Article

pubs.acs.org/EF

Molecular Dynamics Simulation: The Behavior of Asphaltene in

Crude Oil and at the Oil/Water Interface
Fengfeng Gao, Zhen Xu,*, Guokui Liu, and Shiling Yuan*,

Key Laboratory of Colloid and Interface Chemistry, Shandong University, Jinan 250100, China
Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353, China

ABSTRACT: Carboxyl asphaltene is commonly discussed in the petroleum industry. In most conditions, electroneutral carboxyl
asphaltene molecules can be deprotonated to become carboxylate asphaltenes. Both in crude oil and at the oil/water interface,
the characteristics of anionic carboxylate asphaltenes are dierent than those of the carboxyl asphaltenes. In this paper, molecular
dynamics (MD) simulations are utilized to study the structural features of dierent asphaltene molecules, namely, C5 Pe and
anionic C5 Pe, at the molecular level. In crude oil, the electroneutral C5 Pe molecules prefer to form a steady face-to-face
stacking, while the anionic C5 Pe molecules are inclined to form face-to-face stacking and T-shaped II stacking because of the
repulsion of the anionic headgroups. Anionic C5 Pe has a distinct anity to the oil/water interface during the simulation, while
the C5 Pe molecules persist in the crude oil domain. A three-stage model of anionic C5 Pe molecules adsorbed at the oil/water
interface is nally developed.
oil interface.6 Poteau et al. concluded that the charged
asphaltene molecules were more easily to accumulate at oil/
water interface too.18
In the oil eld, it is of prime importance to understand the
behavior of asphaltene molecules at the oil/water interface.12,19
Many experimental technologies are used to investigate the
interfacial phenomena, for example, surface tension measurements,13 interfacial tension measurements,20 vapor pressure
osmometry,21 and small-angle neutron scattering.22 However, it
is still a challenge to understand the aggregation of asphaltene
by experimental methods since this behavior cannot be
explained through the common colloidal interaction models
and the mesoscale aggregation theories.2
Because of the increased computational power over recent
years, computer simulations have proven to be valuable tools to
study the behavior of asphaltene molecules at the molecular
level. Molecular dynamics (MD) simulation, based on empirical
force elds, is an ecient and reliable method to study the
motions of molecular architectures.23,24 MD also allows us to
extract information about dynamic and structural properties at a
microscopic level which is not easy to get though experiments.
In previous research the shape and structure of asphaltene
molecules in aqueous solutions2527 or organic media2830
have been well-established using MD methods. However, there
is still a lack of a fundamental understanding of the properties
of asphaltene molecules at the oil/water interface.
In this work, two types of asphaltene molecules are discussed.
One is the carboxyl asphaltene, and the other has an anionic
carboxylate group on the end of its chain. MD simulations are
performed to investigate the interfacial phenomena and the
dynamic behavior at the molecular level. The present study is
divided into two parts: The rst is the behavior of the two kinds

I. INTRODUCTION
Asphaltenes, consisting of polyaromatic rings and various
proportions of aliphatic chain lengths,1,2 are the heaviest
fractions of petroleum. Since asphaltene molecules can reduce
the interfacial tension, they are always taken as the natural
surfactants in improved oil recovery (IOR).3,4
In the petroleum industry, asphaltene molecules having
carboxyl headgroups have been widely discussed.5,6 Commonly,
asphaltene molecules can form aggregate structures in the bulk
phase of crude oil due to the stacking of polyaromatic rings.7,8
The aggregation causes many problems during production and
transportation; for instance, low solubility,9 high viscosity,10
and precipitation and deposition.11 The aggregation of
asphaltene can also induce serious problems in oil recovery
and transport, such as reservoir plugging and production
pipelines fouled, and so forth.12 Therefore, in IOR, it is
necessary to understand the mechanism of the aggregation
clearly. In the past, dierent aggregation mechanisms have been
proposed. Cameron et al. hypothesized that parts of asphaltene
molecules associated with form micellar structures through Hbonds.13 Islam proposed that the aggregation was caused by the
charge transfer between molecules.14
Besides being present in the bulk phase, asphaltene
molecules are generally considered an important fraction in
stabilizing the oil/water interface.15 However, in numerous
conditions, carboxyl asphaltene transforms from the nondissociated state into the hydrophilic carboxylate asphaltene
easily. The carboxylate functional groups have a strong
inuence on the properties of the asphaltene molecules. Due
to the anionic charged headgroups, the carboxylate asphaltenes
are preferentially adsorbed at positive surfaces, such as
montmorillonite.16,17 In addition, the headgroups also have
important eects on the behavior of the asphaltene molecules
at the oil/water interface. Takamura et al. found that when
carboxyl asphaltene molecules were deprotonated, the
negatively charged carboxylate groups adsorbed at the water/
2014 American Chemical Society

Received: July 27, 2014

Revised: November 17, 2014
Published: November 17, 2014
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results for system A to form system B. The simulation details

are summarized in Table 1.
In the simulation of system A, 24 asphaltene molecules and
crude oil molecules were randomly put into a cubic box of 9
9 9 nm3 designed as the literature.2,35 Then NPT ensemble
was carried out to obtain a reasonable density, and the nal
dimensions of simulation boxes were displayed in Table 1. The
simulation system A1 (Figure 2a) was used to study the
aggregation of the C5 Pe in crude oil, while system A2 (Figure
2b) was performed to investigate the eect of anionic terminal
groups on aggregation. For system A2, the system was made
electroneutral by adding 24 Na+ ions, where each Na+ ion
corresponds to one COO.
System B was explored to study the aggregation structures at
the crude oil/water interface. The initial congurations of
system B were taken from the equilibrated structure of system
A (C5 Pe molecules in crude oil). The boxes of system A were
expanded in the Z-direction, and water molecules were added
to the empty volume to create the crude oil/water interface.
The two new constructed simulation systems were named B1
and B2 (Figure 4a and c), respectively.
3. Details of Molecular Dynamics. All of the initial
congurations were minimized by the steepest descent and
conjugate gradient methods.31 During the energy minimization,
the cuto of Coulomb and van der Waals interactions was 1.2
nm. When the maximum force of the system was converged to
a threshold of less than 1000 kJmol1nm1, the system was
considered to be stabilized.35 The simulations were performed
in the NPT ensembles at 298 K and 0.1 MPa, which caused the
systems to have appropriate densities and box dimensions.
Finally, 200 ns NVT simulations were carried out at 298 K. In
the NVT ensembles, the periodic boundary condition was
applied in all directions. The Berendsen thermostat was used as
the temperature coupling algorithm, and bond lengths were
constrained by the LINCS algorithm.42 The particle-mesh
Ewald (PME) method was adopted to compute the electrostatic interactions.43 The MaxwellBoltzmann distribution was
employed to set the initial atomic velocities of the systems.31
The trajectories were integrated by leapfrog Verlet algorithm.35
The dynamic properties of the simulation systems were
analyzed by the built-in analytical tools in GROMACS.

of asphaltene molecules in crude oil, focusing on the dierence

of their aggregation conguration; the second is about the
asphaltene aggregations at the water/oil interface. The
simulations provide considerable insights into the behaviors
of asphaltene molecules in crude oil and at oil/water interfaces.

II. SIMULATION METHOD

All MD simulations were performed in the GROMACS 4.0.5
software package,31 and the GROMOS 45a3 force eld was
used.32,33 The force eld is widely used in exploring the
dynamics of polyaromatic molecules.34,35
1. Molecular Models. N-(1-Hexylheptyl)-N-(5-carboxylicpentyl)-perylene-3,4,9,10-tetracarboxylicbisimide (C5 Pe)
(Figure 1a) is an prototypical asphaltene model reported in

Figure 1. Two asphaltene models studied in the simulations.

several studies.35,36 In order to investigate the inuence of

charged groups on C5 Pe, the terminal carboxylic headgroup
was deprotonated to be anionic (Figure 1b), which was named
anionic C5 Pe.
The crude oil model was based on that proposed by
Miranda:37,38 alkanes (72 hexane, 66 heptane, 78 octane, 90
nonane, 48 cyclohexane, and 78 cycloheptane molecules) and
aromatics (78 toluene and 30 benzene molecules). The
coordinate and topology les of the crude oil and C5 Pe
molecules were generated by the PRODRG program.39 All
aromatic regions and double bonds were modeled by sp2
hybridized carbons,35 and aliphatic chains were adopted as
united atom structures.40 The anionic asphaltene molecules,
described by van der Waals and Coulomb terms,37 were
neutralized by sodium ions. The simple point charge (SPC)
model was adopted for the water molecules.41
2. Initial Simulation Conguration. In this work, the
simulation systems were divided into two parts. The initial
conguration of asphaltene molecules in crude oil was dened
as system A, and then water was added on one side of the

III. RESULTS AND DISCUSSION

1. Asphaltene Molecular Aggregation in Crude Oil. In
this section, the aggregation behaviors of asphaltene models,
anionic and neutral C5 Pe, in crude oil are discussed. The
aggregate congurations of C5 Pe (Figure 2c) and anionic C5
Pe (Figure 2d) are obviously dierent in crude oil. The former
is more compact. The dierence is likely caused by the Hbonds among the headgroups of the C5 Pe molecules. In the
aggregation of C5 Pe, the electronegative oxygen atom in the

Table 1. Details of the Dierent Systems of Simulations

system
System A1
System A2
System B1
System B2
a

asphaltene molecules

NAsphaltene

NNa+

NWater

System A: Asphaltene Molecules in Crude Oil

C5 Pe
24
anionic C5 Pe
24
24
System B: Aggregated Asphaltene at Crude Water/Oil Interface
C5 Pe
24
4615
anionic C5 Pe
24
24
4698

nal box sizea (nm3)

5.2 5.2 5.2
5.2 5.2 5.2
5.2 5.2 10.4
5.2 5.2 10.4

The initial simulation box size was set at 9 9 9 nm3.

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Figure 2. Snapshots of the initial congurations of system A1 (a) and system A2 (b). The nal structures of the C5 Pe (c) and anionic C5 Pe (d)
simulation in crude oil. In (c) and (d), the crude oil molecules are omitted for clarity. Color scheme: C, gray; H, white; N, blue; O, red; the C5 Pe
and anionic C5 Pe molecules are displayed in the stick model.

Figure 3. Normalized radial distribution functions of C5 Pe (a) and anionic C5 Pe (b) and the according stacking models. The face-to-face stacking
(left) and the T-shaped stacking (right) of system A1 are shown in (a); the face-to-face stacking (left), T-shaped I stacking (middle), and T-shaped
II stacking (right) of system A2 are shown in (b). The stacking models are randomly taken from the trajectories, and the color scheme refers to
Figure 2.

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Figure 4. Initial structures of system B1 (a) and system B2 (c); the nal structures of system B1 (b) and system B2 (d). Time-dependent density
proles of C5 Pe (e) and anionic C5 Pe (f) at the crude oil/water interface. For details, refer to Figure 2.

carboxyl groups attracts the electropositive hydrogen atoms to

form the H-bonds, which are highlighted in Figure 2c. The Hbonds cause small stacks to form and lead to aggregation.
However, due to the deprotonation, H-bonds cannot be formed
between the anionic C5 Pe molecules, which lead to a loose
aggregation conguration in the crude oil.
The stacking models of the asphaltene molecules are
expressed by the normalized radial distribution function
(RDF), g(r)/g(r)max peak, where g(r) is the distribution of
asphaltene molecules away from a reference asphaltene
surfactant molecule, and g(r)max peak is the maximum peak
value of g(r).35 Figure 3 depicts the normalized RDFs of
systems A over the last 100 ns of the simulation. Evidently, the
curves of the RDFs are dierent for system A1 and system A2.

Figure 3a shows that system A1 has one sharp peak (ca. 0.4
nm) and a small peak (ca. 0.75 nm), while the system A2
(Figure 3b) has an additional broad peak (ca. 1.23 nm). The
dierent peaks correspond to dierent stacking models, which
are displayed in Figure 3. The sharp peak at about 0.4 nm
corresponds to the face-to-face stacking, which is formed by the
stacking of polyaromatic systems. The other peaks are due to
the T-shaped (edge-to-face) stacking models, which are
broadened due to the numerous orientations possible. In this
work, the peak at 0.75 nm is dened as the T-shaped I stacking
model, and the peak at 1.23 nm corresponds to the T-shaped II
stacking model. The appearance of the T-shaped II stacking in
system A2 is mainly caused by the negatively charged
headgroup, which increases the distance between the head7371

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Figure 5. Total energy of the system changing as the simulation proceeds for B2 (a) and normalized RDFs of anionic C5 Pe (b).

Figure 6. Left: Snapshots of the congurations of anionic C5 Pe molecules adsorbed to the crude oil/water interface at dierent simulation times.
Right: the corresponding congurations of anionic C5 Pe molecules at the interface. Four molecules are highlighted to follow their movement
through the four snapshots: molecule 1 (yellow), 2 (blue), 3 (pink), and 4 (green).

groups to reduce their repulsion. In other words, the T-shaped

II stacking is another reason to cause the anionic C5 Pe to
aggregate more loosely than the denser C5 Pe aggregations.
The ratio of the peaks in the RDF curves expresses which
stacking is dominant in the nal conguration. In system A1,
the ratio of the face-to-face stacking and the T-shaped I
stacking is about 4:1, illustrating the face-to-face staking is the

primary stacking model of C5 Pe in the crude oil. In the plot for

system A2, there are three peaks according to the face-to-face,
T-shaped I, and T-shaped II stacking models, and their ratio is
about 3:1:3, respectively. The data show that anionic C5 Pe
molecules mainly form the face-to-face and T-shaped II
stackings in crude oil.
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anionic C5 Pe molecules to the interface. Examination of the

density prole (Figure 4f) reveals a trend of the anionic C5 Pe
molecules moving toward the interface. After about 60 ns, the
density peak close to the oil/water interface increases. These
data mean some anionic C5 Pe molecules are already being
attracted to the interface (Figure 6b). In this paper, the anionic
C5 Pe molecules at the interface are dened as interfacial
molecules, which are marked in red in Figure 6b for clarity.
In the second stage, more anionic C5 Pe molecules are
continually attracted to the interface (Figure 6bc) and their
stacking models transform from T-shaped stacking to the faceto-face stacking. In this process, the total energy of the system
decreases quickly compared to stage I and stage III (Figure 5a).
In Figure 4f, the peaks close to the oil/water interface clearly
increase from 60 to 120 ns, denoting more anionic C5 Pe
molecules are adsorbed at the interface during this stage. In the
adsorption process, the molecules already at the oil/water
interface play the vital roles. They attract other anionic C5 Pe
molecules to the oil/water interface through noncovalent
interactions. The stacking pattern is obtained from the
normalized RDFs (Figure 5b). At 60 ns, the ratio of the
three stacking models is about 3:1:2, while it changes to 3:1:1 at
120 ns for stacking of face-to-face, T-shaped I, and T-shaped II,
respectively. The reduction of the peak at about 1.23 nm
indicates that the T-shaped II stacking in system B2 is
vanishing. The two large peaks displayed in Figure 5b represent
the face-to-face stacking and the T-shaped I stacking. Due to
the dominating peak at 0.4 nm, we assume that majority of the
anionic C5 Pe molecules are participating in face-to-face
stacking. The reason for changes in the stacking models is
ascribed to the hydrated headgroups, which are formed after
the headgroups are exposed to the water phase, evidently
reducing the repulsion of the headgroups (Figure 6c).
Stage III reects the anionic C5 Pe molecules in a wellorganized and ordered arrangement at the interface (Figure
6cd). In this process, a slight decrease of the energy prole
suggests that a small adjustment of the system occurs (Figure
5a). The decrease of energy is illustrated by the normalized
RDFs in Figure 5b, where the peak of the T-shaped II stacking
vanishing accompanies the energy decrease. The observed
adsorption process implies that the molecules already exiting at
the interface are very important for the formation of the anionic
C5 Pe slab and that the hydration of the headgroup causes the
stacking model to change to T-shaped II. From the top view in
Figure 6d, we can observe that the anionic C5 Pe molecules
form side-on arrangement at oil/water interface. Their
molecular orientation agrees well with the experimental data
reported using the sum frequency generation (SFG) vibrational
spectroscopy.47 This three-stage model based on the total
energy of the system adequately explains the process of anionic
C5 Pe aggregation from the crude oil to the oil/water interface.
2.2. Formation of the Interfacial Molecules. The formation
of interfacial molecules parallel to the oil/water interface is vital
to catalyze the anionic C5 Pe molecular aggregation. The
interfacial molecules are formed by the H-bond interaction
between the oxygen atoms of the anionic C5 Pe molecules and
the protons of water molecules. This is the key step for the
anionic C5 Pe molecules accumulating at crude oil/water
interface.38,48
Molecule 3 (marked in Figure 6a) is taken as an example to
investigate the formation process of the interfacial molecules.
The snapshots of the anionic C5 Pe molecule over time are
shown in Figure 7. Initially, some water molecules come into

To further validate the result of Figure 3, the possible

stacking congurations of asphaltene aggregations shown in
dynamics process are calculated using quantum chemical
methods. All the energies of the stackings in system A are
explored using PM6, a semiempirical method in the Gaussian09
suite of programs.44 For the C5 Pe molecules, the energies of
the face-to-face stacking and the T-shaped I stacking are
1285.18 kJ/mol and 830 kJ/mol, indicating the C5 Pe
molecules prefer to the face-to-face stacking comparing with
the T-shaped I stacking. For system A2, the energies of the
face-to-face stacking, T-shaped I stacking, and T-shaped II
stacking are 1079.08, 958.31, and 1042.32 kJ/mol,
respectively. Compared to the energies of the stacking
structures, the energy of the T-shaped I in system A2 is higher
than those of other stackings. Therefore, the face-to-face
stacking and T-shaped II stacking are more suitable for the
anionic C5 Pe molecules. From the energy, we conclude that
the face-to-face stacking in system A1 is dominant, while the
face-to-face and T-shaped II stacking are the primary structures
of anionic C5 Pe molecules in crude oil. The conclusions
obtained from quantum calculations are consistent with the
RDFs results shown in Figure 3.
2. Behavior of the Asphaltene Molecules at the Crude
Oil/Water Interface. We investigate the behavior of the two
aggregations of anionic and neutral C5 Pe molecules at the oil/
water interface with the systems B1 and B2 (vide supra). The
density proles (Figure 4e and f) are used to detect the
adsorption process of the anionic and neutral C5 Pe molecules.
The width of the crude oil/water interface is dened as the
length where the water density is 1090% of its bulk value.45
For system B1 and system B2, the interfacial width of the oil/
water interface is about 1 nm.
For the two systems, at the beginning of the simulation, the
asphaltene molecules are distributed in the oil phase (Figure 4a
and c). During the simulation process, the density prole of the
C5 Pe molecules (Figure 4e) has almost no changes, suggesting
the C5 Pe molecules persist in the crude oil all of the time
(Figure 4b). The reason can be attributed to the aromatic
molecules in the crude oil, which hinder the asphaltene
molecules to be adsorbed at oil/water interface.46 However, in
Figure 4f, the peak closest to the interface increases with time
evolution indicating that the anionic C5 Pe molecules are
adsorbed to the interface gradually (Figure 4d). The results
provide further evidence that the headgroups have strong
inuence to the behavior of asphaltene molecules, which is in
agreement with the experimental phenomenon.18
2.1. Three-Stage Model of Anionic C5 Pe Adsorbed at the
Crude Oil/Water Interface. In this section, we focus on the
dynamic process of anionic C5 Pe molecules adsorbed at the
oil/water interface. The total energy of system B2 (Figure 5a)
varies as the simulation progresses, suggesting that the
adsorption process can be divided into approximately three
stages. The density prole and detailed snapshots of the
adsorption process are shown in Figure 4f and Figure 6. In
stage I, the critical event is a few anionic C5 Pe molecules
adsorbed at the oil/water interface from the crude oil phase
(Figure 6ab). Initially, most of the anionic C5 Pe molecules
are distributed in crude oil, and only a few of the anionic C5 Pe
molecules are close to the interface. Then, some water
molecules enter into the crude oil phase by the inuence of
H-bonds, which are formed between the hydrogen atoms in
water and the negatively charged oxygen atoms in the anionic
C5 Pe molecules. Consequently, those water molecules pull the
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Figure 7. Snapshots of molecule 3 from Figure 6a drawn to the interface during the simulation. (a) 0 ns, (b) 1 ns, and (c) 2 ns. H-bonded water
molecules are highlighted.

Figure 8. (a) Scheme of the angles of two anionic C5 Pe molecules, angles between the interfacial molecule and the crude oil/water interface.
Distance and angles in (b) and (c) denote the properties of the group 1 (molecules 1 and 2) and group 2 (molecules 3 and 4).

anionic C5 Pe molecular plane to the oil/water interface is

angle (Figure 8a). Molecule 1 (orange) and molecule 2
(blue), dened in Figure 6a, are taken as group 1; meanwhile,
molecule 3 (pink) and molecule 4 (green) are taken as group 2.
The data for group 1 are shown in Figure 8b, and that of the
group 2 is displayed in Figure 8c. Though both of them can
form face-to-face stacking, the trends of their angles relative to
the interface are dierent.
For group 1, molecule 2 acts as the interfacial molecule
(Figure 6a), and the cosine of angle is close to 1 at the
beginning. As molecule 1 closing to molecule 2, the cosine of
angle is perturbed. After about 12 ns, molecule 1 approaches
molecule 2, and their distance reduces from 3.0 to 0.6 nm as a
result of the noncovalent interactions. Hence, molecule 2 is
forced to leave the crude oil/water interface due to the
hydrophobic interaction of the polyaromatic rings. In the next 8

the crude oil and then connect with molecule 3 (Figure 7a).
The electropositive hydrogen atoms of the water molecules
attract the negative oxygen atoms of the anionic C5 Pe
molecules to form new H-bonds. Then, the anionic C5 Pe
molecule is dragged to the interface due to a hydrophilic
interaction (Figure 7b). At the same time, the aromatic plane is
forced to parallel to the interface under the function of the
numerous H-bonds (Figure 7c). This behavior is energetically
favorable for the anionic C5 Pe molecule to reside at the
interface. Due to the numerous other H-bonding interactions,
more anionic C5 Pe molecules are extracted from the crude oil
and are adsorbed at the interface gradually (Figure 6b).
To study the behavior of the interfacial molecules at the oil/
water interface, the distances and angles of two anionic C5 Pe
molecules are discussed. The angle between two anionic C5 Pe
molecular planes is dened as angle , while the angle of one
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Notes

ns (12 to 20 ns), the cosine of angle trends toward 1,

suggesting the molecule 2 is adsorbed to the interface again due
to the H-bonds between the oxygen in anionic C5 Pe and water
molecules. However, during this period, the distance between
molecule 1 and molecule 2 does not reduce to the minimum
0.4 nm, which indicates the face-to-face stacking has not been
formed between the two anionic C5 Pe molecules. After about
20 ns, the cos is close to 1, and their distance approaches 0.4
nm, implicating that the face-to-face stacking is formed between
the two molecules.
The properties of group 2 (molecule 3 and molecule 4) are
shown in Figure 8c. The cosine of the angle increases to 1 in
the rst 2 ns of the simulation. The data are in agreement with
Figure 7, where the molecular plane becomes parallel to the
oil/water interface at 2 ns due to the H-bond interaction with
water molecules. From 2 to 8 ns, both the angle and the
distance between molecule 3 and molecule 4 show little
variation, similar to the 1220 ns regime of group 1 (Figure
8b). After 8 ns, the distance is minimized, and the cosine of
angle approximately equals to 1, indicating that the face-toface stacking formed. However, in this period, the cosine of
angle (Figure 8c) contains uctuation in comparison to
Figure 8b. This uctuation is the result of the hydrophobic
interaction. That is the delicate balance of the repulsive
hydrophobic interaction and the attractive hydrogen bonding
between the anionic C5 Pe molecules and water. After the
formation of the face-to-face stacking, it presents dierent
tendencies for the two groups at the oil/water interface. Group
1 stays at the interface steady, and group 2 is more prone to
oscillate at the interface. The reason can be ascribed to the
aggregation number; the large aggregation number can defense
the oscillation.

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We gratefully appreciate the nancial support from NSFC
Project (No. 21173128), Key NSF Project of Shandong
province (No. ZR2011BZ0003 and No. ZR2012BM004), and
the HESTP Project of Shandong Province (J13LD01). The
authors thank Dr. Bradley D. Rose, King Abdullah University of
Science and Technology, for helpful discussions and manuscript
editing. We are thankful for support by Program for Scientic
Research Innovation Team in Colleges and Universities of
Shandong Province.

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IV. CONCLUSIONS
In this work, the eects of the terminal groups on asphaltene
molecules have been studied by MD simulations. The simulated
results indicate that the presence of anionic terminal groups on
the aliphatic chains can dramatically inuence the neutral C5 Pe
behavior both in the oil phase and at the oil/water interface. In
crude oil, the carboxyl C5 Pe favors the face-to-face stacking,
while the carboxylate C5 Pe molecules prefer the face-to-face
stacking in addition to the T-shaped II stacking because of the
repulsive interaction of the headgroups. Whats more, the
terminal groups also aect the properties of the C5 Pe
molecules to adsorb at the crude oil/water interface. The
anionic carboxylate C5 Pe molecules can transform from an
aggregate to a stable slab at the interface, while the carboxyl C5
Pe aggregations persist only in the bulk crude oil during the
whole simulation. The adsorption process of anionic C5 Pe
molecules can be explained by the three-stage model: First, a
few asphaltene molecules are brought to the interface through
the H-bond interaction between water and the oxygen atoms of
anionic C5 Pe. Then, more anionic C5 Pe molecules in the
crude oil are drawn to the interface via noncovalent
interactions. Ultimately, an asphaltene slab is formed at the
interface including the face-to-face stacking.

REFERENCES

AUTHOR INFORMATION

Corresponding Authors

*E-mail: xuzhen@qlu.edu.cn.
*E-mail: shilingyuan@sdu.edu.cn.
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