Article

ON THE EFFECT OF TEMPERATURE ON PRECIPITATION AND

AGGREGATION OF ASPHALTENES IN LIGHT LIVE OILS†

Saber Mohammadi1, Fariborz Rashidi2*, Sayed Ali Mousavi-Dehghani1, Mohammad-Hossein

Ghazanfari3

1
Department of Petroleum Engineering, Amirkabir University of Technology, Tehran, Iran

2
Department of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran

3
Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran,
Iran

*Corresponding author. Tel: +98-21-64543190, Fax: +98-21-64542233. E-mail address:

rashidi@aut.ac.ir

†
This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
article as doi: [10.1002/cjce.22555]

Received 12 November 2015; Revised 20 December 2015; Accepted 19 January 2016

The Canadian Journal of Chemical Engineering
This article is protected by copyright. All rights reserved
DOI 10.1002/cjce.22555

This article is protected by copyright. All rights reserved 1

 ABSTRACT
Asphaltene precipitation and deposition is a serious issue in all facets of petroleum production and

processing. Despite the numerous experimental efforts concerning asphaltenes, the effect of

temperature on asphaltene precipitation and aggregation in live oils remains still an elusive and

controversial subject in the available literature. In this work, a series of high pressure-high

temperature depressurization experiments were designed to assess the effect of temperature on

asphaltene precipitation and aggregation in light live oils. Asphaltene related experiments were

performed using high pressure microscope and high pressure-high temperature filtration setup on a

light live oil with low asphaltene content and a high potential of asphaltene formation. The results

of the experiments were interpreted in terms of asphaltene onset pressure, size distribution and

average diameter of the aggregates, fractal dimension of the asphaltene aggregates, and the amount

of precipitated asphaltene. It was found that depressurization process at higher temperatures results

in higher asphaltene onset pressure or earlier formation of the asphaltenes. Visualization

experiments showed that asphaltene aggregates in light live oil are pressure-temperature fractal

structures. Depressurization process at lower temperatures led to the formation of highly porous and

loose aggregate structures with relatively low fractal dimensions. As the temperature of the

depressurization process decreases the mechanism of asphaltene aggregation changes gradually

from reaction limited aggregation to diffusion limited aggregation. This research reveals that

temperature has crucial effects on asphaltene aggregation process in light live oils at elevated

pressures which is of great importance for asphaltene handling and separation. This article is

protected by copyright. All rights reserved

Keywords: asphaltene aggregation, light oil, fractal, high pressure-high temperature, experimental

This article is protected by copyright. All rights reserved 2

 INTRODUCTION
Asphaltenes are one of the most problematic and less understood compounds of the crude oil which

are soluble in aromatics solvents and insoluble in saturated hydrocarbons.[1-5] Any changes in

thermodynamic conditions (pressure, temperature, or oil composition) destabilizes asphaltenes and

represents a variety of problems in both upstream and downstream oil industry.[6–8] Reduction of the

well inflow performance and increasing the overall operating cost, wettability alteration of the

reservoir rock, plugging surface facilities and flow lines, contribution to the catalyst deactivation,

and equipment fouling are some of their detrimental consequences.[1,9] To mitigate the problems

induced by asphaltenes, a thorough understanding of the mechanisms of asphaltene destabilization

(aggregation/precipitation) as well as the effective related factors is essential.[10,11] The asphaltene

stability and the mechanisms of its precipitation and aggregation in crude dead oils or model oils

have attracted massive experimental and modelling research attentions for several decades.[1,12–18]

These works are mostly limited to the synthetic asphaltenes extracted by addition of the saturated

hydrocarbon solvents (e.g. nC5 or nC7) at standard lab conditions. The majority of the previous

works on thermodynamics of asphaltene stability are based on the assumption that asphaltene

destabilization is an instantaneous phenomena and the kinetics effects associated with the

asphaltene precipitation and aggregation have not been considered.[19-23] The many experiments

reported to date indicate that asphaltene aggregation is a gradual and time-dependent process that

occurs very slowly.[12,17,24]

While field experiences and laboratory studies well demonstrate the effects of change in pressure

and oil composition on asphaltene destabilization, the effect of temperature, especially in live oils

(live oils contain dissolved gases which are held by high reservoir pressure), has not been well

understood. Temperature does not show any direct effect on asphaltene destabilization. In regard to

the effect of temperature on asphaltene stability, contradictory and diverse observations have been

reported. A complete review on the effect of temperature on solubility of asphaltenes was done by

Chandio et al.[14] Some results show that the asphaltene solubility decreases with temperature

This article is protected by copyright. All rights reserved 3

rise,[25–27] while others have found that asphaltene solubility increases upon rising the

temperature.[14,28–30] In addition, data published by several researchers show both increasing and

decreasing behaviour for asphaltene solubility with temperature.[18,31–34] Maqbool et al. used optical

microscopy to study the effect of temperature on kinetics of asphaltene precipitation in crude dead

oil at atmospheric pressure.[24] They found that at higher temperatures the onset time of precipitation

is shorter. Mehranfar et al. studied the effect of temperature (25–80 °C) on asphaltene structural

changes in air using atomic force microscopy.[3] They showed that an increase in temperature above

70 oC leads to transition from self-assembled fractal structures to substantially larger liquid phase.

Chandio et al. studied the effect of temperature on solubility of asphaltenes for six different crude

oil samples in the temperature range of 20–95 °C, using automated flocculation onset titration.[14]

They indicated that solubility of asphaltenes increases with increase in temperature and possible

phase transition of asphaltenes takes place with temperature rise. Negahban et al. showed that

decreasing the temperature of the live oil increases the onset pressure of asphaltene precipitation. [35]

Recently, Bahrami et al. performed high pressure-high temperature (HPHT) experiments to study

the effect of temperature on asphaltene precipitation in an Iranian heavy oil reservoir.[36] Based on

the obtained results, asphaltene precipitation increases from 60 oC to 80 oC and it decreases from 80
o
C to 96.1 oC. Despite the above mentioned studies, the reported results are inconsistent and the

majority of the experiments were performed on chemically separated asphaltenes (asphaltene-

solvent-precipitant mixture), crude dead oils, or model oils at atmospheric pressure. HPHT

experimental data on asphaltene solubility and its mechanisms of precipitation/aggregation in live

oils are scarce.

Our literature survey highlights the necessity and value of in-depth investigation of the asphaltene

destabilization in live oil systems (i.e. real oil field asphaltenes) by variation in temperature at

elevated pressures. This issue is more essential in light oil reservoirs because light oils with little

asphaltenes are the most susceptible to asphaltene problems.[4] In this study, in an attempt to fill this

void-a series of HPHT depressurization experiments were performed to study the effect of

This article is protected by copyright. All rights reserved 4

temperature on asphaltene precipitation and aggregation in light live oils. For conducting the HPHT

experiments a high pressure microscope (HPM) and HPHT filtration setup were utilized. The

asphaltene onset pressure (AOP) and size distribution of asphaltene aggregates were monitored by

HPM. HPM photographs were analyzed and processed to determine the fractal dimension of the

asphaltene aggregates as a function of pressure and temperature. The amount of precipitated

asphaltene during depressurization process at different fixed temperatures was measured by HPHT

filtration tests. Finally, the mechanisms of asphaltene precipitation and aggregation at different

temperatures were presented and discussed through different sets of results.

EXPERIMENTAL SECTION
Fluid Characteristics

Asphaltene related tests were performed on an Iranian light oil sample from a reservoir in the

southwest region of Iran. This oil sample was collected using single-phase reservoir sampling

technology to attain a representative fluid for asphaltene study.[37] The general properties of the oil

sample and oil field are summarized in Table 1.

Experimental Apparatus and Procedure

In this work, HPM (model Leica Z16 APO, Germany, with total magnification of approximately

1000X) and HPHT filtration setup were used to perform asphaltene related tests at HPHT

conditions. Figure 1 shows schematic diagram of the HPM setup. The HPM enables direct visual

observation of the solid particles (e.g., asphaltene) at elevated pressures and temperatures. It also

permits to monitor the onset and the growth of asphaltenes as a function of pressure, temperature,

and composition, and hence to better understand the morphological behaviour of the asphaltene

aggregates. It consists of a cell with two sapphire windows, a long focal length camera of high

resolution, and a light source. The cell thickness is 0.3 mm and the diameter of the sapphire is 9.2

mm. However, the cell thickness can be adjusted according to requirements. The cell temperature is

controlled by a circulation bath (manufactured by Huber-GmbH Company) whereas the fluid

pressure inside the cell is maintained using a positive displacement pump. The maximum working

pressure and temperature of the HPM are 103.4 MPa and 455.4 K, respectively.

This article is protected by copyright. All rights reserved 5

Before starting the asphaltene related tests by HPM, pressure-volume-temperature (PVT)

experiments are carried out to obtain the main properties of the oil sample studied here (e.g. well

stream composition, saturation pressure, gas-oil ratio, oil density, isobaric thermal expansion, and

isothermal compressibility coefficients of oil). For asphaltene related tests, the fluid sample is

restored and homogenized for about 1–2 days at temperature of the test and at least 6.9 MPa (~1000

psi) above the initial reservoir pressure. Subsequently, about 70 cm3 to 80 cm3 of single-phase live

oil sample is charged to the PVT cell using a positive displacement pump and stabilized at specified

temperature for about 4–5 days. The high pressure PVT cell is contained inside a thermally

insulated temperature controlled air bath. This air bath is held at a steady temperature to ± 0.2 K, by

a high precision temperature controller. Prior to each depressurization experiment in HPM, the high

pressure cell of the HPM is cleaned with toluene and acetone, then flushed with nitrogen, and

finally vacuumed. The high pressure cell is heated to a pre-specified temperature and is pressurized

with N2 gas to the sample charging pressure. The original equilibrated fluid under consideration is

homogenized at specific pressure and temperature in the PVT cell connected to the HPM system;

then about 1 cm3 of the original equilibrated fluid in the PVT cell is transferred isobarically and

isothermally from the PVT cell to the HPM cell at controlled flow rate. The HPM cell is stabilized

at initial pressure and temperature of the test. Subsequently, the depressurization experiment is

started discontinuously at isothermal conditions with average rate of about -1.16 MPa/hr as the

AOP is detected. It should be emphasized that since the photograph are taken at pressure intervals

of about 0.69 MPa (~100 psi), the estimated AOP by HPM is precise to ± 0.345 MPa. After

detection of the AOP by HPM, in order to study the asphaltene aggregation process, the pressure is

reduced at discrete steps; at each step the pressure is kept constant over time to reach equilibrium

conditions (i.e. no more changes in asphaltene aggregation process). The cell contents are observed

visually and recorded by the HPM video camera during the course of the experiment. High

resolution photographs of the sample are taken at distinct pressure steps over time to monitor the

aggregation process, and ImageJ package, version 1.44 was used for image analysis and processing.

This article is protected by copyright. All rights reserved 6

ImageJ is a Java-based image processing program developed at the National Institutes of Health.[38]

The intensity of the light source, magnification, and focus of the microscope camera are carefully

adjusted and set in order to capture clear digital images of the live oil layers at any time during the

experiments. This procedure is repeated at different fixed temperatures to assess the effect of

temperature on asphaltene aggregation.

In another set of experiments, HPHT filtration tests are conducted with a 0.20 µm Cellulose Nitrate

filter for the same live oil sample, which is used during the HPM experiments. The schematic

diagram of the HPHT filtration setup is shown in Figure 2. To start the test, about 150 cm3 of

single-phase reservoir fluid is transferred isobarically and isothermally into the high pressure PVT

cell. For each experiment, the PVT cell is stabilized at initial pressure and temperature of the test

for about 4 days. After stabilization of the system, the pressure is lowered at pre-defined steps

above and below the saturation pressure. At each pressure step, the cell content is homogenized for

24 hours; then the fluid is displaced through the filter, and a small amount (10 cm3) of well-mixed

fluid sample is expelled from the PVT cell at pressure and temperature of the experiment to flash to

atmospheric condition. Then, the asphaltene content was measured using the IP-143 standard test

(ASTM D6560-00)[39] to determine the amount of precipitated asphaltene. The HPHT filtration

setup can give proper results at the range of pressure and temperature up to 68.9 MPa and 455.4 K.

The instrumental uncertainties in pressure and temperature control of the experiments are

approximately ± 0.02 MPa and ± 0.2 K, respectively.

RESULTS AND DISCUSSION

Feasibility of Asphaltene Precipitation

There are different screening criteria that have proven fruitfully to detect asphaltene precipitation

potential. One of the most common methods to categorize the possibility of oil to demonstrate solid

phase problems is De Boer plot.[40] De Boer plot shows the relationship between difference of initial

pressure and saturation pressure (Pi-Pb) and density of live oil at initial pressure condition (ρor). The

status of the studied live oil sample on De Boer plot regarding to potential of asphaltene

precipitation is shown in Figure 3. Another screening approach to identify crude oil system with

This article is protected by copyright. All rights reserved 7

having asphaltene precipitation potential is colloidal instability index (CII).[41] CII value expresses

the ratio of the total asphaltenes and saturates to the total of aromatics and resins. If oil has CII

value below 0.70, it is defined as stable or unproblematic oil, whereas the CII higher than 0.90 is

considered as unstable or problematic oil. SARA analysis (ASTM D4124-09)[42] was performed to

divide the oil into saturate, aromatic, resin, and asphaltene components, as given in Table 2. Based

on the SARA analysis results, the CII value of the studied oil sample is 1.92 which shows severe

potential of asphaltene precipitation. Also, oil field primary production records in this reservoir has

shown asphaltene-induced operational problems for the studied oil sample. Considered screening

methods (De Boer plot and CII approach) along with field production records represent high

potential of studied oil sample to cause flow assurance problems. Thus, a comprehensive study of

asphaltene precipitation and aggregation behaviour is essential in this reservoir.

Effect of Temperature on Asphaltene Onset Pressure (AOP)

Depressurization experiments are conducted at four different temperatures (408 K, 364 K, 341 K,

and 319 K). The lowest temperature of the experiments is selected based on the wax appearance

temperature (WAT) of each sample to avoid interference with the wax formation. The WAT of the

oil sample (see Table 1) was determined by viscometry technique.[43] Estimated AOPs by HPM and

saturation pressures (Pb) of the studied oil sample at different temperatures are given in Table 3.

AOP is merely defined as the pressure at which asphaltene particles of 0.50 µm size are detected.

According to the obtained results (Table 3), with temperature rise asphaltenes start to precipitate at

higher pressures. This is in conflict with the findings of Negahban et al.[35] The higher AOP at

higher temperature can be attributed to the effect of temperature on solvent power of the oil and/or

the oil viscosity.

Temperature has a dual effect on solvent power of oil, and either increase or decrease of solvent

power of the oil with temperature has been previously illustrated.[18,19,34,35] The oil-asphaltene

solubility parameter difference (δasp-δoil) as a driving force for asphaltene destabilization, controls

the overall interaction energy between asphaltene particles as well as the extent of asphaltene

This article is protected by copyright. All rights reserved 8

solubility in oil. Solubility relations (phase separation) in petroleum reservoir fluids can be well

predicted by solubility parameter (δ) which is defined as follows:[44]

(1)

where -E and V are the cohesive energy (kJ) and the molar volume (m3/mol) of the liquid,

respectively. Taking into consideration the effect of pressure and temperature, the solubility

parameter of live oils can be measured by internal pressure (π) concept which is defined as

follows:[45,46]

(2)

where is the coefficient of isobaric thermal expansion of oil (K-1), and is the coefficient of

isothermal compressibility of oil (MPa-1). In this study, and are determined through the PVT

experiments performed in visual PVT cell over a wide range of pressures and temperatures. The

solubility parameter of asphaltene (δasp) is calculated by the correlations given by Yarranton and

Masliyah.[47]

The oil-asphaltene solubility parameter difference versus pressure and at different fixed

temperatures for the studied live oil sample is presented in Figure 4. From the solubility parameter

point of view, the oil-asphaltene solubility parameter difference controls asphaltene destabilization

or the overall interaction energy between asphaltene particles. As the temperature of the

depressurization experiments increases the oil-asphaltene solubility parameter difference decreases

(Figure 4) and oil becomes better solvent for asphaltene. Therefore, asphaltene destabilization is

delayed and asphaltene should precipitate at lower pressures, which is in contrast to the obtained

results. This contradiction may be related to the reduction of oil viscosity with temperature rise. Oil

viscosity controls the collision frequency of asphaltene particles and affects their rate of

aggregation. The decrease of the oil viscosity with increment of temperature increases the effective

diffusivity and collision frequency of the asphaltene particles which lead to the faster precipitation

of the asphaltenes, and so accelerates the aggregates growth. The changes of single-phase oil

This article is protected by copyright. All rights reserved 9

viscosity as a function of pressure at different fixed temperatures is shown in Figure 5. In this work,

the model-1602 rolling ball viscometer has been used to determine the viscosity of bottom hole oil

sample at elevated pressures and temperatures. As a result of above discussion, at higher

temperatures, the effect of oil viscosity overcomes the solubility effect regarding to the asphaltene

precipitation and results in higher AOP for light oil sample studied here. Wang reported that the oil-

asphaltene solubility parameter difference for dead oils does not significantly change with the

temperature,[48] which is in contrast to the obtained results for the studied live oil sample (see Figure

4). The possible reason for the difference in the results between Wang[48] and the current study is

the effect of temperature on oil composition which affects the solubility behaviour of asphaltene in

oil. Wang performed the experiments on dead oil samples at standard pressure conditions. In dead

oils, the light end components have been lost and temperature does not have any remarkable effect

on composition of the dead oils, and so on asphaltene solubility in oil. While, in this study related

experiments have been performed using light live oil at realistic oil field conditions of pressure and

temperature. In live oils, the composition of the oil is strongly affected by temperature change.

Thus, any change in composition of the oil sample with temperature will affect the oil-asphaltene

solubility relations. It is also confirmed that asphaltenes formed at field conditions and laboratory

conditions are substantially different, and conclusions drawn from laboratory asphaltene studies

which are numerous and much easier to obtain do not necessarily follow for asphaltenes formed at

field conditions.[49]

Effect of Temperature on Size Distribution and Average Diameter of the Aggregates

Measurements and image analysis were done at stable conditions of aggregates growth which is

defined as equilibrated time (tequilib). At equilibrated time no more changes have been observed in

the aggregation process at each pressure step and fixed temperature. For image analysis and

processing, time zero (t = 0.0 hr) is supposed to be the first moment of the appearance of

asphaltenes which is corresponding to the AOP. The HPM detects particles of approximately 0.50

µm and larger. Figure 6 indicates HPM observations of asphaltene behaviour during

This article is protected by copyright. All rights reserved 10

depressurization process at different fixed temperatures. HPM photographs qualitatively show

increase of asphaltene concentration with pressure decrement at different fixed temperatures. Size

distribution and average diameter of the asphaltene aggregates during depressurization process at

different fixed temperatures are shown in Figures 7 and 8, respectively. At 408 K the size

distribution of the aggregates covers a broad range and at lower pressure steps it depicts a bimodal

trend. Also, average diameter of the aggregates versus pressure shows a slow growth of asphaltene

aggregates during depressurization process (Figure 8). Broad/bimodal aggregates size distribution

and slow growth of average diameter of the aggregates at 408 K demonstrate that different types of

aggregate structures are present in the oil which is the main characteristic of slow kinetics of

aggregation or reaction limited control of the aggregation process. As temperature of the

depressurization experiments decreases to 364 K and 341 K, the asphaltene aggregates size

distribution at initial pressure steps is unimodal (Figure 7). Unimodal behaviour of the aggregate

size distribution shows that the diffusion limited aggregation is dominant at initial pressure steps;

with more pressure reduction, the trend of aggregates size distribution changes from unimodal to

bimodal or multimodal and the size growth of the aggregates is slowed down (i.e., reaction limited

control of the aggregation process). Hence, during depressurization experiments at 364 K and 341

K, both diffusion and reaction limited mechanisms are present. At initial pressure steps the

diffusivity of the asphaltene particles control the aggregation process; as pressure decreases the

reaction limited aggregation is more pronounced. The main difference between the characteristic

features of each mechanism is the way that particles stick together. In diffusion limited aggregation

every contact of the particles results in their sticking together, and so fast growth of particles occurs

with time. In slow aggregation or reaction limited aggregation not every contact between the

particles results in their aggregation and it is strongly a function of the number of the particles,

which decreases the aggregation rate compared to the diffusion limited aggregation.[50] At 319 K the

aggregates size distribution exhibits a unimodal behaviour at all pressure steps. In addition, as

temperature decreases to 319 K, average diameter of the aggregates increases sharply in comparison

This article is protected by copyright. All rights reserved 11

to the higher temperatures (408 K, 364 K, and 341 K) (Figure 8). Unimodal aggregates size

distribution and the trend of average diameter of the aggregates show that the aggregation of the

asphaltenes at 319 K is mainly controlled by diffusion mechanism (i.e., fast aggregation at 319 K).

Fractal Dimension of the Asphaltene Aggregates

Fractal dimension (dn) describes the shape and size of the aggregate structures in n dimension (n =

1, 2, or 3), which is essential in understanding the properties of colloidal aggregates. Since the

image analysis methods produce data sets on the basis of two-dimensional images of the aggregates,

in this work the two-dimensional fractal dimensions of the asphaltene aggregates (d2=df) are

measured to illustrate the structure of the aggregates. Fractal dimension of the asphaltene aggregates

imbedded in two-dimensions is described as follows:[51]

(3)

where l is the characteristic length scale (m) and A is the cross-sectional area of the aggregates (m2).

The fractal dimension (df) of the aggregates is calculated from the log-log plot of aggregate

projected area (A) versus the characteristic length (l). The characteristic length scale (l) can be taken

either as the shortest, longest, geometric mean, equivalent radius or diameter (based on area) of an

aggregate.[52] In this work, characteristic length is considered to be the diameter of the aggregates

(dagg) based on area. Here, the software ImageJ (version 1.44) was used to measure the diameter

and area of the asphaltene aggregates.

Two-dimensional fractal dimension quantifies the rate at which the aggregate projected area

increases with respect to the characteristic length. Higher values of df indicate formation of more

dense and compact aggregate structures. Figure 9 illustrates the example graphs for calculation of

the fractal dimension of the asphaltene aggregates at different fixed temperatures during

depressurization experiments. Fractal dimension of the asphaltene aggregates at different fixed

temperatures during depressurization experiments are shown in Figure 10. As the temperature of the

depressurization experiments decreases, larger aggregates with lower fractal dimensions are formed,

i.e., formation of porous and tenuous aggregates. The range of fractal dimensions obtained here are

This article is protected by copyright. All rights reserved 12

in agreement with the other published results for classical colloidal systems. In addition, the

obtained fractal dimensions well confirm the prevalent mechanisms of aggregation predicted by

aggregates size distribution and average diameter of the aggregates (discussed in previous section).

Effect of Temperature on Amount of Precipitated Asphaltene

HPHT filtration tests were designed at different fixed temperatures to investigate the effect of

temperature on amount of precipitated asphaltene in light live oil during depressurization process.

Results of HPHT filtration tests are shown in Figure 11. Asphaltene precipitation behaviour during

depressurization process can be well described by solubility approach. During depressurization

process at each fixed temperature and above the saturation pressure, pressure reduction reduces the

density of the oil and so oil solubility power. Consequently, an increase in amount of precipitated

asphaltene occurs from initial pressure down to the saturation pressure of the oil. Subsequently, at

pressures below the saturation pressure the dissolved gas evolves from the liquid phase and the oil

becomes richer in heavy end components. This leads to the increment of oil solubility power and so

reduction of amount of precipitated asphaltene.[8,53]

Obtained results show that the effect of temperature on asphaltene precipitation is considerable. As

the temperature of the depressurization process increases the amount of precipitated asphaltene

decreases. As shown in Figure 4, the oil-asphaltene solubility parameter difference (δasp-δoil)

decreases with temperature rise (i.e. asphaltene solubility increases) which results in reduction of

asphaltene precipitation. Also, increment of temperature decreases the oil viscosity (see Figure 5)

and so increases the collision frequency of asphaltene particles. Reduction of oil viscosity with

temperature accelerates the aggregates growth and more asphaltenes should be precipitated. Thus,

for aggregation and precipitation of asphaltenes the oil solubility and oil viscosity are in

competition with each other. For the light oil sample studied here, as temperature increases the

effect of oil solubility is much more dominant than the effect of oil viscosity on amount of

precipitated asphaltene. In addition, the variation of asphaltene precipitation with temperature and

below the saturation pressure (i.e. two-phase state) can be attributed to the amount of change in

This article is protected by copyright. All rights reserved 13

 light end components of the oil. With temperature rise during the depressurization process in two-

phase state, more loss of light components occurs which increases the solubility power of the

remained oil for asphaltenes. Thus, asphaltene precipitation below the saturation pressure decreases

with temperature increment.[8]

CONCLUSIONS
In this work, the effect of temperature on mechanisms of asphaltene destabilization

(aggregation/precipitation) in light live oil was studied by HPM and HPHT filtration setup. The

results were discussed through the onset pressure of asphaltene, size distribution and average

diameter of the aggregates, fractal analysis of the asphaltene aggregates and the amount of

precipitated asphaltene at elevated pressures and temperatures. For the range of experiments

performed here, the main observations and conclusions are summarized as follows:

 An increase of AOP with temperature rise was observed for depressurization process in light live

oil. The decrease of the oil viscosity with temperature is the principal driving force in earlier

precipitation of the asphaltene rather than the solubility effect of oil-asphaltene.

 In studied light oil sample, at highest temperature of the experiments (408 K) during

depressurization process the aggregation of asphaltenes is controlled by reaction limited

mechanism. As temperature decreases to 364 K and 341 K the mechanism of asphaltene

aggregation changes gradually and both reaction and diffusion limited mechanisms are present. At

lowest temperature of the experiments (319 K) the aggregation of the asphaltenes is mainly

controlled by diffusion mechanism.

 Visualization of aggregation process by HPM shows that the asphaltenes in live oil are pressure-

temperature dependent fractal-like structures. Depressurization process at lower temperatures

results in formation of larger aggregates with lower fractal dimensions (porous and tenuous

aggregates). As temperature of the depressurization process increases, more compact and dense

asphaltene aggregates are formed.

This article is protected by copyright. All rights reserved 14

 The fractal dimensions of the asphaltene aggregates do not remain constant at all scales by pressure

and temperature variations. Fractal dimension along with size distribution of asphaltene aggregates

can be used to appropriately describe the active/controlling mechanisms of the asphaltene

aggregation process at elevated pressures and temperatures.

 As temperature of the depressurization process increases, the amount of precipitated asphaltene in

studied light live oil decreases.

 Visualization experiments performed by HPM demonstrate that asphaltene aggregation is a kinetics

phenomenon. Neglecting the kinetics effects on asphaltenes destabilization can produce

misrepresentative results leading to ill-informed decisions under operational conditions.

ACKNOWLEDGEMENTS
The first author would like to dedicate this paper to his wife, Sahar, for her kind support, patience,

and encouragement.

NOMENCLATURE
A cross-sectional area of the aggregates (m2, µm2)
AOP asphaltene onset pressure (MPa)
Co coefficient of isothermal compressibility of oil (MPa-1)
CII colloidal instability index
dagg average diameter of the aggregates (m, µm)
df fractal dimension
dn fractal dimension in n dimension (n=1, 2, or 3)
d2 two-dimensional fractal dimension
E cohesive energy (kJ)
Eo coefficient of isobaric thermal expansion of oil (K-1)
GOR solution gas-oil ratio (vol/vol)
l characteristic length scale (m, µm)
P pressure (MPa)
Pb bubble point pressure or saturation pressure (MPa)
Pi initial reservoir pressure (MPa)
Pr reservoir pressure (MPa)
T temperature (K)
Tr reservoir temperature (K)
t time (hr)
tequilib equilibrated time (hr)
U internal energy (kJ)
V molar volume (m3/mol)

This article is protected by copyright. All rights reserved 15

WAT wax appearance temperature (K)

Greek Letters

δ solubility parameter (MPa0.5)

δasp asphaltene solubility parameter (MPa0.5)
δoil oil solubility parameter (MPa0.5)
µo oil viscosity (Pa.s)
π internal pressure (MPa)
ρ density (kg/m3)
ρor density of live oil at reservoir pressure and temperature condition (kg/m 3)

Subscripts

agg aggregate
asp asphaltene
b bubble point or saturation point
equilib equilibrium conditions
f fractal
n dimensionality of fractal dimension
o oil
or live oil at reservoir pressure and temperature condition

This article is protected by copyright. All rights reserved 16

 REFERENCES
[1] E. Durand, M. Clemancey, J. M. Lancelin, J. Verstraete, D. Espinat, A. A. Quoineaud, Energ.
Fuel. 2010, 24, 1051.
[2] M. P. Hoepfner, V. Limsakoune, T. Maqbool, H. S. Fogler, Energ. Fuel. 2013, 27, 725.
[3] M. Mehranfar, R. Gaikwad, S. Das, S. K. Mitra, Th. Thundat, Langmuir 2014, 30, 800.
[4] O. C. Mullins, E. Y. Sheu, A. Hammami, A. G. Marshall, Asphaltenes, Heavy Oils, and
Petroleomics, 1st edition, Springer, New York 2007, p. 87.
[5] J. G. Speight, The Chemistry and Technology of Petroleum, 4th edition, CRC Press, Boca
Raton, Florida 2006, p. 345.
[6] M. A. Aquino-Olivos, E. Buenrostro-Gonzalez, S. I. Andersen, C. Lira-Galeana, Energ. Fuel.
2001, 15, 236.
[7] F. Civan, Reservoir Formation Damage, 2nd edition, Gulf Professional Publishing,
Burlington, Massachusetts, USA 2007, p. 533.
[8] S. A. Mousavi-Dehghani, M. Vafaie-Sefti, G. A. Mansoori, Pet. Sci. Technol. 2007, 25, 1435.
[9] G. P. Oskui, M. A. Jumma, W. Abuhained, “Laboratory Investigation of Asphaltene
Precipitation Problems during CO2/Hydrocarbon Injection Project for EOR Application in
Kuwaiti Reservoirs,” International Petroleum Conference and Exhibition, Society of
Petroleum Engineers, Kuwait, 14–16 December 2009.
[10] S. Macchietto, G. F. Hewitt, F. Coletti, B. D. Crittenden, D. R. Dugwell, A. Galindo, G.
Jackson, R. Kandiyoti, S. G. Kazarian, P. F. Luckham, O. K. Matar, M. Millan-Agorio, E. A.
Muller, W. Paterson, S. J. Pugh, S. M. Richardson, D. I. Wilson, Heat Transfer Eng. 2011,
32, 197.
[11] A. H. Mohammadi, D. Richon, The Open Thermodynamics Journal 2008, 2, 82.
[12] C. W. Angle, Y. Long, H. Hamza, L. Lue, Fuel 2006, 85, 492.
[13] S. Ashoori, A. Abedini, H. Saboorian, K. Q. Nasheghi, R. Abedini, J. Jpn. Petrol. Inst. 2009,
52, 283.
[14] Z. A. Chandio, M. Ramasamy, H. B. Mukhtar, Chem. Eng. Res. Des. 2014, 94, 573.
[15] P. Painter, B. Veytsman, J. Youtcheff, Energ. Fuel. 2015, 29, 2120.
[16] K. Rastegari, W. Y. Svrcek, H. W. Yarranton, Ind. Eng. Chem. Res. 2004, 43, 686.
[17] C. M. Seifried, J. Crawshaw, E. S. Boek, Energ. Fuels.2013, 27, 1865.
[18] R. Storm, J. Barresi, E. Y. Sheu, Fuel Sci. Techn. Int. 1996, 14, 243.
[19] A. Hirschberg, L. N. J. deJong, B. A. Schipper, J. G. Meijer, SPE J. 1984, 24, 283.
[20] K. Kraiwattanawong, H. S. Fogler, S. G. Gharfeh, P. Singh, W. H. Thomason, S. Chavadej,
Energ. Fuel. 2007, 21, 1248.

This article is protected by copyright. All rights reserved 17

[21] A. Pina, P. Mougin, E. Béhar, Oil Gas Sci. Technol. 2006, 61, 319.
[22] J. X. Wang, J. S. Buckley, Energ. Fuel. 2001, 15, 1004.
[23] P. Wattana, D. J. Wojciechowski, G. Bolaños, H. S. Fogler, Pet. Sci. Technol. 2003, 21, 591.
[24] T. Maqbool, P. Srikiratiwong, H. S. Fogler, Energ. Fuel. 2011, 25, 694.
[25] G. Hotier, M. Robin, Rev. Inst. Fr. Pet. Ann. 1983, 38, 101.
[26] J. J. Mcketta, Petroleum Processing Handbook, 1st edition, CRC Press, New York 1992, p.
536.
[27] D. L. Mitchell, J. G. Speight, Fuel 1973, 52, 149.
[28] W. A. Latif, A. A. Khalid, Fuel 1981, 60, 1043.
[29] A. Alizadeh, H. Nakhli, R. Kharrat, M. H. Ghazanfari, Pet. Sci. Technol. 2011, 29, 1054.
[30] I. A. Wiehe, “Tutorial on the Phase Behavior of Asphaltene and Heavy Oils,” AIChE
International Conference on Petroleum Phase Behavior and Fouling, Third Int’l Symposium
on the Thermodynamics of Asphaltenes and Heavy Oils, American Institute of Chemical
Engineers, New York 1999.
[31] G. A. Lambourn, M. Durrieu, “Fouling in Crude Oil Preheat Trains,” Heat Exchangers-
Theory and Practice, J. Taborek, G. F. Hewitt, N. Afghan, Eds., Hemisphere Publishing Corp,
New York 1983, p. 841.
[32] O. V. Rogacheva, V. Z. Gubaidullin, R. N. Gimaev, T. D. Danlilyan, Colloid J. USSR+ 1984,
46, 828.
[33] R. E. Winans, J. E. Hunt, Div. Fuel. Chem. 1999, 44, 725.
[34] S. Verdier, H. Carrier, S. Andersen, J. Daridon, Energ. Fuel. 2006, 20, 1584.
[35] S. Negahban, N. Joshi, A. K. M. Jamaluddin, J. Nighswander, “A Systematic Approach for
Experimental Study of Asphaltene Deposition for an Abu Dhabi Reservoir Under WAG
Development Plan,” International Symposium on Oilfield Chemistry, Society of Petroleum
Engineers, Houston, Texas, 5–7 February 2003.
[36] P. Bahrami, R. Kharrat, S. Mahdavi, Y. Ahmadi, L. James, Korean J. Chem. Eng. 2015, 32,
316.
[37] A. K. M. Jamaluddin, B. Ross, D. Calder, J. Brown, M. Hashem, J. Can. Petrol. Technol.
2002, 41, 25.
[38] T. J. Collins, BioTechniques 2007, 43, 25.
[39] ASTM D6560-00, Standard Test Method for Determination of Asphaltenes (Heptane
Insolubles) in Crude Petroleum and Petroleum Products 143.1, 2000.
[40] R. B. De Boer, K. Leerlooyer, M. R. P. Eigner, A. R. D. Van Bergen, SPE Prod. Facil. 1995,
10, 55.

This article is protected by copyright. All rights reserved 18

[41] A. Yen, Y. R. Yin, S. Asomaning, “Evaluating Asphaltene Inhibitors: Laboratory Tests and
Field Studies,” SPE International Symposium on Oilfield Chemistry, Society of Petroleum
Engineers, Houston, Texas, 13–16 February 2001.
[42] ASTM D4124-09, Standard Test Method for Separation of Asphalt into Four Fractions 2009.
[43] T. G. Monger-McClure, J. E. Tackett, L. S. Merrill, SPE Prod. & Facilities 1999, 14, 4.
[44] J. H. Hildebrand, R. L. Scott, The Solubility of Nonelectrolyte, 3rd edition, Reinhold Pub.
Corp, New York 1950, p. 247.
[45] A. F. M. Barton, CRC Handbook of Solubility Parameters and Other Cohesion Parameters,
2nd edition, CRC Press Inc, Boca Raton, Florida 1991, p. 35.
[46] S. Verdier, S. I. Andersen, Fluid Phase Equilib. 2005, 231, 125.
[47] H. W. Yarranton, J. H. Masliyah, AIChE J. 1996, 42, 3533.
[48] J. Wang, Predicting Asphaltene Flocculation in Crude Oils, PhD Thesis, New Mexico
Institute of Mining and Technology, Socorro, NM 2000.
[49] N. B. Joshi, O. C. Mullins, A. Jamaluddin, J. Creek, J. McFadden, Energ. Fuel. 2001, 15, 979.
[50] I. K. Yudin, G. L. Nikolaenko, E. E. Gorodetskii, V. I. Kosov, V. R. Melikyan, E. L.
Markhashov, D. Frot, Y. Briolant, J. Pet. Sci. Eng. 1998, 20, 297.
[51] N. H. G. Rahmani, T. Dabros, J. H. Masliyah, J. Colloid Interf. Sci. 2005, 285, 599.
[52] B. Gorczyca, J. Ganczarczyk, Environ. Technol. 1996, 17, 1361.
[53] S. A. Mousavi-Dehghani, Experimental and Theoretical Investigation of Asphaltene
Deposition in Natural Gas Injection, PhD Thesis, Tarbiat Modares University, Chemical
Engineering Department, Tehran, Iran 2004.

This article is protected by copyright. All rights reserved 19

 FIGURE CAPTIONS
Figure 1. Schematic diagram of the high pressure microscope (HPM) system.

Figure 2. Schematic diagram of the HPHT filtration setup.

Figure 3. Status of the studied oil sample on De Boer plot.[40]

Figure 4. Oil-asphaltene solubility parameter difference (δasp-δoil) as a function of temperature at

elevated pressures.

Figure 5. Single-phase oil viscosity as a function of pressure and temperature.

Figure 6. Visualization of the depressurization process at equilibrated times (tequilib) for distinct

pressure steps and different fixed temperatures. Each HPM photograph represents the equilibrated

fluid over time at distinct pressure steps and fixed temperature.

Figure 7. Aggregates size distribution of asphaltene at equilibrated times (tequilib) during

depressurization process at different fixed temperatures.

Figure 8. Average diameter of asphaltene aggregates at equilibrated times (tequilib) during

depressurization process at different fixed temperatures.

Figure 9. Example graphs for calculation of the fractal dimension of the asphaltene aggregates at

different fixed temperatures during depressurization process.

Figure 10. Fractal dimension (df) of the asphaltene aggregates at different fixed temperatures

during depressurization process.

Figure 11. Amount of precipitated asphaltene at different fixed temperatures during

depressurization process.

This article is protected by copyright. All rights reserved 20

 Table 1. General Specifications of the Oil Sample and Oil Field

specifications unit value

H2S (mol %)a 0.37

a
N2 (mol %) 0.07
a
CO2 (mol %) 1.44
a
C1 (mol %) 50.68
a
C2 (mol %) 9.26
a
C3 (mol %) 6.11
a
iC4 (mol %) 1.24
a
nC4 (mol %) 2.84
a
iC5 (mol %) 1.04
a
nC5 (mol %) 1.17
a
C6 (mol %) 2.82
a
C7 (mol %) 3.09
a
C8 (mol %) 2.85
a
C9 (mol %) 3.02
a
C10 (mol %) 2.01
a
C11 (mol %) 1.44
C12+ (mol %) a
10.54
molecular weight of C12+ fraction gr/mol 398
sp.gr. of C12+ fraction at 288.7 K - 0.8955
other oil and oilfield properties
reservoir temperature (Tr ) K 408
reservoir pressure (Pr ) MPa 64.2
saturation pressure (Pb) MPab 25.7
o
gravity of dead oil API 33.8
oil density at reservoir pressure and
(kg/m3)c 654.8
temperature (ρor)
solution gas-oil ratio (GOR) vol/vol 259.1
d
wax appearance temperature (WAT) K 312
a
The uncertainty is ±5×10-3. b
The uncertainty is ±5×10-2 MPa.
c
The uncertainty is ±7 kg/m3. d
The uncertainty is ±0.1 K.

This article is protected by copyright. All rights reserved 21

 Table 2. SARA Analysis Results

components unit value

Saturates (mass%)a 64.90

a
Aromatics (mass%) 29.10
a
Resins (mass%) 5.10
a
Asphaltenes (mass%) 0.90
a
The uncertainty is ±5×10-4.

This article is protected by copyright. All rights reserved 22

Table 3. Asphaltene Onset Pressure (AOP) and Saturation Pressure (Pb) of the Oil Sample at

Different Temperatures

saturation pressure a,
temperature (K) AOP b(MPa)
Pb (MPa)

408 25.7 51.7

364 23.5 49.6

341 22.0 48.3

319 20.0 46.9

a
Saturation pressures (Pb) were obtained through the PVT tests.
b
The uncertainty in AOP measurement is ± 0.345 MPa.

This article is protected by copyright. All rights reserved 23

 Figure 1

This article is protected by copyright. All rights reserved 24

 Figure 2

This article is protected by copyright. All rights reserved 25

 Figure 3

This article is protected by copyright. All rights reserved 26

 Figure 4

This article is protected by copyright. All rights reserved 27

 Figure 5

This article is protected by copyright. All rights reserved 28

 Figure 6

This article is protected by copyright. All rights reserved 29

 Figure 7

This article is protected by copyright. All rights reserved 30

 Figure 8

This article is protected by copyright. All rights reserved 31

 Figure 9

This article is protected by copyright. All rights reserved 32

 Figure 10

This article is protected by copyright. All rights reserved 33

 Figure 11

This article is protected by copyright. All rights reserved 34