraffin hydrocarbons (Cis-Cse) known as
paraffin wax and naphthenic hydrocarbons (C30-C60). Hydrocarbon components of
wax can exist in various state of matter (gas, liquid or solid) depending on their
32
temperature and pressure. When the wax freezes it forms crystals [68], the crystals
formed of paraffin wax are known as macro crystalline wax. Those formed from
naphthenes are known as microcrystalline wax (Figure 1.10).
Various crystals forms have been observed in petroleum waxes. Simple solid
solutions of n-paraffm can occur as plates or needles. Although branched chain
and ring containing impurities have been identified as ingredients in the needle
crystals, it is agreed that the needles are simply plastic plate crystals that are
tightly rolled up.
Microcrystalline Macrocrystalline Crystal Deposit Network of Wax
Figure 1.10: Wax crystals
Another form commonly observed is the so-called “mal” crystals, also including
highly branched or ring containing impurities. Waxes that occur naturally during
production and pipelining are rod waxes and those derived in refining processes is
refinery wax. Rod waxes are of high melting point ranging from 74-83 °C and
found to comprise nC35-nC4i together with larger isoalkanes and cyclic alkanes.
Refinery wax is of low melting point, ranging from 27-72 °C and comprises n-
alkanes from nCis-nC32.
When paraffin waxes precipitate from oil, they form platelets of stacked lamella
crystals that can fall into random “house of cards” structures (Figure 1.11), which
is capable of entrapping oil and forming gel. The wax crystals are likely to form a
33
three dimensional structure. The card house structure consists hundreds of

lamellar tacks as shown in the Figure 1.11 t69- 7°].
Figure 1.11: Morphology of wax crystals
1.8.1. Wax crystal morphology
The morphology of wax crystals related with the behaviour of wax on a molecular
level during the crystallization process. This tells the solubility relationship and
the crystal shape. Alkane shows considerable degree of order in the liquid phase.
Due to this pre-existing order, the nucleation occurs. Several solid phase
transitions occur at temperatures slightly below the melting point which relate to
the relative alignment of the n-alkanes molecules. Odd and even number of
carbon shows different morphology. End groups of an even carbon number
molecules are parallel which allowing them to align in a more dense structure,
while end groups of an odd carbon number molecules are not parallel thus
preventing tighter packing structure. Because of long thin molecules of n-alkanes
align; complete disorder in the liquid state only occurs near the boiling point. At
lower temperatures the molecule is likely to align parallel to each other with the
backbone fully stretched, in a square packing arrangement. The ends do not align
and methylene groups are free to rotate. This freedom to rotate prevents the
ordered liquid state in n-alkanes. The transition from the non-aligned to the
aligned state appears to occur relatively quickly in melts according to diamagnetic
susceptibility measurements [71).
34
1.8.1.1. Nucleation and growth of the solidphase
A certain degree of ordering may be possible in crude oil near the melting point
temperature. The nucleation requires ordering and ability of aggregation of chain
segments to form nuclei, forming smaller super saturation. Unforced nucleation
occurs near the melting point, so super cooling is possible. Simultaneously,
heterogeneous nucleation occurs which reduces further super cooling need. So the
crystal nucleating rate is high. The growth of crystal nuclei occurs rapidly and in
random manner in the axis of molecular backbone because the additional
molecules align parallel to molecules within the structure. Thus very thin plates
grow rapidly in outward direction and thicken by addition of successive layers [72-
73]. The solid crystals are held together by Van der Waals forces. So, cleavage of
layers occurs more rapidly than the breaking of a single layer. In the final solid
form, the plate crystal may be flexible and mechanical strength of the crystal
increases as molecular weight of the joining n-alkanes increases.
1.8.1.2. Solid-Solid transition
The parallel arrangement in a square configuration occurs due to order in the

liquid state. The C-C bonds are fully stretched in zigzag manner and free to rotate.
When methylene groups allow the conversion of square packing structure to
hexagonal structure, crystallization occurs. The end groupware aligned in a single
plane having minimum energy. Rotation of methylene groups is still possible. It
gives flexibility and thinness to the solid phase. This phase is known as cm or
rotator phase and persists about 5 °C below the melting point[74J. Further cooling
of och phase restrict the methylene group rotation until they lie in a single plane.
The isothermal transition to non-rotator phase can occur and dense packing of the
methylene groups occurs. It results in an opaque and less flexible structure. The
least dense (3 phase and all odd carbon numbers n-alkanes having the
orthorhombic structure, in which the backbones of the moleculeâre, align at right
angles to the end plane. Even carbon number n-alkanes are able to form this kind
of intermediate solid phase. In even number n-alkane, C-C bonds at opposite ends
35
are parallel and forms more dense structure. It takes place by two carbon atoms
forming monoclinic structure and one carbon atom forms triclinic structure.
1.9. Methods for Controlling Wax Deposition

Different methods are in usednow a day for controlling wax deposition t75-761. They
are 1) Thermal Methods 2) Mechanical Methods and 3) Chemical Methods.
1) Thermal methods
Although these methods assure; trouble free transportation of waxy crudes at
any time but are very expensive as it requires excellent pipelines insulation as
well as heating arrangements with very high and low temperature control. If
temperature control is not there and crude get heated then lower fractions of
crude may create lots of pressure on pipeline wall, so high risk is also involved.
This method is mainly used for short pipelines.
2) Mechanical methods
Mechanical methods include scrapping and pigging. It comes in picture when
the pipeline is choked with the deposition of waxes. It is the best suited method
for early removal of the problem, but it requires lots of mechanical labour. In
many cases it is not feasible also.
3) Chemical methods
Chemical methods include the use of solvents like produced condensate,
xylene, toluene, benzene, carbon tetrachloride, trichloroethylene, carbon
disulphide and terpenes. High specific gravity is an important factor that will
help solvents penetrate and dissolve the paraffin deposition typically on bottom
of the flow-section. Some of the solvent mentioned above are problematic-
chlorinated hydrocarbons causes poisoning of downstream process, aromatic
solvents have low specific gravities and it is difficult to use them on the well
bottom, they also have low flash points and handling becomes difficult, while
36
carbon disulphide is highly effective but it is very highly flammable with toxic
fumes.
Uses of dispersants and detergents causes paraffin molecules to repel each other
and metal surfaces. Naturally occurring asphaltenes can act as dispersants.
Uses of crystal modifiers are effective in limited types of crude oils. They are
polymeric materials which prevent paraffin deposition by disrupting nucleation,
co-crystallizing. Commercially they are called pour point depressants (PPDs).
They are also referred to as wax inhibitors, polymeric additives, flow improvers
and viscosity index improvers.
At present, out of these three methods for controlling wax deposition, chemical
methods, especially crystal modifiers treatment, are widely used in the
transportation of waxy crude oils.
1.10. Pour Point Depressants (PPDs) for Crude Oils
Any material that is present with a crystallizing compound as it crystallizes can

influence crystallization[77). In crude oil, these materials include the solvent where
crystallization is taking place, naturally present materials such as asphaltenes,
resins and water and added materials such as inhibitors and flow improvers. These
materials influence the thermodynamics and kinetics of crystal growth as well as
the solubility of the crystal [77]. Crystallization is the first step of the deposition
mechanism, meaning that changes in crystallization will influence deposition and
gelation. Additionally, some materials that do not influence crystallization are
capable of influencing the fluid flow, gelation and/or deposition of the wax
crystals. Wax additives are chemical added to crude oil to improve its flow
property and viscosity through pipelines 1781. Additives aid in flow ability by a
number of different ways: lowering the cloud point of the system, modifying the
crystal size and shape to retard gel formation by preventing the formation of large
37
wax crystal lattices, reducing the viscosity and modifying the surface of the pipe
wall to prevent deposition t78> 79> 80]. These additives also referred to as wax
inhibitors, pour point depressants, flow improvers, viscosity index improvers and
wax crystal modifiers. They can modify the wax deposition rate and the rheology
of the crude oil. They are typically polymers that contain a long chain to interact
with the wax and side (typically polar) groups to limit co-crystallization and
gelationl78].
When a waxy fluid is cooled below its cloud point, the wax crystals forms and
begins to agglomerate. As the temperature is further reduced, crystal
agglomeration reaches the point at which loose gel structure is formed. The wax
crystal habit is dependent on the crude source and also on the rate of cooling and
degree of agitation during cooling. Wax crystal growth without additive and with
additive shows in Figure 1.12 and Figure 1.13.
38
When crystal modifier is added in minimum concentration, there is modification
in crystal habit size and crystal adhesion. The changes in crystal habit and size and
reduction in tendency of crystal to adhere one another, all combines to reduce the
temperature at which gel structure is built up during cooling of an additive treated
waxy fluid.
Paraffin in solution with additive
m
Above Cloud Point * i
■ * a Nucleator gives many nucEe
m
Many small rather

At Cloud Point
1 thanfew large crystals
Growth Arrestor slows growth,

On Cooling
alters shape, reduced adhesion
On Cooling deed I Pourpoint lowered as

crystals remain separate
m non
Dsn m
Figure 1.13: Wax crystal growth with additive
Various explanations of crystal habit modification can be summarized as follows:
• Inhibition ofsolid transition
The additive inhibits the transition from weaker <xh crystal form to more rigid fi
crystal. The pour point depressant do not alter the cloud point i.e. they do not
alters the formation of och phase [81]. The conclusion is that oh form is unable to
form a strong gel, whereas the more rigid f} phase crystal readily forms a strong
three dimensional structure throughout the fluid at very low solid
concentrations.
39
• Inhibition of the crystal edge growth
Inhibition of the growing edge of the crystal is brought about by
adsorption/absorption or co-crystallization of the crystal habit modifier onto
the fast growing crystal edges. This forces the crystal to grow from the plate
surfaces resulting in a thicker and three dimensional shapes. According to
Holder and Winkler, the mechanism is described in five stages as shown in
Figure 1.15.
1.10.1. Mechanism of pour point depressants
The waxes in crude oil are varying in amount and molecular weight distribution.
When waxy crude is cooled down, the paraffinic wax starts to crystallize in the
form of thin plates, needles or mal-crystals, with the needles most problematic. As
wax components come out of solution, the needles compact into a three
dimensional network. Plates coils on their edges forming hollow needles which
can then form cage like structure [8Il Studies have shown that the wax crystals
modifiers reduce the interlocking three dimensional wax networks [82].
The most widely reported mechanisms by which flow improvers operate to
modify wax crystals are wax crystal nucleation and crystal growth inhibitors I83-93!.
Both mechanisms results in the formation of numerous smaller crystals rather
than fewer larger crystals. Large plate like crystals does not allow the crude oil to
flow while smaller numerous crystals are allowed to flow the crude oil.
• Nucleation mechanismt87> 93!
Upon cooling crude oil with additives, the polymeric additive aggregates or
phase separates before the paraffin waxes phase separate. These polymeric
aggregates form numerous crystalline instead of few large crystals. The
crystalline crystals act as nucleation templates for the crystallization of the
paraffin waxes. The additives that operate via this mechanism are therefore
referred to as crystallization nucleators or promoters. As a result of this
40
interaction between the polymer and the paraffin, the paraffin waxes are
prevented from crystallizing with each other. The resulting wax crystals are
modified and reduced in size and therefore crude oil able to flow.
• Crystal growth inhibition®*’9®
A polymeric additive that is able to delay the crystallization of the paraffin wax
operates through a crystal growth inhibition mechanism. Crystal growth
inhibitors tend to co-organize with the wax molecules, thus retarding the
crystallization of wax crystals. In this way, the wax cohesive energy density;
which is the force responsible for the ordering transformation!961, is minimized.
The affinity for wax crystals to form ordered structures is therefore reduced as
well. The resulting wax crystals are reduced in size as well as structurally
modified.
According to Holder and Winkler the additives have little effect on the weight
and composition of wax precipitated from the crude oil but it affect the size and
shape of the wax crystals t97>98]. The explanation of PPD mechanism can be given
by the theory of crystal growth and dendrite growth. The basic premise around
the theory is that as many crystals faces grow, ‘poisons’ present in the solution will
accumulate around the faces. As a result, the crystal will tend to grow as rapidly as
possible where the impurity concentration is at a minimum.
41
In Figure 1.14, (a) shows how the crystal nucleus ABCD increases in size to EFGH.
Naturally, more poison would be accumulated to the faces EF, FG, GH and HE
then at the comers E, F, G and H. Accordingly, growth will be occurring relatively
faster at the corners. Thus a later stage in crystal growth would be the formation
of crystal such as that in (b), which shows needle like projections developing from
corners of a crystal nucleus. If we see each of the needles, it is not smooth but it is
made of projections which are true crystallographic faces. These projections are
the source of further growth. The end result is that there is a development of
branches at regular intervals with the rapid growth of comers Le. dendrite
structure is formed (c).
Stage-I
Without additive, Ihih lozenge shaped
plates which interlock and overlap
——
Increasing Pour Point Depressants Concentration
— -—
Stage-11
..........................
X Preferential growth at
peaks and thickening
Stage-Ill
................................................... ... — ..............................
■. r\ Dcndritric or Treelike crystals,

-4:--: : J41 thickening process continuing
Stage-IV
Irregular shaped Hocks,
Thickness dimension now
Comparable to He length and
breath
—
i
i
i
—
l
i Tetragonal pyramids and Rhombic prisms,
..........................
i The long dimension is the thickness dimension

I
I
i
*-
» ■
Figure 1.15: Stages of wax crystal modification
42
Thus the additive in the oil acts as a poison and it mount up around the faces of
the wax crystals at cloud point. So the growth of the four faces of wax crystals
become restricted and it grow relatively quicker at the corner and also it becomes
thick. At the large stage typical dendrite is formed. At the higher additive
concentration, the sideways growth of crystal also becomes difficult and even
dendrite cannot be formed. Now the crystal becomes so thick that the growth of
crystal in the XY direction is retarded and it grows only along the Z axis. As a
result the blocks like pyramid crystal resulted. Thus, the shape of the crystal is
changed from orthorhombic to pyramidal shape because of this reason, the ability
of wax crystals to intergrowth and interlock is greatly diminished. The
combination of these two effects lowers the pour point of the crude oil. All the
stages of this mechanism are shown in the Figure 1.15.
' Elevation Vietr: Relative height, Le. ZZ'

ofthe aystal has been exaggerated; real
Figure 1.16: Basic structure of n-paraffin crystal
It is already mentioned that crude oils of different oil fields have different wax
composition and the precipitation waxes of different oils have also different
43
structure. It is good evidence that response to pour depressant is a function of the

structure of precipitating crystal than of the chain length of n-paraffin molecules
of which crystals are made. So to understand the mechanism of pour point
depression, first it is necessary to describe both the lattice structure and growth of
n-paraffinic crystals. The basic structure of n-paraffin crystal is shown in Figure
1.16.
As can be seen from the Figure 1.16 the crystals have the appearance of very thin
diamond shaped plates. These each plates arranged layer upon layer which can be
seen from elevation view. Now if we consider each layer, the n-paraffin molecules
are stacked side by side with their long axis parallel to the Z axis of the crystal.
There are two theories of crystal growth: 1) Gibb’s theory and 2) Frank’s theory.
• Gibb’s theory
According to this theory, each crystal face grows layer by layer in a
discontinuous fashion which is shown in Figure 1.17.
Slow Slow Quick Quick Slow

A B C D £
Figure 1.17: Discontinuous layer addition
A crystal is waiting for nucleation to occur on any of its faces (A). At once, the
nucleation has started (B), growth steps forms and the development of a layer
form very rapidly (C & D), when the new layer has grown to the edges of the
crystal, growth has eliminated itself and the growth stops until the nucleation
on the top of newly formed layer occurs and a new cycle begins.
• Frank’s theory
According to this theory, crystals are not perfect but contain faults. The first
part of the figure shows stacking faults due to n-paraffin molecules which are
44
Chapter-! Introduction
not lining up properly I"l. The second part describes the effect of stacking fault
on the crystal growth.
The diagram (Figure 1.18) shows a hypothetical crystal surface built of block
like molecules. The crystal surface is not smooth since each block is highly out
of lines with some of its neighbours in the crystal surface. Further, the addition
of more blocks would results in the continuous propagation of the fault, along
with simultaneous growth of the crystal. Thus, n-paraffin crystals are not made
up of discrete terraces but consist of extremely shallow solid spirals.
If pour point depressant is present in the solution, then it hinders the
crystallization of the wax molecules. The hindering effect of the pour point
depressant on the wax crystal growth is caused by the incorporation of the
molecules of the polymer at the growing crystal edge or dislocation. The polymer
molecules block the further growth by preventing the further addition of n-
paraffin molecules. Thus, the pour point depressants wall interfere very effectively
with spiral growth [10tM051. However, the growth of the crystal is being
continuously re-initiated, particularly in the Z-axis direction, by n-paraffin
molecules as they come out of the solution. Accordingly new layers can form
readily by the Gibb’s mechanism. The net effect is that when pour point
depressant is present, the wax crystal habit is changed from thin extensively
interlocking plates to more compact crystals tl06l Thus, the pour point of the oil
decrease and the oil can flow easily at low temperature.
45
The simulated mechanism is shown in Figure 1.19 A-F. Wax molecules (1.19A)
tend to crystallize first into discrete needle like structure (1.19B) that associates
into larger structure or gels (1.19C). Polymeric additives with the wax like
components (1.19D) co-crystallize with the wax (1.19E) and stearically hinder the
association of wax structure (1.19F) thereby prevent the formation of larger
structures and gels that inhibit flow and cause wax deposition 11071.
Figure 1.19: Mechanism of wax crystal modification
1.10.2. Factors affecting on performance of pour point depressants
• Effect ofpendant alkyl chains
As molecular weight of paraffin governs the solubility in the oil, the length of
alkyl side chain governs the adsorption of the polymer on the wax. The longer
alkyl polymers are effective in depressing the pour point of the high pour oils,
while the shorter alkyl polymers are effective in low pour oils. If the alkyl
chains are too short, they are adsorbed on the wax below the pour point of the
oil and are ineffective in lowering the pour point and if it is too long then
chains will crystallize the polymer from the oil solution at a temperature above
pour point of the oil. The interaction between additives and crude oil is crucial;
the additives work best when their pendent alkyl chains matched very well to
the paraffin distribution in crude [108!.
46
• Polymer backbone
The polymer backbone is not believed to play a large role in porn: point
depression. It is believed that in most of the cases the backbone only provides a
structure from which the important pendant chains are suspended[109].
• Stability ofHow improver
Additive treated crude oils undergo high shearing stress during transportation,
in this state it should not undergo degradation or breaking into fragment
otherwise it will lose its activity.
• Molecular weight ofpolymer
Increase in molecular weight of polymer increase polymer volume in an oil

solution. The high molecular weight polymer gives high viscosity than low
molecular weight polymers of the same chemical type.
1.10.3. General characteristics of pour point depressants (PPDs)

Crude oils and heavy fuels contain different wax composition, chemistries and
concentrations, depending on their source. Thus, a single pour point depressant
cannot effectively depress the pour point of all crudes. An effective PPD for any
given crude has a waxy character that reasonably matches the crude’s paraffin
chain length. This chain length is necessary to participate efficiently in the co
crystallization phenomena and thus, to depress the pour point effectively.
Pour point depressants typically have following characteristics:
1) A wax like paraffin part, typically mixture of linear alkyl chains of 14 to 25

carbon atoms that co-crystallizes with the oil’s wax forming components.
2) A polar component typically acrylates or acetates that limits the degree of
co-crystallization.
3) They are most often polymers that when attached to the growing wax
crystals stearically hinder the growth, resulting in small crystal.
47
1.10.4. Role of polymeric additives and temperature in changing the viscosity of

the crude oil
The efficiency of the additive in changing the viscosity with temperature depends
upon its stability in oil; it should be soluble in crude oil. Polymeric solubility
increases with increase in temperature provided the molecular weight should be
moderate. Polymer molecule changes from the closed structure to an open
structure as the temperature increases, which results into greater volume and
causes increases the viscosity of the oil.
1.11. Effect of Additives and Composition

Any material that is present with a crystallizing compound as it crystallizes can
influence crystallization EU0]. In crude oil, these materials include the solvent
(generally shorter chain hydrocarbons) where crystallization is taking place,
naturally present material such as asphaltenes, resins and water and artificially
added materials such as inhibitors and flow improvers. These materials can
influence the thermodynamics and kinetics of crystal growth as well as the
solubility of the crystal [110l Crystallization is the first step of the deposition
mechanism, meaning that changes in crystallization will influence deposition and
gelation. Additionally, some materials that do not influence crystallization are
capable of influencing the fluid flow, gelation and/or deposition of the wax
crystals. Petroleum companies have dedicated a significant portion of time and
money to exploit these issues in attempt to mitigate wax deposition.
Additives aid in flowability by a number of different ways: lowering the cloud

point of the system, modifying the crystal size and shape to retard gel formation
by preventing the formation of large wax crystal lattices, reducing the oil viscosity
and modifying the surface of the pipe wall to prevent deposition[90, m-U23.
Extensive research has been conducted on various kinds of wax inhibitors, how
they mitigate wax deposition and the mechanism by which they act. Semi
48
crystalline random copolymers were shown to reduce the yield stress of the
formation of single component wax crystals because of altering of the wax crystal
structure by the amorphous part of the copolymer IU3]. Guo presented similar
results using poly (ethylene butane) also presenting micrographs that showed
drastic changes in crystal size and shape because of the addition of the polymer[u4'
115]. Studies on block copolymers found that wax is capable of crystallizing on the
hairs of aggregated copolymers E116]. Because of the size of the copolymer, it
becomes difficult for the wax crystal to associate with one another to form a gel
[117] EVA copolymers were observed to reduce the cloud point, viscosity and pour
point of Brazilian crude oils by modifying crystals and forming weak aggregates
with the wax [U8]. Further work with EVA copolymers with similar results was
completed on five different Iranian crude oils with a wide range of oil densities,
viscosities, asphaltene content and wax content E112l. Other works have shown
copolymers containing polymethacrylates and acrylic esters can also be effective
wax inhibitors[90>1U-119,120].
Although a wide numbers of polymers can be used as wax inhibitors, their
efficiency is extremely sensitive to both the composition of the oil and the
concentration of the additive added. Using commercially available wax inhibitors,
Garcia examined their efficacy on two groups of crude oil: one group had larger
wax fraction, smaller concentration of shorter chain crystallisable n-alkanes (C23-
C48), higher pour points and lower API gravities than the other [12Il This work
showed that some additives that effectively reduced the pour point for the one
group of oils either minimally impacted or in some cases increased the pour point
for the other group oils. Similar results were seen in another study where five
crude oils and five inhibitors were studied: the best inhibitor for one crude oil
could be the worst inhibitor for another crude oil[122].
Further insight into why this phenomenon is occurring can be seen by looking at
, some of the aforementioned inhibitor studies where the functional group of the
49
inhibitor remained basically the same but alterations to the functional groups were
made [1U> n2> 1H 1,811191. In work on EVA copolymers, it was found that copolymers
with lower vinyl acetates content were more effective wax inhibitors because of
its differing solubility parameter [118]. Additionally, the maximum efficiency of the
inhibitors occurred at intermediate concentrations because of either precipitation
of the copolymer or wax nucleation induced by the copolymer. Similar results
were seen when analysis was completed on two different poly (ethylene butane)
copolymers that differed in the number of side groups in the inhibitor [IW]. The
magnitude of the effect of the reduction of the yield stress for a particular
copolymer was dependent on both the concentration and the n-alkane(s)
crystallizing out of solution. Micrographs showed that at the optimum
concentration, the crystal that formed were very small and did not aggregate very
well. However, at other concentrations, the crystals were much larger
(particularly at lower concentrations) and/or aggregation was more prevalent
(particularly at higher concentrations). These works shows that compatibility
must exist between the n-alkane crystals and the inhibitor in order for them to be
effective. Because of this fact, it is generally accepted that inhibitors can only
work for small range of crude oils, typically dependent on the carbon number
distribution of the crude oilt90> m-I23i.
Although a great deal of work has been dedicated to developing materials that
inhibit wax deposition, very little work has been dedicated to understanding how
the components already present in crude oil influence thermodynamics, gelation
and deposition. Visintin et al. explored the effect of water on the strength of gels
and found that an increase in the water cut led to an increase in the pour point,
yield stress, viscosity and storage modulus of the system tl24J. Some work has
focused on asphaletenes, the heaviest, most polar components of crude oil[125,126].
Garcia et al. showed that flocculated asphaltenes will increase the cloud point of a
crude oil and interfere with the mechanism of crystal inhibition for a particular
50
Chapter -1 In
maleic anhydride wax additive [125]. Using model wax-oil-asphaltjejfte;

,7* ■' ft'<"iSS\
^^
%'
Venkatesan found that addins asphaltenes reduced the gelation temnmjatture jfj
the yield stress when compared to the asphaltene-free model
Corresponding to the decrease in the yield stress was a change in the morphology
caused by the presence of asphaltenes. Tinsley’s works correspond to Venkatesan’s
work, showing the adding a very small amount of asphaltene can cause a small
reduction in the yield stress [127). This result is dependent upon the ratio of wax to
asphaltene: if the ratio is too high then the asphaltenes will be unable to influence
the properties of the crystallizing system. However, if an excessive amount of
asphaltenes are added, asphaltene aggregates will be present before the wax
precipitates out of solution. When this happens, these aggregates do not enter the
crystal structure of the wax and act as nucleation sites for wax precipitation,
consistent with Garcia’s conclusion [125l
Although they are the major components of both crude oil and wax deposits, only
a small portion of work has been dedicated to paraffins. Early work looking at
binary n-paraffin mixtures showed that combining two nearby n-alkanes caused
lower than expected cloud points and pour points because of the interaction
effects between the two n-alkanes [97].
More recent work by Paso analyzed the effect of paraffin composition on the
gelation abilities of n-alkane systems [128]. Solubility work showed that a
polydisperse wax system had a larger supersaturating ratio at the cloud point than
a monodisperse wax system. This higher supersaturating ratio indicates that the
polydisperse system will have faster precipitation kinetics at the nucleation point.
Further, for a given wax percentage of 0.5 %, it was shown using rheometry that a
monodisperse C36 system was unable to form a gel, whereas a polydisperse wax was
able to form a gel. This phenomenon was explained by the fact that polydisperse
paraffin crystals have nanoscale surface roughness to provide points of strong
crystal-crystal interaction.
51
1.12. Aims and Objectives
As discussed earlier, to convert crude oil into useful products it has to be

transported to refinery. As per studies and practical experiences of crude oil
companies, pipelines are the most economically viable way of crude oil
transportation. Main problem associated with the transportation of crude oil are:
1) Wax deposition and 2) Restartability after prolong shutdown. So it is necessary
to keep the crude oil in a flowing fluid state. Several methods exist to keep the
crude oil in a fluid state for its transportation. The proposed methods may be
applicable depending upon the characteristics of the crude oil and the available
facilities. Taking into consideration all the techno-economic aspects, additive
treatment is the most suitable method for the transportation of crude oil, which
can depress the pour point and improve the flow characteristics and efficiently
reduces the restart pressure of the crude oil at minimum expected temperature.
The objective of this investigation is to synthesize new polymeric additives by

different synthetic process. Studies on shear rate, shear stress, pour point,
viscosity, viscosity index etc. of the crude oil are of great importance in relation to
their behaviour and functioning. A class of additives with definite characteristics
of the crude oil in view of the problematic functioning of the crude oil with
reference to the technology of treating them for a variety of purpose. These
aspects open up a vast vista of variables whose specific nature and characteristics
should be accounted for in terms of the structural features of the moieties, the
molecular forces arising there from and the factors that inhibit or enhance one or
the other specified characteristics.
A flow improver is generally very specific in nature and may affect differently the
various crude oils. As already mentioned, flow is an important characteristic of
crude oils; highly viscous crude oils are difficult to pump out and transport long or
even short distances. Problems concerning exploration of crude oils invariably
affect the economy of drilling, pumping, refining operations. However, this
52
investigation concerns only with the pumping and transportation difficulties as

arising out of the rheological characteristics of the crude oils.
The objectives of the study are thus manifold which could be categorised as under:
1) To study the physical-rheological characteristics of the Indian crude oils.
2) To synthesize number of nitrogen containing polymeric additives with

certain functional groups.
3) To characterize the newly synthesized polymeric additives and to study

their effect on the various Indian crude oils in different compositions and
at varying temperatures, the properties accepted for evaluation being
mainly pour point and rheological characteristics.
4) To differentiate and classify the newly synthesized polymeric additives as

pour point depressants and/or flow improvers and to evaluate their
efficiency on a relative scale.
5) To correlate their affectivity with the molecular geometry and other

associated characteristics and forces and to arrive at certain generalizations.
6) To study the effect and mechanism of polymeric additives on crude oil of

five different oil fields of Gujarat (India). Five oil fields are:
i. Langhnaj (North Gujarat)

ii. Jolwa (South Gujarat)
iii. Gandhar (South Gujarat)
iv. Balol (North Gujarat) and
v. Lanwa (North Gujarat)
53

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I <n

Crude oil is naturally occurring, toxic, flammable liquid consisting complex

The supply, production and consumption of petroleum influence national

and natural gas are considered as non-renewable energy sources.

movement toward the generation of renewable energy is therefore under way to

Petroleum and petroleum-based chemicals are important in manufacturing plastic,

can be used in different ways. Refineries separate different petroleum products by

materials were mostly used for waterproofing and embalming. Commercial

exploitation of petroleum, largely as a replacement for oils from animal sources

gas, once flared-off as an un-needed by-product of petroleum production, is now

similar materials are sedimentary rocks containing kero^en, a complex mixture of

1.2. Petroleum Formation

Petroleum, also called crude oil, is a thick, flammable, yellow-to-black coloured

buried under sediments or deposited in other oxygen-poor environments begins a

1.3. Petroleum Composition

Crude oil varies greatly in appearance depending on its composition. It is usually

hydrocarbons; the most commonly found molecules are paraffin or wax,

naphthenes, aromatics and more complicated chemical like asphaltene. Each

chemical properties, like colour and viscosity.

Table 1.1: Elementary composition of crude oil

Element %by wt.

Metals <1000 ppm

molecule, although trace amounts of shorter or longer molecules may be present

for energy, from cooking to heating to transportation.

The cycloalkanes, also known as naphthenes, are saturated hydrocarbons which

The aromatic hydrocarbons are unsaturated hydrocarbons which have one or

have a sweet aroma. Some are carcinogenic.

Asphaltenes are operationally defined as the non-volatile and polar fraction of

petroleum that is insoluble in n-alkanes (i.e. pentane or heptane). As a result,

asphaltenes constitute a solubility class of crude oil components, rather than a

asphaltene generally increase -with increasing carbon number of n-alkane

precipitant. Asphaltene are characterized by fused ring aromaticity, small aliphatic

the asphaltene molecules. The aromatic carbon content of asphaltene is typically

in the range of 40 to 60%, with a corresponding H/C atomic ratio of 1.0-1.2. A

large percentage of these aromatic carbon rings are interconnected in the

molecular structure and, consequently, the asphaltene molecules appears flat or

asphaltene was depicted as stacks of flat sheets of condensed aromatic systems,

suggested the asphaltene molecules to be disc-like with polyaromatic fused ring

cores containing polar functional groups. It is currently accepted that asphaltene

consist of aromatic compounds with tt-tt interactions, which undergo acid-base

suggested asphaltene structure [13).

Figure 1.1: Hypothetical asphaltene molecules

181 are related to the aggregation and precipitation of asphaltene. Investigations

the presence of aromatic hydrocarbons [19).

1.4. General Properties of Crude Petroleum

1. Indicate crude oil quality and

assessment of the character of the crude oil.

petroleum. Nevertheless, density is still used to give a rough estimation of the

nature of petroleum and petroleum products.

petroleum. The API gravity is related to specific gravity by following formula.

Degree API = (141.5/Specific gravity at 15 °C) - 131.5

gravity and API gravity C21’22^.

1.4.3. Pour point

1.4.4. Cloud point

wax appearance temperature or cloud point[26-27> 28l Cloud point is of importance

test method is used for determining cloud point of petroleum oils.

1.4.5. Bottom sediment and water content

removable suspended droplets or as an emulsion. The sediment dispersed in crude

sediments are principal components of the sludge that accumulates in storage

tanks and must be disposed of periodically in an environmentally acceptable

manner. Knowledge of water and sediment content is also important in

ASTM D4377 and ASTM D4928.

1.4.6. Water content by Dean and Stark method