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Proceedings of the ASME 2017 36th International Conference on Ocean, Offshore and Arctic Engineering

OMAE2017
June 25-30, 2017, Trondheim, Norway

OMAE2017-62366

ASPHALTENES: WHAT DO WE KNOW SO FAR

Abdulaziz S. Al-Qasim Mohammed Alasker


Saudi Aramco Saudi Aramco
Dhahran, Eastern Province, Saudi Arabia Dhahran, Eastern Province, Saudi Arabia

ABSTRACT composition of petroleum to develop correlation studies and


Serious operational problems caused by asphaltene improve the prediction of asphaltene phase behavior.
deposition during oil production have driven the ongoing effort
to understand this phenomenon. Many studies have focused on INTRODUCTION
related asphaltene precipitation flocculation and deposition in Asphaltene properties and problems are discussed utilizing
oil reservoirs and flow assurance in the wellbores. Experimental Middle-Eastern oil reservoir data. The paper includes a section
techniques and theoretical models have been developed trying that highlights the differences between asphaltene and wax, and
to understand and predict asphaltene behavior. Nevertheless, related compositions, to enhance our understanding of each
some ambiguities still remain with regard to the characterization component. This in turn leads to improved simulation results.
of asphaltene in crude oil and its stability during the primary, The literature related to asphaltene phase behavior is reviewed
secondary, and tertiary recovery stages within the near-wellbore and a description of modeling asphaltene deposition,
regions. precipitation, and flocculation is presented. Serious operational
The paper will review asphaltene in crude oil systems: problems caused by asphaltene deposition during oil production
asphaltene properties and their impact on oil production, have driven the ongoing effort to understand this phenomenon.
including the effects of pressure, temperature, and composition. Many studies have focused on related asphaltene precipitation
Asphaltene content is an important factor in determining the flocculation and deposition in oil reservoirs and flow assurance
properties of a crude oil. Three main methods are used to in the wellbores.
measure the asphaltene content in laboratory: the first method Experimental techniques and theoretical models have been
called SARA, which separates dead oil into saturates, developed trying to understand and predict asphaltene behavior.
aromatics, resins, and asphaltenes depending on their solubility Nevertheless, some ambiguities still remain with regard to the
and polarity. The second is aliphatic hydrocarbon titration using characterization of asphaltene in crude oil and its stability
dead oil; in this method the asphaltene precipitation point is during the primary, secondary, and tertiary recovery stages
detected by the asphaltene precipitation detection unit (APDU). within the near-wellbore regions. This paper reviews the
The third method is the depressurization of a live oil literature related to asphaltene precipitation, flocculation, and
bottomhole sample, this method depends on monitoring the deposition. Field cases related to asphaltene precipitation are
flocculation point due to light transmittance caused by the studied and discussed in the paper. This paper will also
infrared laser [3]. highlight the economic impact of asphaltene on production and
Solubility and density parameters trends are proportional maintenance cost.
to the pressure depletion until the pressure reaches the bubble
point. Below the bubble point pressure (Pb), the solubility and DEFINITION OF ASPHALTENE
density are inversely proportional to the pressure. The solubility The classic definition of asphaltenes is based on the
increases linearly with temperature until the reservoir solution properties of petroleum residue in various solvents.
temperature, after that, it decreases linearly as the temperature The word asphaltene was coined by J.B. Boussingault to
increases. These advanced measurements facilitate an describe the constituents of bitumens (asphalts), he found in
understanding of petroleum heavy constituents. Anew research Eastern France and in Peru [4]. He named the alcohol insoluble
field called “Petroleomics” has started receiving more attention; solid obtained from the distillation residue, as "asphaltene,"
it is based on integrating the different knowledge of chemical since it resembled the original asphalt [32]. Asphaltenes are

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impure hydrocarbons often referred to as nitrogen sulfur oxygen osmometry (VPO) has become the prevalent method for
(NSO) compounds, because they contain nitrogen, sulfur, and determining asphaltene molecular weights. However, the value
oxygen hetero-atoms. Some of these hetero-atoms substitute for of the molecular weight from VPO must be weighed carefully
carbon in the aromatic rings. The NSO compounds have the since the measured value of the molecular weight is a function
highest molecular weights and are the heaviest components in of temperature and solvent molecular properties. Reported
crude oils [14]. The NSO compounds are defined also by the molecular weights from ultracentrifuge and electron microscope
standard test method for n-heptane/n-pentane as the crude studies are high, in contrast to those from solution viscometry
components that are insoluble in low molecular weight alkanes and cryoscopic methods, which are low [24]. Table 1 shows the
(i.e. n-heptane and n-pentane) and as the most polar fraction of elemental composition of asphaltene fractions precipitated by
crude oil. The molecular weight of asphaltene ranges between a different solvents.
thousand and several hundred thousands, due to this fact, their
molecular weights are usually reported in terms of distribution TABLE 1: COMPOSITION OF ASPHALTENE FRACTIONS
curves [15]. PRECIPITATED BY DIFFERENT SOLVENTS ACCORDING
TO SPEIGHT AND MOSCHOPEDIS [27]
STRUCTURE OF ASPHALTENE
Our knowledge of the asphaltene structure is very limited.
Asphaltenes are composed of fused benzene-ring networks, but
contain other atoms and are not true hydrocarbons [15].
Asphaltenes are not crystallized and cannot be separated
individual components or narrow fractions. Thus, the ultimate
analysis is not very significant, particularly taking into
consideration that the neutral resins are strongly adsorbed by
asphaltenes and probably cannot be quantitatively separated
from them. Also, not much is known of the chemical properties
of asphaltenes. However, analytical chemists have made
considerable efforts to characterize the asphaltenes in terms of OIL CHARACTERIZATION
chemical structure and elemental analysis as well as by Asphaltene content is an important factor in determining
carbonaceous sources. A number of investigators have proposed the properties of a crude oil. A convenient laboratory method
model structures for asphaltenes, resins, and other heavy called SARA has been developed to quantify the asphaltene
fractions based on physical and chemical [24]. Figure 1 shows a fraction in this process. This technique separates dead oil (oil
general structure model of asphaltene. with no gaseous components) into saturates, aromatics, resins,
and asphaltenes depending on their solubility and polarity. A
schematic representation of this method is shown in Figure 2.
The advantage of the SARA method is that it is a simple
procedure that can be performed in many laboratories [3]. One
type of SARA screening method is the colloidal instability
index (CII). The CII is the ratio of the unfavorable components
to the favorable components of the oil as shown in Equation 1.

S  As
CII  , (1)
R  Ar
Where S is the percentage of saturates, AS is the percentage of
asphaltenes, R is the percentage of resins, and Ar is the
FIGURE 1: GENERAL STRUCTURE MODEL OF percentage of aromatics in the oil. If the CII is greater than one,
ASPHALTENE [15] the amount of unfavorable components exceeds the amount of
favorable components in the system. Consequently, the
The physical and chemical properties of asphaltenes are asphaltenes are likely to be unstable. However, the SARA
different from those of neutral resins. The reported molecular analysis has several disadvantages that become apparent when it
weight of asphaltene varies considerably depending on the is used for purposes beyond its original intent. For example,
method and conditions of measurement. A major concern in dead oil lacks the gaseous components that are dissolved in live
reporting asphaltene molecular weight is the oils, and so the results are not representative of how the oil
association/aggregation of asphaltenes which can exist at the would act under reservoir conditions. In addition, laboratory
conditions of the method of measurement. Vapor pressure methods may vary greatly, and the solubility of asphaltenes

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varies with the type of n-alkanes used to precipitate them. This
means that single oil could have two or more SARA results
depending on the precipitant used. Because of its simplicity,
SARA analysis has become a widespread means for comparing
oils, but often, because variations in laboratory technique are
not reported, comparisons between laboratories may not be
valid. Nevertheless, the SARA method is a reasonable first step
for categorizing dead crude oil, it provides sufficient
characterization for both downstream refining needs and for
upstream concerns, where live-oil properties are needed. There
are two other methods to characterize crude oil besides the
SARA method. The first is aliphatic hydrocarbon titration using
dead oil; in this method the asphaltene precipitation point is
FIGURE 3: DEPICTION OF FLOCCULATION AND
detected by the asphaltene precipitation detection unit (APDU).
DEPOSITION, UNIVERSITY OF FLORIDA
The second method is the depressurization of a live oil
bottomhole sample; this method depends on monitoring the
flocculation point due to light transmittance caused by the ONSET PRESSURE
infrared laser [3]. Another important term is the flocculation onset pressure,
which is defined as the pressure at which the oil fraction reaches
a threshold limit that initiates the asphaltene flocculation and
precipitation. For example, when the CO2 concentration is high
enough, asphaltene dissolved in oil begins to flocculate; the
reason for this is attributed to the injected CO2 that dissolves
into smaller adjacent droplets of oil, and then swell, extracting
light hydrocarbons from the oil and inducing flocculation [12].
Also, the onset of asphaltene flocculation is defined as the least
amount of flocculants in which aggregated asphaltene particles
appear [30].

EFFECT OF PRESSURE ON ASPHALTENE


PRECIPITATION
FIGURE 2: SARA ANALYSIS [3] Asphaltene consists of molecules with a wide range of
densities. It is suggested that high-density molecules will
ASPHALTENE IN OIL RESERVOIR precipitate after the onset pressure, and then the molecules with
There are five main factors that govern the level of the intermediate densities precipitate at lower pressures [1].
asphaltene perception Asphaltene precipitation has implications on production in
-Pressure: (i.e., natural depletion) terms of reservoir natural depletion. Generally, solubility and
-Temperatures density parameters trends are proportional to the pressure
-Alternation of crude oil composition (i.e. CO2 injection, depletion until the pressure reaches the bubble point [19].
solvent addition, etc.) Below the bubble point pressure (Pb), the solubility and density
-Properties of asphaltene of asphaltene precipitation are inversely proportional to the
-Electrical phenomena (i.e., streaming potential generation pressure trend. Figure 4 shows an approximate depiction of
due to the flow of asphaltenes containing oil in density and solubility behavior with pressure depletion
conduits or porous media) (assuming constant temperature).

Precipitation, flocculation, and deposition


Before discussing main factors that affect the asphaltene
perception, important terminology needs to be defined.
Precipitation is the process that triggers the appearance of
asphaltene particles. However, when those precipitated particles
aggregate, they form bigger particles called ‘flocs’ and that
process is called flocculation. Deposition is the process of
exchanging flocs between the solution phase (i.e., oil) and the
rock surface [10]. Figure 3 shows a clear distinction between
the deposition and flocculation process.

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From Figure 4 and Figure 5, we can conclude that the
maximum asphaltene precipitation is expected to occur at or
close to the bubble point pressure (Pb). Since pressure
decreases below the bubble point, the light components separate
from oil and move into the gas phase. Therefore, asphaltene
solubility increases and some precipitated asphaltene dissolve
back into the oil solution. As pressure decreases, above the
bubble point, the asphaltene content of the crude oil decreases
and the minimum content of asphaltene occurs near the
saturation pressure (Pb) as shown in Figure 5.
Actual field experience indicates less asphaltene
precipitation problem, when the pressure is below the bubble
point, than when the pressure is at the bubble point [19]. Many
field tests (i.e., Hassi-Messaoud field in Algeria and Mata
Acema field in Venezuela) show that the heavier crudes
FIGURE 4: DEPICTION OF DENSITY AND (containing a higher amount of asphaltene) have much less
SOLUBILITY BEHAVIOR WITH PRESSURE precipitation problems compared to the highly under-saturated
DEPLETION light crudes (contain small asphaltene content). Formation sand
and silt help expedite the formation of deposits when the
The density and solubility increase below the bubble point temperature drops where the dissolving power in the heavier
due to the liberation of the lighter hydrocarbons and gases from crude is much greater than that the of lighter crude [17].
a crude oil, which in turn increases the asphaltene solubility. Experimental observations showed that the temperature
Furthermore, the crude will be much denser due to this gas has the same effect on the recovery of asphaltenic and non-
liberation. The amount of asphaltene precipitating will be asphaltenic oils; however, the experimental studies showed that
opposite to the behavior of density and solubility as a function higher oil recovery will be anticipated from non-asphaltenic oil
of pressure. Also, an increase in the amount of dissolved gas in compared to asphaltenic oil at the same temperature [12].
live oil is associated with the lower solubility of asphaltene in
that oil [17].
Figure 5 shows an approximate depiction of the amount of
asphaltene as a function of pressure depletion (assuming
constant temperature). The loss of light hydrocarbon
components constituting a crude oil reduces the amount of solid
deposits that can be held in a solution, which reduces the
dissolving power of the crude.

FIGURE 6: DEPICTION OF ASPHALTENE


SOLUBILITY AS A FUNCTION OF
TEMPERATURE [18]

EFFECT OF TEMPERATURE ON ASPHALTENE


PRECIPITATION
During primary oil recovery, the reservoir temperature
change is usually negligible; however, the change will be
FIGURE 5: DEPICTION OF THE AMOUNT OF noticeable during secondary and tertiary recovery. According to
ASPHALTENE AS A FUNCTION OF PRESSURE the literature, there is no clear trend for temperature effect on
DEPLETION asphaltene due to the variation of the crude composition. Some
researchers [18] suggested that the asphaltene solubility
increases linearly with temperature until the reservoir

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temperature, after that, asphaltene solubility will decreases
linearly as the temperature increases shown in Figure 6. Some EOR screening consists mainly of:
authors claimed that a reduction in precipitation could be - Evaluating available information about the reservoir, oil,
expected when temperature increases, whereas others claimed rock, water, geology and previous performance.
the opposite. Generally, temperature dependence cannot be - Supplementing available information with certain brief
easily guessed based on the discrepancy in the temperature laboratory screening tests.
dependence results between the researchers. This indicates that - Selecting those processes that are potentially applicable
more collaborative work is needed to analyze the temperature and eliminating those that definitely are not.
dependence.
These are the first steps in an enhanced recovery
ALTERNATION OF CRUDE OIL COMPOSITION implementation sequence. Subsequent steps would include
One common problem during gas drives or CO2 injection further evaluation of candidate processes (if more than one
is asphaltene instability, which induce precipitation and may satisfies the screening criteria), pilot test design, pilot test
cause pore-throat-plugging or wettability reversal [18]. implementation, pilot test evaluation, scale-up forecasting, and
Asphaltenes become unstable as the volume fraction of aliphatic finally, commercial venture. Laboratory test results, together
components increases. It was experimentally proven that, if a with the reservoir engineering analysis, form the basis for
crude oil has a flocculation point, then the region of asphaltene estimating the enhanced recovery potential of a candidate
instability would be located between the flocculation point and reservoir.
just below the bubble point [11]. Figure 7 explains this in detail.
Also, experiments show that denser asphaltenes have a higher ELECTRICAL PHENOMENA
tendency to precipitate initially than less denser asphaltenes Asphaltenes exist in crude oil either in the molecular form
[18]. or in the form of an association of a relatively small number of
molecules [21]. Several ultracentrifuge experiments were
performed to investigate the molecular weight; the results
showed that asphaltene exists in crude oil as particles with a
diameter of 30 to 65 oA [22]. Asphaltene electrical effects were
tested by using a crude oil. It was concluded that crude oil
containing asphaltene has an electrical effect and the streaming
potential caused by the flowing crude oil may cause asphaltene
to precipitate [9]. Several tests were conducted to examine the
reversibility process of asphaltene precipitation and the results
showed that it is a reversible process [7].

DIFFERENCES BETWEEN WAX AN ASPHALTENE


There has been some confusion between the definition of
asphaltene and other terms such as asphalt, resin, and wax in the
literature. Therefore, it is important to give a basic definition for
each term and highlight the most important distinguishing
FIGURE 7: REGION OF INSTABILITY DEPICTION parameters between them.
BASED ON ELLISON AND GALLAGHER [11]
ASPHALT
CO2 injection is one of the main factors that induce asphaltene Asphalt is a mixture of high molecular weight complex
precipitation and instability. The degree of swelling is compounds that flocculates out of oil and contains asphaltene
dependent on the pressure, temperature, and oil composition. particles surrounded by resins, oil, and other liquid entities in
CO2 can improve oil production by reducing the interfacial the crude oil trapped in the flocculated mass [15]. Asphalt, is
used generally to designate the combination of asphaltene and
tension or Increasing mobility ( ), i.e., reducing
resins. It is a term used commonly for refinery products, called
viscosity. Asphaltene precipitation is initiated by CO2 when the ″petroleum asphalt″ and ″refinery asphalt″ [32]. Based on the
critical content of CO2 is exceeded. The critical content point of results from studies of asphalts and related bituminous
CO2 is dependent on a reservoir oil composition, temperature, substances, a classification scheme was developed as presented
and pressure and must be evaluated at an early stage of EOR in Figure 8 [1], and modified later by Pfeiffer [20]. The study
screening (i.e. pilot design) for EOR [15]. suggested that asphalt can be classified into artificial asphalts
and natural asphalts. Artificial asphalts are man-made or
synthetic and include basically petroleum-derived asphalts and,
to a lesser extent, coal tar, water-gas tars and other substances.

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Natural asphalts include bituminous materials laid down in Knowledge of the properties and behavior of the resins could be
natural deposits, such as those in Trinidad and the Bermudez useful in remedial actions when there is a need for additives or
lakes, and also those in natural bitumens [5]. acid treatment.

WAX
Wax, sometimes called ″Paraffin,″is defined as saturated
hydrocarbons with between 18 and 34 carbon atoms in a chain
of complex mixtures of high molecular weight alkanes ranging
between 360 and 500. Waxes are organic deposits caused by
changing wellbore conditions that upset the chemical
equilibrium so that various materials in the crude oil precipitate
out of the solution. It is of a crystalline structure and can be soft
with a high proportion of trapped oil such as Vaseline, or can
form hard deposits such as candle wax. Paraffins usually exist
in waxy crudes and create production problems and formation
damage. To eliminate these problems, the deposited paraffin
must be removed. Crude wax or paraffin deposits consist of tiny
crystals that tend to agglomerate and form granular wax
FIGURE 8: DESIGNATION AND CLASSIFICATION OF particles about the size of table salt grains. Deposited paraffin
NATURAL ASPHALT ACCORDING TO ABRAHAM [1] may also contain crude oil, sand, silt, corrosion products, scale,
and often water [15]. ASTM or API methods can be used for
Asphalt is classified into three fractions: conventional wax determination in crude oils. Both methods
- Neutral resins: insoluble in Alkalies and acids and involve cooling the oil to a specific temperature, precipitating
completely miscible with crude oil. the waxes, collecting, and weighing them. This normally results
- Asphaltenes: insoluble in light gasoline and petroleum in compounds containing an average of 22 or more carbon
ether. atoms being precipitated.
- Carboids (free carbons): found at high temperatures, Often iron sulfide and heavy wax are misidentified as
completely insoluble in benzene. asphaltenes, where asphaltenes are often found mixed with wax
or oil. One way to differentiate between them is by a melting
Note that both asphaltene and neutral resins are completely
test and a weak acid solubility test. Asphaltene solubility can be
soluble in benzene, chloroform, and carbon disulfide.
determined by conducting a series of titration experiments on
tank oil [27]. To understand the behavior of waxy crude, we
need to know the cloud point, pour point, wax content, and
RESINS
yield stress of the particular crude. When the temperature drops
On the other hand, resins are polycyclic molecules that
too low for wax to remain dissolved in the crude, it precipitates
exist in the oil in true solution and tend to adsorb easily in
out of the solution and deposits itself on pipeline walls, or
common adsorbents (i.e. clay and silica gel) and have a
inside facilities. The temperature at which the wax crystals can
molecular weight ranging between 250 to 1000 [14]. Other
first be detected is called the cloud point. The cloud point is
references reported that the molecular weights of resins range
also sometimes referred to as the wax appearance temperature
from 1100 to 2800 [27]. The resin fractions constitute the main
(WAT). When the operating temperature in a pipeline system
non-hydrocarbon part of residues with high contents of
drops below the cloud point, wax crystals will begin to form
heteroatoms [32]. Under normal conditions, asphaltenes are
and deposit. As the temperature drops further, more wax will
held in suspension by resins. Changes in the crude composition
come out of the solution until the crude in the pipeline
or pressure and temperature can alter their association with the
effectively gels up. The temperature at which this occurs is the
resins [3]. Resins play an important role in stabilizing and
pour point. When the crude in the pipeline gels up, a certain
peptizing of asphaltene molecules and help reducing the
force, yield stress, is required to shear the waxy crude and
flocculation and precipitation of the molecules out of the
restart the flow. Crude is generally considered to have a high
solution
wax content when there is more than about 10% wax, and a low
wax content when there is less than about 4%. Some examples
of low wax content crude are shown in Table 2.

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TABLE 2: LOW WAX CONTENT CRUDE OILS
ACCORDING TO IPIMS [15]

Although the wax content of all these crude is 4%, there are
considerable differences in the pour point. As shown in Table 2,
we notice that the Malaysian Labuan crude would gel up at 90
o
C, whereas the Saudi Arabian Light crude would gel only if the
temperature drops below -36 oC. Table 3 summarizes the
behavior of waxy crude that have relatively high pour points. FIGURE 9: SEVERITY OF WAX DEPOSITION
(HTTP://OMRPUBLIC.IEA.ORG)

TABLE 3: HIGH WAX CONTENT CRUDE OILS Designers and operators of the pipeline need to thoroughly
ACCORDING TO IPIMS [15] evaluate the above factors when waxy crude is found in their
system. When deciding how to manage the production and
transportation of waxy crude, it is important to consider both
capital and operating cost over the whole life cycle of the field
for different options.
A development plan for managing a waxy crude field will be
different and probably more costly than a non-waxy crude field.
Hence, early prediction in terms of compositional simulators,
especially for wellbore vicinity is very important. There are
several models being developed that take into account wax
deposition in the wellbore. Waxy crude production can be
handled using the following options [15]:
- Using wax inhibitors, growth modifier, or dispersants
Wax formation in crude oil flowing in pipelines (Figure 9) can - Using a pour point reducer
be predicted by sampling and analyzing the crude based on the - Using dilution, in order to minimize wax content
following four properties: - Using sophisticated pipeline insulation techniques
- Cloud point: measured using the cold finger technique or - Using heating systems or steam tracing for the pipeline
cross polar microscopy
- Pour point: measured using differential scanning ASPHALTENE PROPERTIES
calorimetry (DSC) Production and processing operations of crude oil require
- Wax content: measured using solid phase analysis a thorough understanding of phase behavior. Pressure-volume-
- Carbon distribution: measured using high temperature gas temperature (PVT) properties play a crucial role throughout the
chromatography (HTGC) life of the reservoir. Reservoir fluid properties provide the main
input for any simulator used to predict asphaltene precipitation
It is important to use a representative sample of the crude for or describing the fluid properties as a function of pressure,
testing and to follow the correct experimental procedures in temperature, and composition. Consequently, accurate PVT
order to achieve the most accurate results. These results may be properties are required to get appropriate and representative
used as the base input parameters for a simulation model. Waxy simulation results. As mentioned earlier, the main factors
crude with high cloud points and pour points will need a special affecting asphaltene precipitation are pressure, temperature, and
design to take into account the operational challenges. composition. However, a good understanding of properties’
behavior is needed. These properties are density, solubility,
viscosity and molecular weight, which can be directly affected
by any changes in pressure, temperature, or composition. For
that purpose those four factors will be highlighted in detail in
the following sections.

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DENSITY ρ  1  .3447 H / C –  0.5396  . (2)
Density is a physical property strongly related to the
molecular topological characteristics and also to the molecular The results of the study showed that the density increases
size of the molecules [25]. Density can be easily determined in as the H/C ratio decreases and that the introduction of heavier
a lab and it is often used to calculate other thermo-physical atoms in the molecule may cause an increase in the molecular
properties. It is suggested that at a constant temperature, the interactions due to the presence of heteroatoms. The authors
density parameters trend is proportional to the pressure highlighted that the calculation of asphaltene density using
depletion until the pressure reaches the bubble point [19]. average structures by molecular dynamic simulations was
Below the bubble point pressure (Pb), the density is inversely subject to large errors; however, it generated values that are
proportional to the pressure trend as shown in Figure 10. qualitatively correct and in the right range.
Yarranton and Masliyah [31] conducted several
experimental works that include density measurements. Density
was measured using the Anton Paar device. It was measured for
solutions of asphaltene in toluene at concentrations of 0 to 1.14
wt.%. The regular solution behavior was assumed due to the
low concentration obtained. The asphaltene density then can be
determined indirectly from Equation 2 and Equation 3, utilizing
a plot of the inverse mixture density versus asphaltene mass
fraction as shown in Figure 11.

1  1
1 1 
   x , (3)
 M T   A T  A
1
A  , (4)
SI

FIGURE 10: DEPICTION OF DENSITY BEHAVIOR Where


WITH PRESSURE DEPLETION (AT CONSTANT
ρM is the mixture density (kg/m3)
TEMPERATURE)
ρT is the toluene density (kg/m3)
ρA is the average asphaltene density (kg/m3)
Asphaltene density can be indirectly determined from
xA is the asphaltene mass fraction
measurements of a known concentration of asphaltene in
S is the slope of the mixture density plot
toluene using the Anton Paar device [31]. During the past few
I is the intercept of the mixture density plot
years, molecular dynamics and molecular mechanics
simulations have been successfully used to describe and
determine thermodynamic properties such as density [28].
Recently, density values for average structures of asphaltenes
from the Berri Middle-Eastern field have been calculated using
molecular dynamic simulations [8], it has been found that the
densities of different solid products of crude oil correlate very
well with the H/C ratio and also with solubility. Rogel and
Carbognani [23] carried out a simulation study that utilizes
″molecular mechanic and molecular dynamic simulations″ to
determine the density of average structures of various
representative asphaltenes samples. The effect of structural
aspects such as H/C ratio on the calculated densities was
investigated as well. The study compared the calculated
densities using molecular simulations with experimental values.
The initial density for the average structure was estimated from
a correlation between the density and H/C ratio based on FIGURE 11: DEPENDENCE OF ASPHALTENE-
experimental data that include asphaltenes from virgin and TOLUENE MIXTURE DENSITY ON ASPHALTENE
processed crude oils. This correlation is the following: CONCENTRATION ACCORDING TO
YARRANTON AND MASLIYAH [31]

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The study concluded that the scattered results in density Where
determination illustrate the difficulty in obtaining distributions ΔU vap is the internal energy (J/mol) of vaporization
and explain the small amount of data on asphaltene densities in
the literature. The study suggested more testing for the vil is the liquid phase molar volume (m3/mol)
correlation to verify the density determination robustness on  il is the solubility parameter (MPa1/2)
asphaltenes density from other sources and with different
solvents.
VISCOSITY The solubility parameter can be correlated to molar mass using
Viscosity variations are known to match those of the Equation 7 by treating asphaltene as a homogenous
volume of a colloidal aggregate occupied per unit mass of composition. The effect of temperature on the solubility
asphaltene [16]. When precipitation occurs, asphaltene fines parameter of asphaltene is shown in Figure 12. The solid line
may alter the viscosity of the transporting phase which is oil represents a linear regression line through the data points. The
phase. The precipitation tends to increase the oil viscosity and figure clearly indicates that the solubility parameter of
the deposition of heavier components tends to make the oil asphaltene decreases linearly with temperature. This trend can
lighter and therefore reduces its viscosity. The viscosity be explained by the fact that as the temperature of a crude oil
alteration can be modeled in two different ways [15]: decreases, the crude solubility decreases as well and can no
longer keep the particles in suspension. As a result, the particles
will settle and form deposits. A linear decrease of the asphaltene
- Generalized Einstein model
solubility parameter with temperature has also been reported by
µ Hirschberg et al. [13].
 1  aCP , (5)
µ0
where
a = 2.5 (default value)
Cp is the volume concentration of precipitate
μ0 is the oil viscosity at Cp=0

- Krieger and Dougherty model


µ C
 (1  CP P )  ηCP 0 , (6)
µ0 CP 0
Where
η is the intrinsic viscosity, η = 2.5 for spherical colloids
Cp0 is the volumetric concentration for maximum packing,
equal to 0.65 for spheres packing.

SOLUBILITY
Several attempts were made to model asphaltene solubility
FIGURE 12: SOLUBILITY PARAMETER OF
using experimental measurements of density which is then
ASPHALTENE AS A FUNCTION OF TEMPERATURE
correlated with molar mass. Asphaltene solubility in crude oil
FOR P = 100 BAR AS INDICATED BY YEN AND
has been the subject of several theoretical investigations.
CHILINGARIAN [32]
Hirschberg et al. [13] combined Hildebrand regular solution
theory with a Flory-Huggins theory to express asphaltene
solubility in crude oil as a function of molar volume and the The effect of pressure on the solubility parameter of
solubility parameter. Since asphaltenes are mixtures of asphaltene at T = 300 K is shown in Figure 13. The solid
molecules, the solubility can be determined using flash line represents a linear regression line through the data
calculation. With the large molecules size of asphaltenes, it is points. It indicates that the solubility parameter of
necessary to use the Flory-Huggins theory. The solubility asphaltene is not affected very much with the change in
parameter is defined as follows: pressure. However, as discussed earlier, Leontaritis and
Mansoori [19] suggested that at constant temperature, the
solubility parameter’s general trend is proportional to the
ΔU vap 1/2
 il  ( ) , (7) pressure depletion until the pressure reaches the bubble
vil point. Below the bubble point pressure, the solubility is
inversely proportional to the pressure trend as depicted in
Figure 14. Generally, pressure holds dissolved gases and

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light hydrocarbon components in solution and helps and resins. However, mass spectrometry and molecular
maintain a constant temperature. As pressure drops, the diffusion provide distinctive and accurate measurements of
temperature drops, because of gas expansion. As a result, asphaltene molecular weight and size.
the heavier components will settle and form deposits.
- Mass spectrometry
Mass spectrometry depends on measuring the ratio of ion
charges (resulting from an electromagnetic field) to mass. Mass
spectrometry can identify molecules based on the knowledge of
their mass, provided that the molecule can be ionized (i.e.,
charged and vaporized). One of the main resources for
asphaltene studies using mass spectrometry is the National High
Magnetic Field Laboratory at Florida State University. Table 4
shows a summary of mass spectrometry measurements with a
short description for each technique.

- Molecular diffusion
Molecular diffusion basically depends on monitoring the
FIGURE 13: SOLUBILITY PARAMETER OF diffusion of individual molecules using special measuring
ASPHALTENE AS A FUNCTION OF TEMPERATURE techniques (i.e., fluorescence techniques). The slower the
FOR T = 300 K AS INDICATED BY YEN AND diffusion, the larger the molecule size and vice versa. This type
CHILINGARIAN [32] of measurement is very helpful, because the estimated molecule
size is used to infer the molecule weight by a comparison with
model compounds [26]. Table 5 shows a summary of mass
spectrometry measurements with a short description for each
technique.

TABLE 4: MEASUREMENT METHODS USING MASS


SPECTROMETRY IN TERMS OF MOLECULAR
WEIGHT, COURTESY OF SCHLUMBERGER [26]

FIGURE 14: DEPICTION OF SOLUBILITY


BEHAVIOR WITH PRESSURE DEPLETION (AT
CONSTANT TEMPERATURE)

MOLECULAR WEIGHT
Asphaltenes’ molecular weight is difficult to measure since
it depends on three factors [30]:
- Nature and amount of solvent (can be controlled by using
specific types of solvents that prevent aggregation)
- Temperature
- Contact time

Most of the available asphaltene modeling techniques were


developed before the recent advancements in measuring the
asphaltene molecular weight. Researchers [24] believe that
asphaltenes exhibit a wide range of molecular weight. There is
still some debate about the size/structure of individual
asphaltene molecules. Several techniques have been recently
developed to study heavy oil fractions such as asphaltenes, wax,

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TABLE 5: MEASUREMENT METHODS USING REFERENCES
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