Journal of Petroleum Science and Engineering 190 (2020) 107095

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Effect of CO2 on the dynamic and equilibrium interfacial tension between

crude oil and formation brine for a deepwater Pre-salt field
Santiago Drexler *, Elton L. Correia , Ana Carolina Jerdy , Leandro A. Cavadas , Paulo Couto
LRAP (Enhanced Oil Recovery Lab), Universidade Federal do Rio de Janeiro, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Interfacial tension (IFT) between oil and brine is key to determine the Capillary Number, which governs capillary
Interfacial tension forces in the porous medium. As a result, changes in IFT affect the displacement efficiency and the residual oil
CO2 flooding saturation having direct impact on the Recovery Factor. Fluids in Pre-salt fields (offshore Brazil) have particular
Pre-salt reservoirs
characteristics, such as high salinity in the brines, elevated content of asphaltenes and resins in the oils and high
WAG
Reservoir fluid characterization
CO2 content in the produced gas for some fields. The effect of CO2 on the IFT depends on complex electrostatic
Capillary forces and acid-base equilibria, and cannot be predicted by a single fluid property. This work presents the experimental
Dynamic IFT study of the effect of CO2 dissolution on the IFT between a Pre-salt oil with a high total base number (TBN) and
non-negligible total acid number (TAN) and a high salinity brine using the pendant drop technique. The oil and
its asphaltenic fraction were characterized by Fourier-transform infrared spectroscopy, nuclear magnetic reso­
nance spectroscopy, and elemental analysis identifying characteristic functional groups and indicating both
acidic and basic polar functional groups. CO2 dissolution resulted in an IFT increase of 56% evidencing that,
despite the high TBN of this oil, basic groups have low surface-activity. Moreover, a study of IFT as a function of
pH showed that the maximum IFT was found in strongly acidic environments, but constant IFT values were
obtained at neutral and basic pH values. Thus, the interfacial activity is governed by asphaltenes and resins with
polar groups of varying acid/base behavior. The presence of CO2 also accelerated the dynamic behavior of IFT
reducing the equilibrium time by 70%. This is caused by the reduction of oil viscosity, which impacts the
relaxation time and enhances the diffusion of surface-active species towards the interface. The results in this
work evidence that the CO2 content should be considered when modeling fluid properties for this type of res­
ervoirs, as it affects the oil-brine IFT. In addition, for this oil with high content of surface-active compounds and
non-negligible TAN and TBN, CO2 flooding does not contribute to reduce the IFT. Therefore, the efficiency of this
Enhanced Oil Recovery technique in this type of field relies on viscosity reduction, miscible displacement and
wettability alteration rather than IFT reduction.

1. Introduction however, temperatures were found to be moderate between 60 and 70

�
C (Cezar et al., 2015; Henriques et al., 2012).
Offshore Pre-salt fields in Brazil have been among the most impor­ Transportation of fluids from production platforms is challenging
tant assets in the Oil and Gas Industry for the last ten years reaching due to the large distances of over 200 km to the coast (Filho et al., 2015).
productions over 1.5 million barrels per day (Mejia Sanchez et al., The application of CO2 and water alternated with gas (WAG) injection in
2019). One of the greatest exponents in Santos Basin, Lula Field, has Lula Field is aimed as an Enhanced Oil Recovery (EOR) method that
over 6 billion barrels of oil equivalent (boe) reserves (Henriques et al., simultaneously reduces the emissions of this greenhouse gas. In this
2012). Initial characterization of its fluids rendered light oil (28� API) regard, gas flooding and WAG were taken into consideration since the
and gas to oil ratio (GOR) up to 230 m3/m3, with up to 12% volume of early days of the development of Lula Field (Hauville et al., 2014). The
CO2 (Nakano et al., 2009). However, further publications reported GOR first pilot for the injection of CO2-enriched natural gas in Lula field was
values up to 350 m3/m3 with CO2 contents of up to 20% (Tadeu et al., reported in 2011 (Pizarro and Branco, 2012). In this pilot test, CO2
2015). Ultra-deep waters result in high pressures (over 8000 psi); enrichments up to 50% were applied obtaining successful results in

* Corresponding author. Rua Moniz Arag~ ao 360 Bl 4, Cidade Universit�

aria, Rio de Janeiro, 21914-594, Brazil.
E-mail address: [email protected] (S. Drexler).

https://doi.org/10.1016/j.petrol.2020.107095
Received 20 December 2019; Received in revised form 17 February 2020; Accepted 17 February 2020
Available online 20 February 2020
0920-4105/© 2020 Elsevier B.V. All rights reserved.
S. Drexler et al. Journal of Petroleum Science and Engineering 190 (2020) 107095

terms of connectivity of the reservoir and sustained well productivity. where they are positively charged.
CO2 flooding is a mature EOR technique which has been applied for Lashkarbolooki et al. studied the effect of CO2 dissolution in brine on
over 60 years. The main mechanisms for incremental oil production in the IFT for oils with different concentrations of acid groups and found
miscible flooding are viscosity reduction and oil swelling (Lake, 1989). that carbonated brine resulted in higher interfacial tension for more
Stalkup discussed the physical properties that affect sweeping and acidic oils. They also reported that the hydrophobicity of the native
displacement efficiencies in immiscible gas flooding (Stalkup, 1978). At surfactants in the crude oil sample increased when CO2 was dissolved in
high pressures and moderate temperatures, CO2 density is in the same the brine. In addition, they studied the dynamic behavior of IFT
order of magnitude than that of average oils reducing the effects of concluding that the mass transfer and surface orientation of native
gravity segregation. However, the viscosity ratio between CO2 and oil is surfactants is affected by CO2 diffusion in the oil phase (Lashkarbolooki
unfavorable (i.e. much lower than 1), giving place to WAG to improve et al., 2017). In posterior research (Lashkarbolooki et al., 2018), the
mobility ratio increasing the sweeping efficiency. authors investigated the dynamic IFT between different oils and brines
The most relevant operational parameters including common prob­ at elevated pressures and temperatures. They found that the key factors
lems in WAG projects, such as poor injectivity and corrosion among controlling the change of IFT are the concentration and nature of acid
others, were reviewed elsewhere (Christensen et al., 2001). A more and basic compounds and the pH of the aqueous phase. In contrast,
recent publication presented a sensitivity analysis of key aspects of WAG pressure and temperature did not show a critical effect. Also, their re­
and gas flooding, i.e. gas and water injected volumes and well pattern sults supported the idea that CO2 diffusion in crude oil acts as a mass
design (Perera et al., 2016). One key variable for modeling reservoir transfer barrier for the efficient packing of the surface-active compo­
scenarios is interfacial tension (IFT), as it is directly related to the nents. This diffusion has a contrary effect to that of the ionization of
Capillary Number which represents the ratio between viscous and basic compounds in acid environments. As a result, the IFT will depend
capillary forces (Sheng, 2010). Nevertheless, there is no straightforward on which of these phenomena overcomes.
relationship between CO2 mole fraction and oil-brine interfacial tension, Another work by the same group (Lashkarbolooki and Ayatollahi,
since this physical property depends on complex intermolecular forces 2018) analyzed the IFT between oils with different total acid numbers
including electrostatic, acid-base and other interactions. (TAN) and asphaltene and resin contents and brines with different sa­
Several studies presented the effect of CO2 dissolution on the inter­ linities and pH values. Their experiments showed that the TAN alone is
facial tension between oil and water phases. For systems with low not enough to define the interfacial activity of different crude oils. The
concentration of surface-active components (i.e. decane and water), the distribution of functional groups (such as those containing Sulfur, Ni­
increment in CO2 mole fraction results in lower IFT values (Georgiadis trogen and Oxygen) in the oil and the pH of the aqueous phase proved to
et al., 2011). Another work (Sun and Chen, 2005) obtained the same be determinant in the resulting IFT. Moreover, both seawater and
trend for live oil and brine (salinity of 2969 ppm) obtaining a decrease of deionized water showed the same trends for the variation of IFT with
30% from the initial IFT for a CO2 mole fraction of 65% in the oil phase. pH.
Compounds containing polar functional groups in the oil such as The cited bibliography evidences that the effect of CO2 dissolution on
alcohols (Moradi et al., 2014) and carboxylic acids (Hoeiland et al., IFT involves the contribution of complex phenomena and is dependent
2001; Sayed et al., 2019) have effect on the IFT. Most of the components on the specific composition of the aqueous and oil phase. Given the
with interfacial activity concentrate in the asphaltene and resin fractions characteristic of the Pre-salt scenario, the investigation of the effect of
of the oil (Buckley et al., 1998). The capability of asphaltene and resins CO2 on IFT is of great relevance to study fluid-fluid interactions in these
in crude oil to decrease interfacial tension with the aqueous phase was reservoirs either for reservoir characterization or EOR research pur­
thoroughly discussed elsewhere (Lashkarbolooki et al., 2016; Lashkar­ poses. This work proposes an experimental investigation of the effect of
bolooki and Ayatollahi, 2016; Schorling et al., 1999). The composition CO2 dissolution on the dynamic and equilibrium interfacial tension
of the asphaltenes has a greater effect on their surface activity than their between a crude oil and brine characteristics of Pre-salt reservoirs. Its
overall concentration (Yang et al., 2014). In addition, the efficiency of main objective is to understand the variation of IFT as CO2 is introduced
these polar compounds as surfactants is affected by the other compo­ in the system, in correlation with the properties of the fluids in this
nents in the oil phase, such as the composition and concentration of challenging reservoir environment.
paraffin fractions and the presence of light fractions such as dissolved
gas (Doryani et al., 2015). Also, properties of the aqueous phase such as 2. Materials and methods
ionic composition (Buckley and Fan, 2007; Kakati and Sangwai, 2017;
Lashkarbolooki et al., 2016; Mahmoudvand et al., 2019; Tichelkamp Formation brine was reproduced in laboratory following the
et al., 2015) and pH (Ashrafizadeh et al., 2012; Hutin et al., 2016; Hyde composition of the formation water from a Brazilian Pre-salt field re­
et al., 2018; Ramakrishnan and Wasan, 1983) are of paramount ported by Shell Brasil (Table 1). The operator also provided a sample of
importance to determine the activity of these amphiphilic compounds crude oil (Oil B) from the same field. In addition, a synthetic oil (Oil M,
and, thus, the IFT between oil and brine. Buckley and Fan (2007) 71.1 wt% n-C16 and 28.9 wt% toluene) was prepared matching the ratio
identified the concentration of asphaltenes, total acid number (TAN), between asphaltenes and saturates from the Pre-Salt oil sample. The
total basic number (TBN) and oil viscosity as the most relevant param­ reagents were acquired from Sigma-Aldrich with a purity of 99.9%.
eters to influence oil-brine IFT. The contribution of each one of them Fluids were characterized using the following procedures. Formation
depends on the pH of the aqueous phase. Particularly, while TAN has an
effect at basic conditions, TBN is significant in acid environments.
Table 1
Ultra-low IFT was achieved for oils with TAN over 0.1 at pH values
Pre-Salt formation brine composition.
greater than 10 indicating the increased surface activity of acid com­
pounds in basic environments. Ions Concentration [ppm]
CO2 dissolution in the brine phase decreases the pH due to the Naþ
57580
equilibrium of carbonic acid (Bhatt et al., 2019). For oils with acidic or Ca2þ 24250
basic surface-active compounds, this shift of pH has a strong influence Mg2þ 2120
Kþ 1200
on the ability of these compounds to reduce IFT (Lashkarbolooki and Ba2þ 24
Ayatollahi, 2018). Asphaltenes and resins forming acids (i.e. sulphonic Sr2þ 1260
or carboxylic acids) will be ionized in basic environments showing SO2-
4 54
greater interfacial activity at high pH. On the other hand, compounds Cl 139900
TDS 226388
with basic groups (i.e. amines) are more active at low pH solutions

2
S. Drexler et al. Journal of Petroleum Science and Engineering 190 (2020) 107095

brine conductivity and pH were measured using a Mettler Toledo Sev­ the system, and finally nitrogen was used to dry it.
enExcellence meter. SARA analysis was performed by IP 143 n-heptane Density and viscosity of dead and recombined fluids were calculated
precipitation method (asphaltenes) and medium pressure liquid chro­ with commercial software. For oil phases, PVTSim Nova 3.3, (Calsep)
matography (saturates, resins and aromatics). In addition, total acid with the Soave-Redlich-Kwong equation of state (EOS) and the Peneloux
number (TAN) and total base number (TBN) were calculated using the volume correction was used. Brine properties were calculated with OLI
ASTM D664 procedures, and gas chromatography (GC) was performed studio 9.6 (OLI Systems Inc.) with the Mixed Solvent Electrolytes þ
in an Agilent HP7890B with a DB-Petro column. Finally, the API gravity Soave-Redlich-Kwong EOS.
was measured in a Mettler Toledo DM40 density meter, and dead oil IFT measurements are time-dependent, mostly due to the diffusion
viscosity was measured in an Anton Paar SVM 3000. process of surface-active species to the interface (Georgiadis et al.,
The asphaltene fraction of the crude oil was separated using n-hep­ 2011). This dynamic behavior introduces uncertainties when analyzing
tane following the procedure by Franco et al. (2013). The character­ the data because the equilibration process can take several hours. A
ization was made by Fourier-transform infrared spectroscopy (FTIR) logarithmic function was used to model the data set for each experiment.
with a Nicolet 6700 spectrometer (Thermo Scientific) using a DTGS KBr Since this function is not asymptotic, a threshold value of 0.01
detector and nuclear magnetic resonance (NMR) with a Bruker AV400 mNm 1h 1 was taken as the stabilization limit derivative. Using this
using 16 scans. Carbon, hydrogen, nitrogen and sulfur contents were threshold value to calculate the stabilization time for each data set made
obtained for both crude oil and asphaltenes by elemental analysis using it possible to calculate the equilibrium IFT with the fitting logarithmic
the procedures in ASTM D5291 performing triplicate analysis of all function.
samples with a maximum standard deviation of 0.81 wt%. The numerical procedures involved in the calculation of the IFT
IFT measurements were made at 60 � C and 1000 psi using a high- value from the drop profile were already discussed in the literature
pressure high-temperature (HPHT) Drop Shape Analyzer (DSA) appa­ (Anastasiadis et al., 1987; Song and Springer, 1996). Finally, all exper­
ratus designed by Kruss and Eurotechnica. Fig. 1 shows the scheme for iments were repeated 3 times, and the results shown in this work are the
the experimental setup used for the tests. Different tests were made to mean values, with the error bars representing the standard error of the
analyze the effect of both the CO2 dissolution in the fluids and the pH of mean.
the aqueous phase.
For experiments with dead fluids (no CO2), the DSA chamber was 3. Results and discussions
first filled with brine and then all lines were bled. The pressure and
temperature were raised to reach stabilized experiment conditions. 3.1. Fluid characterization
Then, the drop of oil was injected into the chamber using a u-shaped line
giving start to the experimental run. Measurements were taken every 30 The gas chromatography (GC) analysis of crude Oil B is shown in
s. Table 2, and the SARA composition, total acid and basic numbers (TAN
Recombination of dead oils and brines with CO2 was carried out and TBN) are presented in Table 3. It can be observed that although the
following the procedures detailed elsewhere (Drexler et al., 2019). In the TAN/TBN ratio is lower than one indicating a more basic behavior; both
experiments containing CO2-saturated fluids, degassed brine was first TAN and TBN have non-negligible values, indicating the presence of
pumped into the chamber, all lines were bled, and test conditions were both acid and basic groups in Oil B. In addition, the resin and asphaltene
set. Then, the CO2-saturated brine was pumped towards the chamber, contents suggest that Oil B has a considerable concentration of
pushing the degassed brine back to a piston cell. After injecting at least interfacial-active components.
three times the total volume of the system, the drop of oil saturated in Elemental analysis characterization of Oil B and its asphaltene
CO2 was formed and the experiment began. After all experiments, the fraction is reported in Table 4. The relative strength of each of these
cleaning routine consisted of flowing toluene and pure water through contributions is yet to be assessed. As expected, the asphaltenes have a
the oil and brine lines, respectively. Then, methanol was used to flush lower H/C ratio than the crude oil due to their higher degree of

Fig. 1. DSA apparatus experimental setup for IFT measurements at HPHT.

3
S. Drexler et al. Journal of Petroleum Science and Engineering 190 (2020) 107095

Table 2 according to Silverstein et al. (2014), free OH occurs in the 3700-3450

Pre-salt oil chromatography. cm 1 range, whereas intermolecular bonds of OH occur between 3550
Component wt% Component wt% and 3200 cm 1, which actually includes the identified peak. This may
indicate that OH exists bonded to the asphaltenes molecules, thus
C3 0.00 C12 2.68
iC4 0.01 C13 3.12 contributing to their acidity. Furthermore, the identification of both
nC4 0.01 C14 3.03 C–– O and C–O groups in these ranges can indicate the presence of esters
iC5 0.12 C15 3.29 in the sample.
nC5 0.18 C16 2.90 Proton nuclear magnetic resonance (NMR) characterization of the
C6 0.48 C17 2.85
Mcyclo-C5 0.21 C18 3.15
asphaltene fraction using the work by Silverstein et al. (2014) to identify
Benzene 0.00 C19 2.89 the functional groups is reported in Table 6. The results agree with the
Cyclo-C6 0.19 C20 2.62 FTIR characterization, confirming the presence of aliphatic and aro­
C7 0.94 C21 2.54 matic carbon-hydrogen bonds and hydroxyl groups.
Mcyclo-C6 0.48 C22 2.47
The impact of CO2 dissolution on density and viscosity for crude Oil B
Toluene 0.03 C23 2.39
C8 1.72 C24 2.38 and synthetic Oil M were assessed using the procedure described in the
C2-Benzene 0.08 C25 2.31 previous section. The results in Fig. 2 show that CO2 has low (below
m&p-Xylene 0.09 C26 2.33 1.5%) impact in density for both oils, which is an input variable for
o-Xylene 0.05 C27 2.37 density calculation using the Drop Shape Analysis (DSA) technique. On
C9 2.11 C28 2.39
C10 2.61 C29 2.45
the other hand, viscosity was significantly affected by CO2 dissolution,
C11 2.56 C30þ 39.97 resulting in a decrease of over 80% of its initial value for crude Oil B.
This affects the dynamic behavior of the IFT measurements, as discussed
in the following section.
Table 3
SARA analysis and total acid and base numbers of Pre-salt crude oil. 3.2. Interfacial tension measurement
Pre-salt Oil
As stated before, pendant drop IFT measurements are characterized
Saturates (wt%) 64.06
Aromatics (wt%) 25.98 by a decrease in IFT with time before reaching an equilibrium state.
Resins (wt%) 8.46 Fig. 3 shows the dynamic behavior for the four systems of this work. The
Asphaltenes (wt%) 1.50 diamond marks indicate the equilibrium time for each system. It is
TAN (mg KOH/g) 0.37
possible to notice that the presence of CO2 results in a decrease in the
TBN (mg KOH/g) 4.00
stabilization time for systems. For Oil M, the equilibrium time decreased
by 1 h. On the other hand, Oil B had a greater reduction (about 6 h). This
may be related to the reduction in the viscosity of both oil phases due to
Table 4 the CO2 dissolution. Rahman et al. related the viscosity of the fluid to the
Mass percent elemental analysis for Oil B and its asphaltene fraction. relaxation time of the interfacial tension experiments. As the viscosity
N% C% H% S% H/C depends directly on the molecular interactions within a fluid, it has a
Oil 0.48 83.5 11.31 0.216 1.35 critical role in the diffusion of active components from the bulk to the
Asphaltene 1.78 81.1 9.03 1.30 1.11 interface (Rahman et al., 2019). Therefore, a reduction in the equilib­
rium time is expected if the bulk viscosity is decreased with the presence
of CO2. Oil B has an elevated viscosity in the absence of CO2, and the
unsaturation and higher concentration of heteroatoms. The presence of
dissolution of this gas reduces its viscosity over five times (Fig. 2). This
sulfur may indicate the existence of acid groups, whereas nitrogen
impacts the equilibrium time, obtaining a 70% reduction to the value
suggests the presence of basic functional groups. In agreement with TAN
calculated for the dead crude oil. In contrast, while CO2 reduced the
and TBN measurements, this indicates that this crude oil may have both
viscosity of Oil M three times, the viscosity of this synthetic oil is an
acid and basic functional groups in the polar fractions, which contribute
order of magnitude lower than that of the crude oil. As a result, the
to interfacial interactions.
dissolution of CO2 does not affect the equilibration time of Oil M
The functional groups in the asphaltene fraction were identified by
significantly. This indicates that the long time required for its stabili­
Fourier transform infrared spectroscopy (FTIR) using data in the liter­
zation may be due to another factor beyond our scope and needs further
ature (Silverstein et al., 2014; Wilt et al., 1998) to identify wave
investigations.
numbers of characteristic groups in the asphaltene fraction of crude oils
Equilibrium oil-brine IFT was plotted for dead and CO2-saturated oils
(Table 5). The identified hydroxyl group may be bonded to a molecule of
B and M in Fig. 4. Comparing both dead oils (with no dissolved CO2),
the sample or could represent residual water in the sample. Nonetheless,
crude Oil B has an IFT over 20 mN/m lower than synthetic Oil M. This
evidences the interfacial activity of asphaltenes and resins in this crude
oil, which results in an IFT of 10.5 mN/m with the brine. In addition,
Table 5
saturating the fluids with CO2 decreased the IFT between Oil M and
Functional groups identified in the asphaltene fraction by FTIR
spectroscopy.
brine over 20% from the value obtained without CO2 dissolution. This is
1
in agreement with trends found for oils with light or intermediate al­
Wave number (cm ) Functional group
kanes as major components in which CO2 partitioning contributes to
3403 OH increase the interaction between the oil and aqueous phase (Georgiadis
2920 CH2 þ CH3
2850 CH2 þ CH3
1697 C¼O Table 6
1604 C¼C aromatic Functional groups identified through Proton NMR.
1461 CH2 þ CH3
Domain in ppm Functional group
1376 CH3
1306 C–O 7.271 CH aromatic
1031 C–O 2.544 OH
872–719 CH aromatic 0.882–1.280 CH2 þ CH3

4
S. Drexler et al. Journal of Petroleum Science and Engineering 190 (2020) 107095

Fig. 4. Equilibrium interfacial tension of oils M and B in the presence and

absence of CO2 at 60 � C and 1000 psi. The full line indicates the brine pH for
each condition.

They reported that, although oils with high TAN tend to have higher IFT
in acid environments in which acid compounds show lower surface ac­
tivity, the IFT behavior with pH does not depend only on the absolute
TAN. The functional groups on acid and basic compounds in the crude
oil will be more important in determining their surface activities at
different pH values. In oils with basic compounds that show high
interfacial activity when ionized, CO2 injection reduces the interfacial
tension due to the reduced pH of the carbonated brine (Lashkarbolooki
et al., 2018).
In the previous section, Oil B was evidenced to have a distribution of
acid and basic compounds. Following the discussion of the last para­
graph, CO2 injection reduced the pH of the aqueous phase from 5.4 to
2.4. Therefore, the increase of IFT with pH found for Oil B indicates that,
even though its TAN/TBN ratio is lower than 1, basic compounds are not
Fig. 2. Viscosity (top) and density (bottom) of dead and CO2-saturated oils B
the main surface-active agents in this oil. The relatively low IFT value
and M at 60 � C and 1000 psi.
obtained for dead Oil B may be the results of amphiphilic compounds
that are more active at slightly acid or even neutral or basic environ­
ments, such as those containing acid groups. This set of results supports
the idea that measurement of acid and basic numbers is not sufficient to
predict the effect of pH on the IFT between crude oil and brine. For this
Pre-Salt crude with high TBN, acid compounds showed to be more
efficient in decreasing IFT than their basic counterparts.
To further investigate the effect of pH on IFT between oil B and the
formation brine, 0.1 M NaOH and HCl solutions were used to adjust the
aqueous phase pH in a range between 3 and 9.5. IFT between Pre-salt oil
and each of these aqueous solutions was measured at 60 � C and atmo­
spheric pressure, and the results were represented as a function of pH in
Fig. 5. In agreement with the previous discussion, the results show that
the acidic pH (3) corresponds to the minimum activity of the surface-
active compounds leading to a greater IFT. For the slightly acidic con­
ditions that correspond to the range of the degassed Pre-salt formation
brine, a decrease in IFT was observed. However, with further increase in
pH to neutral and basic conditions the IFT plateaus. Thus, for this oil
Fig. 3. Dynamic behavior of interfacial tension for oils M and B in the presence
and absence of CO2 at 60 � C and 1000 psi. The diamonds indicate the stabili­
zation time. The full lines represent oil with no CO2 and the dashed lines
represent CO2- saturated oil. Orange lines stand for Oil M and blue lines for Oil
B. (For interpretation of the references to colour in this figure legend, the reader
is referred to the Web version of this article.)

et al., 2011; Honarvar et al., 2017).

In contrast, CO2 dissolution had the opposite effect for Oil B
obtaining an increase on the IFT of 56% for CO2-saturated fluids
compared to the experiments with dead oil and brine. This indicates that
IFT is pH-sensitive for this crude oil with considerable TAN and TBN and
high content of asphaltenes and resins. As cited in the introduction of
this work, Lashkarbolooki and Ayatollahi (2018) discussed the effect of
pH on IFT for oils with different TAN, asphaltene and resin fractions. Fig. 5. Interfacial tension between Pre-salt oil and brine as a function of pH
(adjusted with 0.1 M HCl and NaOH) at 60 � C and atmospheric pressure.

5
S. Drexler et al. Journal of Petroleum Science and Engineering 190 (2020) 107095

with non-negligible TAN and TBN, there is no increase in surface activity Declaration of competing interest
of the polar compounds at basic pH.
Previous investigations of the effect of pH on IFT for different types The authors declare that they have no known competing financial
of crudes evidenced that, given the complex composition of both phases, interests or personal relationships that could have appeared to influence
there is no general trend based on a single property of the oil. Al-Rossies the work reported in this paper.
et al. (2010) obtained a maximum IFT for the neutral pH range for three
different crudes, but there was no quantification of the acidity of their CRediT authorship contribution statement
polar compounds. Lashkarbolooki and Ayatollahi (2018) found a
decrease of IFT with pH for a heavy oil with TAN greater than 1, and a Santiago Drexler: Conceptualization, Methodology, Investigation,
maximum IFT at neutral pH for the lighter oils with TAN lower than 1. In Writing - original draft, Supervision, Project administration. Elton L.
their article, the TBN was not reported and the salinity is over five times Correia: Investigation, Validation, Writing - review & editing. Ana
lower than the one used in our experiments. They concluded that the Carolina Jerdy: Software, Writing - review & editing. Leandro A.
sole measurement of the TAN is not sufficient to predict the effect of pH Cavadas: Investigation. Paulo Couto: Project administration, Funding
on IFT, and the different polar functional groups in the oil must be acquisition.
considered.
The scenario presented in this work consists of a high salinity Acknowledgements
aqueous phase and an oil with a TAN/TBN ratio lower than 0.1. Evi­
dence of acid functional groups was found in the characterization of the This research was carried out in association with the ongoing R&D
oil and the asphaltene fractions. The results in Fig. 5 indicate a very low project registered as ANP nº 20163-2, “An� alise Experimental da Recu­
activity of strong polar basic compounds, and a greater interaction of peraç~ao de Petro�leo para os Carbonatos do Pr�e-sal do Brasil atrav�es de
neutral and acid components. However, given the plateau of the curve at Injeç~
ao Alternada de CO2 e Agua"
� (UFRJ/Shell Brasil/ANP), sponsored
high pH values, the surface activity of this crude oil is not governed by by Shell Brasil under the ANP R&D levy as “Compromisso de Inves­
components with strong acid behavior. A combination of compounds timentos com Pesquisa e Desenvolvimento”. This study was financed in
with different ranges of acidity and basicity, whose activity was only part by the Coordenaç~ ao de Aperfeiçoamento de Pessoal de Nível Su­
hindered at strongly acidic pH, may be responsible for the low IFT values perior- Brasil (CAPES) - Finance Code 001.
found for this oil. These results support recent research (Drexler et al.,
2019) that evidenced the low activity of basic components of the same References
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contact angle and interfacial tension. NAFTA 61, 181–186.
4. Conclusions Anastasiadis, S.H., Chen, J.K., Koberstein, J.T., Siegel, A.F., Sohn, J.E., Emerson, J.A.,
1987. The determination of interfacial tension by video image processing of pendant
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consideration.

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