Article

pubs.acs.org/EF

Precipitation of Asphaltenes and Resins at the TolueneSilica

Interface: An Example of Precipitation Promoted by Local Electrical
Fields Present at the SilicaToluene Interface
Socrates Acevedo,* Jimmy Castillo, and Edgar Hernan Del Carpio
Escuela de Qumica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas 1041-A, Venezuela
ABSTRACT: Adsorption and desorption of asphaltenes and resins occurring at the silicatoluene interface were used as a tool
to investigate phase separation or precipitation promoted by the surface. Adsorption isotherms for this system were obtained as
usual, employing commercial silica plates immersed in toluene solutions. After the adsorption of the sample (asphaltenes,
asphaltene subfraction A2, resins I, and resins II), the plate was removed, contacted with and retracted from toluene to remove
trapped solution, and then immersed again in fresh toluene to measure the desorption. In all cases, the amount desorbed was
either insignicant or a small fraction of the amount expected. This could be analyzed in terms of precipitation at the interface
promoted by local electrical elds present at the silicatoluene interface; these elds promote molecular polarization, dispersion
interactions, and piling up, leading to precipitation. As a result, when the plate with the adsorbed precipitate (material of very low
solubility in toluene) is contacted with fresh toluene, desorption is either insignicant or very low. The combine eects of the
local electrical elds, molecular polarization, and dispersion interactions are so eective that resin precipitation at the above
interface was also obtained. These ideas were found coherent with preliminary atomic force microscopy (AFM) measurements
performed on asphaltenes deposited on a glass surface.

pyridinic-, and pyrrolic-type functional groups.12 Similar results,

with regard to the presence of these functional groups, were
reported earlier by Abdallah and Taylor using XPS and an
stainless-steeltoluene interface.13 The presence of a pyrrolic
functional group in asphaltenes is an interesting nding,
probably related to metal porphyrines. Step-wise adsorption
isotherms for asphaltenes dissolved in toluene using several
mineral rocks as substrates were reported by Mendoza de la
Cruz and collaborators.14 These stepwise adsorption isotherms
were reported for the rst time by Acevedo and co-workers.15
These may be the result of either adsorption of aggregates or
cluster formation at the interface (see the discussion below).
Film thickness in the 20298 nm range, measured by
ellipsometry, was reported by Labrador and collaborators
using the tolueneasphaltene solutions and glass plates as the
surface.16 These thicknesses were somewhat supported by the
report of Castillo et al. on a similar system (chloroform
asphaltenes/glass plates), where stalagmite-type columns up to
200 nm were measured using white light interferometric
microscopy.17 The adsorption behavior of Athabasca bitumen
C7 asphaltene over a macroporous silicaalumina, kaolin, at
room temperature was compared to polynuclear heteroatom
aromatic model compounds. Authors found that up to one
point in concentration adsorption was independent of the
heteroatom content.18 A higher molar mass adsorption for
resins compared to asphaltenes was reported for toluene
heptane solutions using powdered metals as substrates, a result
related to surface morphology.19 A strong dependence of
asphaltene adsorption kinetics with concentration was

INTRODUCTION
Adsorption of asphaltenes at both organic and inorganic
interfaces is a well-known phenomenon reported many times in
the literature.130 Dynamic adsorption of asphaltenes on quartz
and calcite packs and their eect on wettability were
documented.1 Several thermodynamic models were proposed
to account for asphaltene adsorption on mineral surfaces.2,4,68
X-ray photoelectron spectroscopy (XPS) and secondary ion
mass spectrometrytime of ight (SIMSTOF) were used by
Gray et al. to study the surface after asphaltene adsorption on
kaolinite.3 Maximum thickness of the asphaltene layer was
estimated at 11 nm, and no preferential adsorption of nitrogen
or sulfur compounds was observed.3 NiO nanoparticles
supported on nanoparticulated alumina were employed as an
asphaltene adsorbent.4 According to these authors,4 complete
eective adsorption times were observed after 2 min.
Thermocatalytic reactions of asphaltenes adsorbed on nanoparticulated metal oxides were reported by Nassar and coworkers.5 The use of nanoparticles has been suggested for the
fast removal of asphaltenes from oils.6 It was reported that in
situ preparation of NiO nanoparticles in crude oil led to
asphaltene eective removal close to 2.8 g of asphaltenes/g of
NiO.9 Massive precipitation of asphaltenes from crude oil,
promoted by chromatography-grade commercial silica, was
reported some time ago;10 thus, these high uptakes of
asphaltenes by nanoparticles are expected. Correlations
between molecular parameters and adsorbate uptakes were
documented by Lopez-Linares et al.11 working with vacuum
and visbroken bitumen, using modied kaolinites. A combined
quartz crystal microbalance (QCM) and XPS method was
employed to explore the adsorption of asphaltenes on a gold
surface.12 XPS analysis of adsorbed and bulk asphaltene
demonstrated the presence of carboxylic-, thiophenic-, suldic-,
2014 American Chemical Society

Received: April 10, 2014

Revised: July 2, 2014
Published: July 22, 2014
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with respect to crude oil for asphaltenes and resins I were about 15
and 10%, respectively.
Separation of Resins II. These were obtained from the DAO above
using the following chromatography procedure. For this, a continuous
extraction chromatography was assembled by placing commercial silica
gel (100 g, 130270 mesh) soaked with n-heptane within a Soxhlet
extractor. The DAO (5 g) dissolved in 10 mL of n-heptane was placed
at the top of the column, and the extraction was accomplished by
employing boiling solvent and using the following solvent gradient:
heptane, heptane/toluene (1:1), toluene, toluene/chloroform (1:1),
chloroform, and chloroform/methanol (1:1). The complete procedure
lasted for about 98 h to aord 25% of resins II. Recovery was about
96%.
Thin-layer chromatography plates or TLC glass plates (2 cm length
and 1 cm width), covered with silica 60 with a pore diameter of 60 ,
pore volume of 0.8 mL g1, and mean diameter size of 1012 m,
obtained from Merck, were used here. The available area, close to 35
m2 g1, was determined using solutions of p-nitrotoluene as described
earlier.21
Asphaltene subfraction A2 was obtained from asphaltenes using the
reported PNP method.32 Solubility of this fraction in toluene, close to
10%, is similar to the fraction for asphaltenes.
Methods. Calibration Lines and Calculation of Both Solution
and Surface Concentrations. Both surface and solution concentrations were calculated using procedures similar to others reported
earlier.21 The concentrations in the range from 0 to 3000 mg L1 for
asphaltenes and asphaltene subfraction A2 and in the range from 0 to
1000 mg L1 for resins were used. To avoid saturation of the
ultraviolet (UV) detector, concentrationabsorbance calibration
curves were obtained with four dierent cell paths (cm) and four
dierent concentration ranges (mg L1) as follows: (1) 1, 0400; (2)
0.5, 400600; (3) 0.2, 6001500; and (4) 0.1, 15003000. For these
paths and ranges, straight calibration lines with r2 > 0.99 were
obtained. Both adsorption and desorption measurements were made
by duplicates and at dierent times (24, 48, and 72 h).
Adsorption isotherms were measured by placing 7 mL of the
toluene solution in small stoppered vials. The silica TLC plates were
then immersed in toluene and contacted with the solution during the
required time.
Desorption isotherms were obtained after the adsorption experiments as follows: After an adsorption contact time of 72 h and at
selected surface concentrations F, the TLC plate was removed from
the toluene solution, immersed for a few seconds (510 s; removing
time, see below) in fresh toluene to remove small quantities of
solution attached to the plate, and then reimmersed in fresh toluene to
allow for desorption for 24 h. After this time, absorbance was
measured and the corresponding solution concentration was plotted
against the above surface concentration F. Because in all cases
desorption was very small, values of F corresponding to the
adsorption process were used for plotting purposes.
To check reliability of desorption results, for some F values, the
removing time was varied within a 30 s period. No signicant change
in the desorption measurements was detected.
AFM Measurements. For AFM measurement of electrical potential
range coming from glass surface alone, the instrument tip was placed
at several vertical locations from the glass plate and the corresponding
potential was recorded. Zero reference of the vertical axis was taken
equal to the axis corresponding to the potential minimum. In this way,
values of electrical potential against vertical distance were plotted. For
asphaltenes, a 10 mg L1 solution in toluene was prepared and a drop
of this (about 0.2 mL) was placed on the glass plate. Evaporation to
dryness of this solution under nitrogen ow was allowed, and the
deposited sample was examined under the AFM instrument. Results
were obtained and plotted as described above for the glass plate alone.
Proles or cross-section heights of deposited sample, measured from
the glass surface with the instrument tip, aorded values close to 200
nm high.

accounted for in terms of aggregate formation in solution. The

results for the toluene/silica system were adjusted to a secondorder irreversible process.20 This was coherent with the very
slow desorption process measured earlier.21 A QCM method
was employed to examine adsorption of asphaltenes, resins, and
asphalteneresin mixtures dissolved in heptanetoluene
mixtures adsorbed onto gold.22 Adsorption of resins on
asphaltene surfaces lead to both multilayer formation and
asphaltene dispersion into heptane.23 Such formation of the
resin multilayer was coherent with previous results.24 Steps and
other features of the isotherms, apparently consistent with
micelle and hemimicelle aggregates, were reported when the
adsorption on rock minerals from toluene solutions was
studied.25 Adsorption on several clays, such as kaolinite, ilite,
and montmorillonite, from toluene solutions was reported.26
Several techniques, such as N2 adsorption, X-ray diraction,
small-angle X-ray scattering (SAXS), and others, were
employed to analyze the results.26 Adsorption of asphaltene
functionalities, such as carboxylic, pyrrolic, and other, on
goethite (FeOOH) suspended in heptol was reported.27
Irreversible adsorption of much diluted solutions of asphaltenes
ltered on freshly cleaved mica was reported and studied using
atomic force microscopy (AFM).28 When unltered samples
were tried, large objects with nger lengths in the few
micrometer range were observed.28 The adsorption of
asphaltenes and resins from toluene solutions onto quartz
and feldspar and their eect on the mineralaqueous properties
were reported; after the adsorption, no change in eletrophoretic
mobility of these minerals was detected.29 Studies of adsorption
of asphaltene solutions in toluene onto clay minerals in the
presence of water show that the adsorption was reduced but
not eliminated by the presence of water.30 A very recent review
on asphaltene adsorption and other interesting relevant issues
have been reported.36
Because of compliance of obtained isotherms to simple
adsorption models, such as Langmuir and others, it has been
assumed that asphaltene adsorption at the toluenesilica
interface is a reversible process. However, as shown in a
previous adsorptiondesorption study, desorption into toluene
from a silica surface of previously adsorbed asphaltenes was
insignicant, thus suggesting an irreversible adsorption
process.20,21 In fact, massive asphaltene precipitation was
promoted by contacting the crude oil (25 mL) with commercial
silica (5 g).10 The amount of asphaltenes precipitated in this
way approached the total asphaltene content when the
temperature approached 150 C. Very signicant quantities of
precipitate were observed even at 0 C.10
In addition to asphaltenes, in this work, the adsorption
desorption studies were extended to include the asphaltene
subfraction A2, resins I, and resins II. As we did earlier,31 we
call resins I the subfraction co-precipitated with asphaltenes and
resins II the subfraction that remains in the deasphalted oil or
DAO; asphaltene subfraction A2 was obtained from asphaltenes
using the p-nitrophenol or PNP method.32

EXPERIMENTAL SECTION

Materials. Asphaltenes and resins I were obtained from extra-heavy

Cerro Negro oil [American Petroleum Institute (API) gravity = 8.3]
by dilution with 40 volumes of n-heptane using reported procedures.31
In this case, rather than diluting with toluene, the oil was heated (60
C) and n-heptane was added under mechanical stirring. After working
up, the precipitated solid (asphaltenes + resins I) was placed within a
Soxhlet and the resins I were extracted as described earlier.31 Yields
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Table 1. Yieldsa,b and Elemental Analysisc of Samples Studied

sample

H/C

asphaltenes
asphaltene subfraction A2
resins I
resins II

15
2030b
18
17

82.34
81.88
83.1
80.8

8.16
8.00
10.1
9.6

1.4
1.4
0.8
0.7

5.64
4.78
4.1
4.7

1.19
1.17
1.46
1.43

With respect to the crude oil (this work). bWith respect to the asphaltenes. cElemental analysis for resins is taken from ref 31.

RESULTS
Yields and elemental analysis are shown in Table 1. As shown,
elemental analysis is similar for resins I and resins II. Other
measurements reported for these resins, such as molecular mass
distribution [determined by size-exclusion chromatography
(SEC)] and Mn [vapor pressure osmometry (VPO), with
toluene], were also similar.31 As shown, no signicant
dierences between asphaltenes and asphaltene subfraction
A2 were found.
Figure 1 shows the toluene solutionsilica isotherm
measured for both asphaltenes and asphaltene subfraction A2

concentration range. As shown, general trends of both samples

in Figure 1 are similar and any possible structural dierence
between asphaltenes and asphaltene subfraction A2 is not
reected in these isotherms.
A comparison of adsorption isotherms for resins I and resins
II, plotted in Figure 2, shows no signicant dierences. These
isotherms were measured after 24 h. As shown, large quantities
of sample were also adsorbed in both cases.

Figure 2. Comparison of adsorption isotherms measured at the silica

toluene interface for sample resins I and resins II, measured after 24 h.

Table 2 shows results for adsorption and desorption for

asphaltenes. Here, the rst and second columns correspond to
Figure 1. Isotherm measured at the toluenesilica interface
corresponding to asphaltene and asphaltene subfraction A2 samples,
registered after 72 h of contact at room temperature. Isotherms are Htype, meaning that, at high dilution, the nal solution concentration is
insignicant (see the text).

Table 2. Adsorption and Desorption Results for Asphaltenes

in the 03000 mg L1 range after 72 h (see the Experimental

Section). Isotherms were also measured at 24 and 48 h; apart
from aording smaller surface concentrations, these show no
signicant dierences with the isotherm measured at 72 h, and
hence, they are not shown here. According to the literature,33
these isotherms are of type H, meaning that, at nal solution
concentration CF 0, the nal surface concentration F > 0.
This is emphasized by the vertical line drawn at CF = 0. This
revels that anity between the surface and solute is very high.33
Using the method described,21 we estimate that a F close to 7
mg g1 would be required to saturate the silica surface with a
monolayer of asphaltenes; as seen in Figure 1, this is close to
values of F corresponding to CF = 0. Thus, adsorption
equivalent to multilayers is expected at any CF, except for
extreme diluted concentrations (less than 10 mg L1). Very
large values of F were observed in the investigated CF

CIa (mg L1)

CFb (mg L1)

Fc (mg g1)

CDd (mg L1)

400
600
800
1000
1500
2000
2500

238
361
564
706
1124
1333
2356

52.5
57
67.8
78.7
106.6
115.6
166

6.5
7.2
9.5
12.2
16.4
19.6
23.9

a
Initial solution concentration. bFinal solution concentration corresponding to the adsorption process, measured after 72 h. cFinal surface
concentration corresponding to the adsorption process, measured after
72 h. dFinal desorption concentration measured after 24 h.

adsorption experiments, whereas the third column corresponds

to concentrations measured during desorption. Because
desorption was very small and for plotting purposes, we use
F measured in the adsorption experiments. Desorption of
adsorbate could not be detected below initial concentrations of
400 mg L1 (corresponding to F = 238 mg L1 for asphaltenes
and below 200 mg L1 for resins I and resins II; see Table 1).
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Figure 3 is a comparison of adsorption and desorption

experiments performed as described above. Desorption experi-

Figure 4. Comparison of AFM measurements of electrical potential of

a glass plate alone with the electrical potential corresponding to
asphaltenes deposited on a similar glass plate. Vertical lines mark the
range of potential measured (minimum to zero), and the arrows
illustrate the potential range in each case.

asphaltenes is about 4.4-fold the range measured for the glass

surface alone.

DISCUSSION
The results above are consistent with precipitation of sample at
the interface. As mentioned above, massive asphaltene
precipitation was observed when crude oils were contacted
with powdered silica10 (see the Introduction); thus, asphaltene
precipitation at the interface could be predicted. However, resin
and asphaltene subfraction A2 precipitations are new results.
Apparently, the surface promotes the formation of clusters or
aggregates at the interface, which eventually leads to partial
sample precipitation. The precipitated sample would then be in
equilibrium with a very small quantity in solution, as suggested
by the results of the desorption experiments (see Figure 3).
Apparently, the electrical eld prevailing at the surface tends to
align the sample molecules in ways that enhance their
interaction. The large amount of precipitated material,
equivalent to many molecular layers, strongly suggests that
the eld eect extends into the solution well beyond the
interface itself. This is coherent with the AFM results, where
the eld eect propagates up to 560 nm (see Figure 4 and
below).
Although in the asphaltenes case aggregate adsorption from
the solution could not be discarded, this is not the case for
resins, where aggregates in toluene have never been reported.
Thus, the main eect should be precipitation promoted by the
surface.
Dipole moments, in the range from 4 to 8 D for asphaltenes
and between 2 and 4 D for resins have been reported by Goal
and Firoozabadi;34 thus, dipolar interactions with the silica
surface could be predicted. Apparently, interaction with the
eld aligns the sample molecules in such a way to enhance
polar and dispersion interactions, which propagates away from
the surface, leading to precipitation. Thickness of the interface
will thus grow until eld eects become small compared to RT.
Figure 5 depicts a crude simulation of the interactions
described.

Figure 3. Comparison of adsorption and desorption isotherms for

asphaltenes (top) and resins I (bottom), both measured at the silica
toluene interface, with adsorption measurements after 72 h for
asphaltenes and 24 h for resins, at room temperature, and desorption
measured after 24 h.

ments for the asphaltene subfraction A2 yielded results similar

to asphaltenes and are not shown here. Operationally, the
desorption experiment is the result of placing a silica plate
loaded with F (mg g1) of sample in contact with fresh
toluene, and then after 24 h, the small quantity desorbed from
the plate will give the CD shown by the red points in Figure 3.
In all cases, these desorbed values were very small, being a bit
higher for resins.
It is very important to note that F, the nal adsorbed
quantity, is in equilibrium with CD rather than with CF, as
should be the case for any adsorption process. AFM results for
both the glass plate surface and asphaltenes deposited over the
glass plate surface are compared in Figure 4. Attraction and
repulsion between the surface and instrument tip are shown to
the right and left of the minimum, respectively. It is important
to note that, for the asphaltene case, the potential is both
deeper and wider than the case measured for the glass surface
alone. Thus, the vertical attraction potential range for
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of aggregates formed in solution is not a condition for further

clustering at the interface. Clustering at the interface, followed
by sample precipitation, apparently accounts for the results
presented here for both asphaltenes and resins.
The above results and comments have both industrial and
academic importance; from the academic point of view, it open
a question on thermodynamic models currently used to
simulate asphaltene adsorption on rock mineral because all of
them assume adsorption equilibrium. As shown above, the
quantity of asphaltene in solution, which is in equilibrium with
the solid at the surface, is a minute quantity unrelated to the
quantity predicted by the adsorption isotherm. From the
industrial point of view, as shown by the AFM results,
asphaltene deposition on the mineral surface extends eld
eects to distances several fold compared to the original
surface, suggesting that, under favorable conditions, asphaltene
and resin precipitation could grow unlimited, leading to the
well-known asphaltene separation during production and other
industrial operations. On the other hand, total precipitation by
mineral surfaces could be used for DAO preparation and as an
alternative method for asphaltene quantication in crude oils.

Figure 5. Model for arrangement of molecules of sample (asphaltenes

or resins) at the toluenesilica interface. The gure represents a side
view of the multilayer. As shown here, the local electric eld aligns
molecules with permanent or induced dipole, up to a height marked by
the dashed line, where the multilayer reaches a thickness d and where
the eld eect either vanishes or becomes smaller compared to RT.
The gure is not to scale and highly schematic.

These arguments are coherent with the AFM measurements

plotted in Figure 4, where electrical potential measurements for
both glass alone and asphaltenes deposited on glass are
compared. As shown, the electrical potential for the asphaltene
case is stronger and extends well beyond the interface up to a
distance about 500 nm above the surface. Thus, asphaltene
deposition enhances the electrical potential several fold, and
such enhancement is coherent with the observed precipitation
at the interface and with piling up eects (see below).
Although precipitation of asphaltenes is an expected result10
(see Introduction), it is interesting that the same evidence for
precipitation is observed for resins (see Figure 5). We believe
that, in both asphaltenes and resins, besides polar interactions,
dispersion interactions are essential for the observed precipitation at the interface. This should come about through
induced polarization by the surface eld. Once the rst
molecular layers are properly aligned by the electric eld near
the interface, precipitation will be enhanced by the action of
dispersion interactions. The high molecular mass of asphaltenes
and resins and their main structural features (polycyclic
aromatic and aliphatic rings) lead to high polarizability and,
hence, signicantly induced polarization near the interface. It
this well-known that polarizability increases with molecular
volume.35
Extreme piling up of asphaltenes adsorbed at the glass
chloroform interface was reported by Castillo et al., where
stalagmite-type columns of asphaltenes, with heights up to 200
nm, scattered over the entire glass surface were observed.17
This important nding is coherent with the results and
discussion described above. A reasonable account of these
ndings17 would be that the stalagmite dimensions, height and
width, should be determined by the height (distance d in Figure
5) and the width of the electrical local eld. As mentioned
above, using both ellipsometric16 and AFM methods, lengths in
the 200 nm to a few micrometers28 range have been found for
asphaltene clusters at the corresponding interfaces. These
arguments and ndings are coherent with the present AFM
results (see above and Figure 4).

AUTHOR INFORMATION

Corresponding Author

*E-mail: socrates.acevedo@gmail.com.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The nancial support provided by projects FONACIT
(G2005000430) and CDCH (AI-03-12-5509-2004, PG-03-005732-2004, and PI-03-00-5648-2004) is gratefully acknowledged. The authors also thank Lic. Betilde Segovia for
administrative assistance.

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