Journal of Petroleum Science and Engineering 51 (2006) 26 – 36

www.elsevier.com/locate/petrol

Inhibition of asphaltene precipitation in Brazilian crude oils using

new oil soluble amphiphiles
Luiz Carlos Rocha Junior, Maira Silva Ferreira, Antonio Carlos da Silva Ramos *
Departamento de Tecnologia Quı́mica — Universidade Federal do Maranhão, São Luis — MA, Brazil
Accepted 4 November 2005
Dedicated to Prof. Rahoma Sadeg Mohamed

Abstract

Asphaltene and resins are heavy fractions of petroleum responsible for serious problems during petroleum production. These
problems include the formation of organic deposits in oil reservoirs; wells, transport pipelines and equipment, and can significantly
increase the production operational costs. The nature and behavior of asphaltene in crude oils is complex and changes in
temperature, pressure and composition of crude oils during production can result in precipitation of asphaltene components.
Potential solutions for these problems include physical removal of deposits, solvent washes and treatment with dispersant agents.
The use of soluble amphiphile oils provides the most practical and economical solution for deposits treatment. In this work, the
inhibitory capacity of a number of new chemical additives to asphaltene precipitation was examined in three types of Brazilian
crude oils. Low molar mass ethoxylated nonylphenols, vegetable oils (coconut essential oil, sweet almond, andiroba and
sandalwood oil) and organic acids (linoleic, caprylic and palmytic) displayed highest capacity to inhibit asphaltene deposition.
The dissolution capacity of some additives was evaluated for two asphaltenic deposits in aliphatic solvents. The remarkable
solubilization effect displayed by dodecylbenzenesulfonic acid, confirmed the importance of acid–base interactions in this process.
The results also revealed distinct mechanisms for asphaltene solubilization/dispersion in aliphatic solvents and inhibition of
asphaltene precipitation in crude oils.
D 2006 Elsevier B.V. All rights reserved.

Keywords: Asphaltene; Deposit; Precipitation; Polymeric dispersants; Amphiphiles

1. Introduction soori, 1988, Ramos, 2001). Deposits formation during

Organic deposits formation is a problem that seri-
ously affects the petroleum industry worldwide with
drastic economical implications which depend on the
extension of the phenomenon. In the literature there are
many accounts relating the problems generated by the
deposition of heavy fractions in the various steps of the
production process (Islam, 1994; Leontaritis and Man-
* Corresponding author.
E-mail address: akarloss@ufma.br (A.C. da Silva Ramos).
0920-4105/$ - see front matter D 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2005.11.006
petroleum production causes several operational trou-
bles such as total or partial blocking of pipelines and
reservoirs, changes in wettability and equipment
damages. Changes in the balancing of the crude oil
phases during production and processing may lead to
the formation of solid phases through the precipitation
of heavy fractions, such as asphaltenes, resins and
paraffin.
Due to their aggregative nature (Ramos et al., 2001;
Ramos, 2001; Mohamed et al., 1999a; Loh et al., 1999),
asphaltene and resins are important deposit forming
crude oils heavy fractions. These fractions are consti-
 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
tuted by molecules with polycondensated aromatic
rings and lateral aliphatic chains, acid–base functional
groups and complexed metals (León, 1998; Al-Sahhaf
et al., 2002), varying in size as well as in their aggre-
gation tendency. The IP143/84 (1989) procedure,
defines asphaltene as a precipitated of crude oil fluid
produced by the addition of an exceeding portion of n-
heptane, thus forming amorphous particles soluble in
toluene or benzene.
Measures for solving asphaltene precipitation and
deposition problems are typically three fold: (a) the
development of theoretical models (Vasquez and Man-
soori, 2000; Pacheco-Sanchez and Mansoori, 1998;
Victorov and Firoozabadi, 1996; Islam, 1994; (b) the
study of asphaltene interfacial and colloidal behavior in
crude oils and model systems (Ramos, 2001; Ramos et
al., 2001; Mohamed et al., 1999a; Carbognani, 2001)
and; (c) the estimation of chemical additives for the
inhibition of asphaltene precipitation (Chang and Fog-
ler, 1994a,b; Mohamed et al., 1999b; González and
Middea, 1991; Rogel and León, 2001).
With respect to the estimation of chemical additives
for the inhibition of asphaltene precipitation, several
procedures are used to remove or prevent deposits
formation throughout the production, transportation
and refining operations, among which we can cite:
mechanical removal, use of ultrasonic techniques,
cleaning with solvents, removal with hot fluids or
water steam and the addition of inhibitors and disper-
sants (Ramos, 2001). Solvent treatment comes to be an
excellent alternative; however the most applicable such
as toluene, xylene, benzene and chlorate solvents, are
flammable, carcinogenic, dangerous for handling and
harmful for the environment. In addition, many of those
techniques may cause pauses in the production.
Using of substances which effectively stabilize or
solubilize asphaltene in crude oils is either a preventive
or remedial measure which, in addition, saves costs and
ease its application (Stephenson, 1990).
Market products with amphiphile agents are used as
asphaltene precipitation inhibitors and the Pfeiffer mi-
celle (Pffeifer and Saal, 1940), one of the first attempts
to explain crude oils colloidal behavior, is still used as
to justify the additives effect on the asphaltene stabili-
zation. In several researches it is assumed that asphal-
tene particles are kept dispersed in crude oils due to
interactions between natural surfactant polar groups
(resins) and asphaltene superficial charges.
The analysis of changes in crude oils composition by
low molecular mass n-alkane titration is a common
technique to identify the additive’s affectivity over
asphaltene and, in this case, such affectivity depends
27
on the higher additive’s capacity to maintain the asphal-
tene stabilized in the oil phase (Ramos et al., 2001;
Mohamed et al., 1999b; Subodhsen et al., 1999).
Commercial additives are mixtures difficult to char-
acterize once they are produced with no scientific cri-
teria and, in general, they are effective only with crude
oils already tested (Boer et al., 1992).
A few studies have presented alternatives to identify
and develop more effective substances. Nevertheless,
due to the complex nature of the crude oils it is neces-
sary to estimate these substances with as many types of
crude oils as possible in order to obtain more sustain-
able results. Usually, the studies have addressed the use
of nonionic amphiphiles, such as the ethoxilated non-
ylphenols for asphaltene stabilization process (Gonzá-
lez and Middea, 1991; Loh et al., 1999; Mohamed et
al., 1999b; Ramos et al., 2001, Ibrahim and Idem,
2004a), and the importance of acid–base interactions
for asphaltene dissolution process in aliphatic solvents
(Chang and Fogler, 1993, 1994a,b; Ramos et al., 2001).
In the search for new inhibitors, the low solubility of
certain substances in crude oils has become a barrier for
the development of more effective mixtures as well as a
restriction for those products practical use. Ramos et al.
(2001), selected diverse polymers with functional
groups similar to the ones usually found in the research
concerning asphaltene stabilization in crude oils and
aliphatic solvents, being most of them total or partially
insoluble in the estimated crude oils.
In the literature, few studies have evaluated the use
of vegetable oils for preventing asphaltene precipita-
tion. Vegetable oils are mixtures that, due to their
chemical nature, are more soluble in crude oils which,
in addition, contain some substances with characteris-
tics similar to those found in amphiphiles already esti-
mated. Cashew-nut shell liquid, for example, almost
totally formed by phenolic compounds with linear un-
saturated alkyl chains (fifteen carbon atoms) meta-sub-
stituted in aromatic rings, performed well in the
peptization and inhibition of asphaltene precipitation
(Moreira et al., 1999). It was also observed that changes
in pressure and temperature can cause an increase in the
asphaltene stability, thus reducing the inhibition rate
necessary for preventing its deposition (Aquino-Olivos
et al., 2001; Boer et al., 1992).
The use of vegetable oils as inhibitors of asphaltene
precipitation is a plausible economical measure because
of its low production cost, cheaper than the cost of the
majority of the commercial highly elaborated products
used as dispersants, its easy handling and operational
application which does not cause environmental threats.
Yet, essences and vegetable oils present in their chem-
28 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
ical composition substances with functional groups
already estimated in the literature as effective in the
inhibition of asphaltene precipitation (Moreira et al.,
1999), besides the fact that these substances are chem-
ically compatible with crude oils, and thus usable dur-
ing the production process without affecting the crude
oil original quality.
In this work, vegetable oils and derivatives were
estimated against those of certain classical amphiphiles,
in situations involving both, the asphaltene precipita-
tion and the asphaltene solubilization capacity in ali-
phatic solvents.
2. Experimental section
The A, B, C crude oils used in this work came from
important Brazilian petroleum fields, and the asphal-
tenes were separated from the crude oils according to IP
143/84 procedure (1989), Ramos et al., 2001. To obtain
the asphaltenes, n-heptane, n-pentane and toluene were
used (all three purchased from Carlos Erba, with purity
higher than 99%). The obtained asphaltenes were la-
beled as C7I-insoluble in n-heptane or as C5I-insoluble
in n-pentane.
The following substances were evaluated as asphal-
tene precipitation inhibitors:
(i) Ionic surfactants — dodecylbenzenesulfonic acid
(DBSA) purchased from Hoechst; sebacic acid,
from BHD; caprylic acid, also from BHD; linoleic
acid, from Acros Organics; palmytic acid, from
Vetec; salicylic acid, from Isofar; 8-hydroxyquino-
line acid, from Merck; alizarin, also from Merck;
m-hydroxybenzoic acid, from Sigma; cetyltri-
methylammonium bromide (CTAB) from Aldrich;
ethylparaben and methylparaben from Sigma; so-
dium dodecyl sulfate (SDS) from Sigma; poly
(ethylene-co-acrylic acid) from Aldrich;
(ii) Nonionic surfactants — (nonylphenols ethoxy-
lated — Renex), Renex 18, Renex 40, Renex
100 and Renex 1000, from Oxiteno;
(iii) Vegetable oils — soy oil, buriti oil, copaı́ba oil,
pequi oil, babaçu oil, sweet almond oil, resin oil,
andiroba oil, arruda sabina oil, Brazil nut oil,
grape seed’s oil, essential eucalyptus oil, pepper
Jamaican essential oil, pinewood essential oil,
sandalwood essential oil, coconut essential oil,
lemon essential oil. All the oils were commercial
samples, purchased in São Luis, State of Maran-
hão, Brazil, and were used as received;
(iv) Vegetable oil derivatives — a-terpinene, g-ter-
pinene, linalyl acetate, linalool and eugenol (all
from Dierberg S.A. oil essentials industry—
Brazil).
The asphaltene precipitation onset was determined
by n-heptane titration of the crude oil, and the particle
formation was viewed with the help of an Olympus
BX51/BX52 optical microscope. The additive effec-
tiveness to inhibit precipitation was estimated by com-
paring the precipitation onset either, with or without the
use of additives. The additive’s capacity to solubilize
asphaltene was estimated in aliphatic solvents (n-hep-
tane and n-pentane), considering the ones that better
affected the asphaltene precipitation. Asphaltene con-
centration in the supernatant was determined by means
of a Cary50 type spectrophotometer from Varian, in the
visible region (400 nm), and the increase in the asphal-
tene concentration was considered either, as a marker of
the additive’s inhibitory effectiveness or ineffectiveness
in the asphaltene precipitation.
3. Results and discussion
3.1. Asphaltene precipitation onset in crude oils
The evaluated crude oils presented different charac-
teristics, as shown in Table 1 for C7I and C5I asphal-
tene content and for the precipitation onset. Yet, crude
oil C presents a great amount of suspended paraffin.
Generically, crude oils A and B are classified as asphal-
tenic, but the latter derives from a mixture of several
crude oils, and C is a paraffinic crude oil.
A, B, and C crude oils individual precipitation onset
is shown in Table 1 and represents the smallest n-
heptane amount to produce precipitation, as determined
by optical microscopy. Experiments were carried out at
28 F 1 8C, in duplicate, and the results were used as
reference to estimate the capacity of the additives to
inhibit asphaltene precipitation. On the other hand, in
this work, the precipitation onset was used just as
reference to estimate the additive’s effectiveness to
hold the asphaltene within the oil phase. Recent
works (Ibrahim and Idem, 2004b,c) have shown that
asphaltene precipitation behavior is a function either, of
Table 1
Onset of precipitation at a temperature of 28 F 1 8C and asphaltene
content for different Brazilian crude oils
Petroleum Onset precipitation C5I (wt.%) C7I (wt.%)
(mL n-heptane/g oil)
A 3.1 F 0.1 7.7 F 0.3 4.2 F 0.3
B 2.2 F 0.1 3.3 F 0.5 1.2 F 0.4
C 2.8 F 0.1 7.0 F 0.3 2.8 F 0.4
 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
the crude oil nature or the structural characteristics of
the asphaltene molecules; yet, they also show that the
asphaltene stabilization mechanism is equally a func-
tion of the additive’s nature.
In some cases, the effectiveness can be related with a
significant decrease in the amount of precipitated
asphaltene, not necessarily occurring onset shifting
(Ibrahim and Idem, 2004b,d). Yet, it can be verified
that the conditions along the processing and production
of crude oils are different from those found in the
laboratory and, in this case, our results furnish only
an indication that supposedly favors the practical use of
these substances that, for sure, need further accurate
estimation under field conditions.
For the three crude oils, the C5I asphaltene content
was always bigger than C7I asphaltene, which is a
characteristic found in crude oils from different sources
(Fotland et al., 1993). The fact that the B crude oil
presents lower precipitation onset compared with the A
and C crude oils, added with the A crude oil higher C5I
and C7I asphaltene content against the A and C crude
oils, is not related with the asphaltenes tendency toward
precipitation. In Brazil, asphaltene precipitation is usu-
ally found in light crude oils with lower asphaltene
content. Nevertheless, problems related to asphaltenes
deposition are frequently observed in light crude oils
and derivatives in the diverse production stages, irre-
spective of its origins.
3.2. Inhibitors effect on asphaltene precipitation in
crude oils
Ramos et al. (2001) reported troubles when solubi-
lizing some additives already tested in other studies.
Either the insolubility or partial solubility can lead to
Fig. 1. Inhibition capacities of chemical additives: Renex 18, 40 and
100 in oil-A.
29
Fig. 2. Inhibition capacities of chemical additives: Renex 18, 40 and
100 in oil-B.
mistaken experimental interpretations and turn unviable
the practical use of those substances.
In this work, it was carefully observed whether the
additives, throughout the estimated concentration range
(about 8% in weight), were or not soluble in the crude
oils, either by the lack of solids or emulsions. That
amount represents a far higher percent compared with
the one used in loco (about a few parts per million);
however it was necessary in order to establish a rela-
tionship between the structural parameters of the addi-
tive molecules and their effectiveness to inhibit
asphaltenes precipitation.
In this work the graphs show only the soluble addi-
tives that acted better as inhibitors of asphaltenes pre-
cipitation in the evaluated concentrations. All probes
concerning the study of asphaltenes precipitation were
carried out under the same experimental conditions,
with uncertainty of (0.1 mL/g for each measurement).
3.2.1. Renex effect over the precipitation onset
Renex ethoxylated chain increase was followed by a
higher insolubility in the crude oils, reason for which
the Renex 1000 was found insoluble in the three oils, as
confirmed by the presence of particles viewed by opti-
cal microscopy. The remaining three Renex were solu-
ble within the estimated concentration range. Figs. 1 2
and 3 show the Renex effect on the asphaltene precip-
itation in A, B and C crude oils. The dotted line shows
the precipitation onset without additives and the exper-
imental points over this line show the additive’s effi-
ciency to inhibit the asphaltene precipitation as induced
by the addition of n-heptane.
Three Renex (18, 40 and 100) were effective in the
inhibition of asphaltenes precipitation, disregarding the
crude oils nature. These results reinforce the capacity
attributed to ethoxilated nonylphenols to inhibit crude
30 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
oils from different sources (Ramos, 2001; León et al.,
2001; González and Middea, 1991; Loh et al., 1999).
The higher the Renex concentration the higher its inhi-
bition effect in the crude oils, being Renex 18 and
Renex 40 the ones which yielded better results, espe-
cially with the A and B crude oils. With crude oil C, the
three Renex acted similarly in the inhibition of asphal-
tenes precipitation, provably due to the Renex smaller
solubility in this crude oil and, consequently, their
higher affinity with the asphaltene surface.
One should notice that (Fig. 4) the Renex 18 effect
over the three oils is very alike indicating, in principle,
that the asphaltene stabilization mechanism is identical
for the estimated crude oils.
3.2.2. Organic acids effect on the precipitation onset
As to evaluate the effects of the hydrocarbon chain
length, the presence of functional groups and the oc-
currence of double bounds, the following organic acids
were tested: palmytic acid, linoleic acid, caprylic acid,
sebacic acid and salicylic acid (see Fig. 5, for their
chemical structures).
The acids were tested with crude oils A and C and
the best results were found in the following order:
palmytic acid, linoleic acid and caprylic acid, as
shown in Figs. 6 and 7. Within the estimated range of
concentration, an increase in the additive’s concentra-
tion is proportional to the asphaltenes precipitation
inhibition effectiveness.
The sebacic acid, with the same number of carbon
atoms as the caprylic acid and with two functional
groups in the extremity, did not show any inhibitory
effect in the asphaltenes precipitation, reason for
which was not included in Figs. 6 and 7. Similar
results as the ones presented by the sebacic acid
were also observed in two different crude oils, sug-
Fig. 3. Inhibition capacities of chemical additives: Renex 18, 40 and
100 in oil-C.
Fig. 4. Effect of Renex 18 on the asphaltene precipitation onset in
crude oils A, B and C.
gesting that the stabilization mechanism probably
occurs due to the adsorption of just one functional
group, reinforcing former proposals related with
asphaltenes stabilization produced by the additives
surfactant activity (Ramos et al., 2001). In the same
context, we suggest that the carboxyl functional group
from the sebacic acid interacts with species in the
asphaltene particle surface, exposing the hydrocarbon
chain to the external medium.
Palmytic acid best effect, compared with the caprylic
acid, can be correlated with the increase in the alkyl
chain length, consequently increasing its surfactant
character. This result, also obtained for the two crude
oils, reinforces the former proposal for the asphaltene
stabilization.
The linoleic acid, which has two double bonds with
larger hydrocarbon chains than the palmytic acid, be-
cause of its character prominently polar, was less effi-
cient in the asphaltene stabilization process.
The salicylic acid, which chemical structure presents
functional groups similar to those of organic acids
and Renex, produced a strong destabilization in the
asphaltene reducing the A crude oil precipitation to
2.9 mL of n-heptane/g oil and the B crude oil to
1.0 mL n-heptane/g oil, both accounting for 3% wt/wt
of the additive.
In general, results concerning the organic acids study
suggest that the balance between the additive lyophilic
and lyophobic portions rule the asphaltenes stabiliza-
tion process.
3.2.3. Vegetable oils’ effect on the precipitation onset
The choice of vegetable oils as potential asphaltene
inhibitors is backed by the following factors: first be-
cause of the importance of finding new substances with
higher solubility; second because of the good results
 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
Fig. 5. Organic acids chemical structure: (a) palmytic acid (hexadecanoic acid); (b) linoleic (9,12-octadecadyenoic acid); (c) caprylic acid (octanoic
acid); (d) sebacic acid (decanodyoic acid) and salicylic acid.
obtained in the present tests with organic acids, taking
into account the fact that vegetable oils are mixtures
rich in free organic acids or forming glycerides; third
because they are easy to obtain and are cheaper than
most polymeric dispersants commercially used and,
finally, once Maranhão State is plenty in such sub-
stances, their use could lead to positive socio-econom-
ical consequences.
Essential vegetable oils were randomly chosen
according to their availability in São Luis city; never-
theless we tried to estimate products of different nature,
especially the more abundant ones.
Tests were conducted in crude oils A and C. As
vegetable oils sold in São Luis market lack quality
control varying in their composition according to the
way they are processed (raw matter, mixing with adul-
Fig. 6. Inhibition capacities of chemical additives: organic acids
(palmytic, linoleic and caprylic) in oil A.
31
terants, etc.) (Vasconcelos, 2000), special care was taken
as to estimate at least three different samples of vegetable
oils for each type of crude oil. In Fig. 8, the asphaltene
onset represents the average value of at least two vege-
table oil samples that presented the closer values.
As viewed in Fig. 8, the essential coconut oil per-
formed excellently in the inhibition of A crude oil
asphaltene precipitation, as compared with other addi-
tives, fact that, in principle, recommends its application
in field tests.
Good results in the inhibition of asphaltene precip-
itation were also obtained for andiroba oil, sandalwood
essential oil, pinewood essential oil, Brazil nut oil,
grape seed oil, pepper Jamaican essential oil and
sweet almond oil and equivalent results were observed
for the same additives in C crude oil.
Fig. 7. Inhibition capacities of chemical additives: organic acids
(palmytic, linoleic and caprylic) in oil C.
32 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36

Fig. 8. Asphaltene precipitation onset in crude oil A as a function of the additives amount.

For pepper Jamaican essential oil, for example, the 3.3. Chemical additives evaluation in asphaltene
inhibitory effect on the asphaltene precipitation in solubilization
crude oils A and C could, in principle, be attributed
to the presence of eugenol, a substance which presents a Initially, as we are dealing with a polydisperse sam-
phenolic group and is highly concentrated in this oil ple (crude oil fraction), it was necessary to estimate the
(Mouchrek Filho, 2000). Experiments using an eugenol asphaltene behavior in toluene as to relate it with the
standard, however, showed a poor effect on the asphal- spectrophotometer response. The aim of this study is to
tene stabilization process (in the A crude oil, 3.14% wt/ determine a wavelength that allows the monitoring of
wt eugenol shifted the precipitation onset from 3.1 to asphaltene concentration. Fig. 9 shows the UV–vis;
3.3 mL n-heptane/g oil). Eugenol molecular structure is spectra-taken for different C5I and C7I asphaltene con-
similar to that of some nonylphenolic resins, which also centration in crude oils A and C. Although the profile
had little effect in the asphaltene precipitation inhibi- of the curve shows a lack of absorption peaks, this is a
tion, compared with the nonylphenols (Renex) or native typical behavior of polydisperse systems (characteristic
resins (León et al., 2001). Probably the bigger effect of of crude oil fractions).
the pepper Jamaican essential oil found in this work can 400 nm was the selected wavelength to investigate
be attributed to the presence of other substances in this the asphaltene concentration because that is a wave
oil. This result, together with the good effects found range that allows the application of the Lambert–Beer
when using these vegetable oils in the inhibition of the law (considering up to 1.0 unit absorbance readings as
A and C crude oils asphaltene precipitation, suggest maximum) and also due to literature references (Brüg-
that they can be fractioned as to allow the identification gemann and Freitas, 1995), that recommend the check-
of substances with greater capacity to inhibit asphaltene
precipitation, as reported by Moreira et al. (1999),
during the application of cashew-nut oil shell liquid,
where it was proved that, beside the oil, two substances
containing phenolic groups in their chemical structure,
cardanol and polycardanol, obtained from their frac-
tionation, were also active.
Up to this date, however, there are no systematic
studies that establish a relationship between the addi-
tive efficiency in inhibiting asphaltene precipitation
induced by the addition of flocculants and its efficien-
cy in the field. As a rule, all substances pointed out in
this article must be further tested in the field during
production, where asphaltene precipitation conditions
can substantially differ from experimental laboratory Fig. 9. Absorbance spectra obtained from a solution of C5I and C7I in
conditions. toluene at 28 F 1 8C.
 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36 33

Fig. 10. Absorbance as a function of C7I and C5I asphaltene concentration from A and C crude oils, in toluene.

ing of polyaromatic hydrocarbon concentration in that In the asphaltene solubility study, only the additives
wavelength range. listed in Figs. 12 and 13, soluble in n-heptane and
Asphaltene C7I and C5I calibration curves (in A and n-pentane within the determined concentration range,
C crude oils) in toluene (T = 28 F 1 8C room tempera- were tested. Model solvents such as the n-heptane and
ture) presented a linear behavior within the evaluated n-pentane are more representative in this case, once
concentration range, as shown in Fig. 10 for the C7I-A they are crude oil derivatives and simulate the oil low
asphaltene, and they were further used to study the dielectric constant.
asphaltene solubilization in aliphatic solvents as to Fig. 12 shows the results of asphaltene C7I solubil-
determine their concentration in the supernatant. ity, from oil A, in n-heptane. Dodecylbenzenessulfonic
In order to determine the kinetics of the solubili-
zation/dispersion, preliminary tests were undertaken
with some of the additives, as shown in Fig. 11 for
the octanoic acid (caprylic acid) and for the andiroba
vegetable oil, in which an initial increase of the
absorbance can be observed, followed by a plateau
region or saturation, as well as two distinct behaviors:
on the one hand it occurs the absorbance increasing in
function of time, on the other the absorbance remains
unchanged.
The stabilization time for asphaltene absorbance was
about 70 h for the andiroba oil and 90 h for the octanoic
acid. After that, only small oscillations in the readings
were observed, with no more than 3% variation with
respect to the absorbance value. To be sure, all experi- Fig. 11. Kinetic study of C7I and C5I asphaltene solubilization from
ments on the additives efficiency in aliphatic solvents crude oil A in n-pentane and n-heptane, respectively, as a function of
were carried out during at least 168 h (seven days). the octanoic acid and andiroba vegetable oil combined action.
34 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36

Fig. 12. C7I asphaltene from oil A — solubilization in n-heptane in presence of additives.

acid (DBSA) had an excellent performance as well as
the Renex 100. Similar behavior was observed for
asphaltene C5I in n-pentane (Fig. 13). Proof of the
dodecylbezenesulfonic acid (DBSA) effectiveness in
dissolving C7I and C5I deposits, corroborates former
reports by Boer et al. (1992), Chang and Fogler (1993),
Loh et al. (1999), and Ramos et al. (2001), revealing the
importance of acid–base interactions in the asphaltene
dissolution process. Weak acids, however, such as lino-
leic and octanoic ones, did not present significant
results.
Nevertheless, DBSA presented less expressive
results on the asphaltene precipitation inhibition. This
result points out that the asphaltene stabilization mech-
anism in crude oils is different from the asphaltene
stabilization mechanism in crude aliphatic solvents,
reinforcing the idea that, in crude oils, the asphaltene
can be dispersed by additives due to hydrophobic inter-
actions with asphaltene particles, while solubilization is
the process that controls the additive activity on asphal-
tene in aliphatic solvents.
In practice, vegetable oils did not have any effect in
the solubilization tests with a model solvent, with the
best result furnished by coconut essential oil and Brazil
nut oil.
Results with C7I and C5I asphaltene of C crude oil
match the ones previously obtained for crude oil A; yet,
they prove that DBSA and Renex efficiency does not
depend on the asphaltene source used in this experiment.
4. Conclusions
In this work several substances were screened and
selected as potential asphaltene precipitation inhibitors
and/or as potential asphaltene deposit solubilizers. Once
operational variables in the field may be very distinct
from laboratory experiments, the necessity of evaluating
these substances bin locoQ is emphasized. Low molecular
mass ethoxilated nonylphenols performed well in the
inhibition of asphaltene in Brazilian crude oils, confirm-
ing the efficiency of these substances in diverse sources
of crude oils. Nevertheless, one observed restriction was

Fig. 13. C5I asphaltene from oil A — solubilization in n-pentane in presence of additives.
 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
Renex insolubility due to an increase in the ethoxilated
chain. The stabilization mechanism for Renex 18 and
Renex 40 (in the three tested crude oils) does not depend
on the crude oil origin.
It was also confirmed that vegetable oils could be
used as inhibitors, while revealing products rather sol-
uble in crude oils compared with various insoluble
polymeric dispersants, turning these results practical
and economically valuable. Vegetable oils that per-
formed better were sweet almond, andiroba, coconut
essential oil and sandalwood essential oil.
Organic acids such as palmytic, linoleic and caprylic
acid showed fairly efficient in the asphaltene precipita-
tion inhibition, addressing towards an asphaltene stabi-
lization mechanism as a function of its surfactant
capacity. These results also indicate that vegetable
oils can further be fractioned while searching for sub-
stances with higher inhibition potential.
With respect to the studies on asphaltene solubility
in aliphatic solvents, even when the solvents simulate
the crude oils apolar medium they may not be repre-
sentative of crude oils. In this case, it is also noted the
scarcity of studies that establish a relationship between
the additives effectiveness and their capacity in the
field, as for example when one attempts to solubilize
deposits in the transport pipeline. Yet, our study proves
that DBSA and Renex efficiency does not depend on
the asphaltene nature. Renex 18 and Renex 40 pre-
sented less significant results and Renex 100 performed
slightly better. These results were practically opposite
to the ones found for the asphaltene precipitation inhi-
bition and, in principle, they point out that both the
asphaltene solubilization in aliphatic solvents and the
precipitation inhibition mechanisms in crude oils are
distinct with respect to the interactions between asphal-
tenes and additives.
Acknowledgments
The authors thank the Brazilian agencies CAPES,
for financial support, and CNPq, for the research grants,
and address especial thanks to Prof. Watson Loh, for
some useful discussions.
References
Al-Sahhaf, T.A., Fahim, M.A., Elkilani, A.S., 2002. Retardation of
precipitation by addition of toluene, resins, deasphalted oil and
surfactants. Fluid Phase Equilib. 194–197, 1045 – 1057.
Aquino-Olivos, M.A., Buenorostro-Gonzalez, E., Andersen, S.I.,
Lira-Galeana, C., 2001. Investigations of inhibition of asphaltene
precipitation at high pressure using bottomhole samples. Energy
Fuels 15, 236 – 240.
35
Boer, R.B., Leelooyer, K., Eigner, M.R.P., van Bergen, A.R.D.,
1992. Screening of crude oils for asphalt precipitation: theory,
practice, and the selection of inhibitors. Soc. Pet. Eng., SPE
25185, 339 – 349.
Brüggemann, O., Freitas, R., 1995. Determination of polycyclic
aromatic hydrocarbons in oils samples by micellar eletrokinetic
capillary chromatography with photodiode-array detection.
J. Chromatogr. A 717, 309 – 324.
Carbognani, L., 2001. Dissolution of solid deposits and asphaltene
isolated from crude oil production facilities. Energy Fuels 15,
1013 – 1020.
Chang, C.-L., Fogler, H.S., 1993. Asphaltene stabilization in alkyl
solvents using oil-soluble amphiphiles. Soc. Pet. Eng., SPE
25185, 339 – 349.
Chang, C.-L., Fogler, H.S., 1994a. Stabilization of asphaltene in
aliphatic solvents using alkylbenzene-derived amphiphiles: 2.
Study of the asphaltene–amphiphile interactions and structures
using Fourier transform infrared spectroscopy and small-angle
X-ray scattering techniques. Langmuir 10, 1758 – 1766.
Chang, C.-L., Fogler, H.S., 1994b. Stabilization of asphaltene in
aliphatic solvents using alkylbenzene-derived amphiphiles: 1. Ef-
fect of the chemical structure of amphiphiles on asphaltene stabi-
lization. Langmuir 10, 1749 – 1757.
Fotland, P., Anfindsen, H., Fadnes, F.H., 1993. Detection of asphal-
tene precipitation and amounts precipitate by measurement of
electrical-conductivity. Fluid Phase Equilib. 82, 157 – 164.
González, G., Middea, A., 1991. Peptization of asphaltene by various
oil soluble amphiphiles. Colloids Surf., A 52, 207 – 217.
Ibrahim, H.H., Idem, R.O., 2004a. CO2-Miscible flooding for
three Saskatchewan crude oils: interrelationships between
asphaltene precipitation inhibitor effectiveness, asphaltenes
characteristics, and precipitation behavior. Energy Fuels 18,
743 – 754.
Ibrahim, H.H., Idem, R.O., 2004b. A method for evaluating the
kinetics of n-heptane-induced asphaltene precipitation from vari-
ous Saskatchewan crude oils during light hydrocarbon flooding.
Fuel 84, 311 – 314.
Ibrahim, H.H., Idem, R.O., 2004c. Correlations of characteristics of
Saskatchewan crude oils asphaltenes with their asphaltene precip-
itation behavior and inhibition mechanisms: differences between
CO2- and n-heptane-induced asphaltene precipitation. Energy
Fuels 18, 1354 – 1369.
Ibrahim, H.H., Idem, R.O., 2004d. Interrelationships between asphal-
tene precipitation inhibitor effectiveness, asphaltenes characteris-
tics, and precipitation behavior during n-heptane (Light Paraffin
Hydrocarbon) -induced asphaltene precipitation. Energy Fuels 18,
1048 – 1083.
IP 143/84, 1989. Standard Methods for Analysis and Testing of
Petroleum and Related Products.
Islam, M.R., 1994. Role of asphaltene on oil recovery and mathemat-
ical modeling of asphaltene properties. In: Yen, T.F., Chilingarian,
G.V. (Eds.), Asphaltene and Asphalts, 1. Elsevier Science B.V.,
Amsterdam, The Netherlands, pp. 249 – 298.
León, V., 1998. Nuevos enfoques sobre la visión molecular de un
crudo pesado. Vis. Tecnol. 5 (2), 131 – 137.
León, O., Contreras, E., Dambakli, G., Epidel, J., Acevedo, S.,
2001. The influence of the adsorption of amphiphiles and
resins in controlling asphaltene flocculation. Energy Fuels 15,
1028 – 1032.
Leontaritis, K.J., Mansoori, G.A., 1988. Asphaltene deposition: a
survey of field experiences an research approaches. J. Pet. Sci.
Eng. 1, 229.
36 L.C. Rocha Junior et al. / Journal of Petroleum Science and Engineering 51 (2006) 26–36
Loh, W., Mohamed, R.S., Ramos, A.C.S., 1999. Aggregation of
asphaltene obtained from a Brazilian crude oils in aromatic sol-
vents. Pet. Sci. Technol. 17, 147 – 163.
Mohamed, R.S., Loh, W., Ramos, A.C., 1999a. Aggregation behavior
of two asphaltenic fractions in aromatic solvents. Energy Fuels 13
(2), 323 – 327.
Mohamed, R.S., Loh, W., Ramos, A.C., Delgado, C.C., Almeida,
V.R., 1999b. Reversibility and inhibition of asphaltene precipita-
tion in Brazilian crude oils. Pet. Sci. Technol. 17, 877 – 896.
Moreira, L.F.B., Lucas, E.F., González, G., 1999. Stabilization of
asphaltene by phenolic compounds extracted from cashew-nut
shell liquid. J. Appl. Polym. Sci. 73, 29 – 34.
Mouchrek Filho, V.E., 2000. Estudos analı́ticos e modificações quı́-
micas por metilação e acetilação do eugenol contido no óleo
essencial extraı́do das folhas da espécie Pimenta dióica Lindi.
São Carlos, 124 p. Tese (Doutorado) — Instituto de Quı́mica de
São Carlos. Universidade de São Paulo.
Pacheco-Sanchezand, J.H., Mansoori, G.A., 1998. Prediction of the
phase behavior of asphaltene micelle/aromatic hydrocarbon sys-
tems. Pet. Sci. Technol. 16 (3–4), 377 – 394.
Pffeifer, J.P.H., Saal, R.N., 1940. Asphaltic bitumen as colloid system.
J. Phys. Chem. 44 (2), 139 – 148.
Ramos., A.C.S., 2001. Asfaltenos em petróleos brasileiros: agregação
em solventes aromáticos, desenvolvimento de aditivos e estabil-
ização de emulsões. Campinas, 275p. Tese (Doutorado) — Facul-
dade de Engenharia Quı́mica. Universidade Estadual de
Campinas.
Ramos, A.C.S., Haraguchi, L., Notrispe, F.R., Loh, W., Mohamed,
R.S., 2001. Interfacial and colloidal behavior of asphaltene
obtained from Brazilian crude oils. Pet. Sci. Eng. 32, 201 – 216.
Rogel, E., León, O., 2001. Study of the adsorption of alkyl-benzene-
derived amphiphiles on an asphaltene surface using molecular
dynamics simulations. Energy Fuels 15, 1077 – 1086.
Stephenson, W.K., 1990. Producing asphaltenic crude oils: problems
and solutions. Pet. Eng. Int., 24 – 31.
Subodhsen, P., Clark, P.F., Pruden, B.B., 1999. Flow loop apparatus to
study the effect of solvent, temperature and additives on asphal-
tene precipitation. Pet. Sci. Eng. 23, 133 – 143.
Vasconcelos, A.F.F., 2000. Estudos analı́ticos de caracterização do
óleo de copaı́ba. Dissertação de mestrado. Universidade Federal
do Maranhão, 109 p.
Vasquez, D., Mansoori, G.A., 2000. Identification and measurement
of petroleum precipitates. J. Pet. Sci. Eng. 26, 49 – 55.
Victorov, A.I., Firoozabadi, A., 1996. Thermodynamic micellization
model of asphaltene precipitation from petroleum fluids. AIChE J.
42 (6), 1753 – 1764.