Article

pubs.acs.org/EF

Mass Transfer between Crude Oil and Water. Part 2: Eect of Sodium
Dodecyl Benzenesulfonate for Enhanced Oil Recovery
Anthony Hutin,*,, Jean-Francois Argillier, and Dominique Langevin
IFP Energies nouvelles, 1-4 Avenue de Bois Preau, 92852 Rueil-Malmaison Cedex, France
Laboratoire de Physique des Solides, CNRS UMR8502, Universite Paris-Sud, Batiment 510, 91405 Orsay Cedex, France

ABSTRACT: In enhanced oil recovery, synthetic surfactants are usually added to decrease the interfacial tension between oil
and water. When alkaline are used, endogenous natural surfactants bearing acidic groups that can be found in acidic or heavy
crude oils are activated in situ by ionization; they accumulate at the oilwater interface and reduce the interfacial tension. These
crude oils are called interfacially reactive. In alkaline surfactant ooding, the interaction between synthetic surfactants and
natural surfactants allows for the acquisition of ultralow interfacial tensions, lower than 103 mN/m. When reactive crude oils
and water at dierent pH values are contacted, mass transfers of natural species (asphaltenes, naphthenic acids, etc.) from oil to
water are observed. We report an experimental study of the inuence of sodium dodecyl benzenesulfonate (SDBS) on mass
transfer between oil and water phases, in which the nal pH of the water phase was measured as a function of the SDBS
concentration and initial pH. We also developed a model to account for the inuence of the SDBS concentration on exchanges
between the reactive crude oil and the aqueous phase. We found that the nal pH of the water phase increases when the SDBS
concentration increases, revealing a larger transfer of oil species into water. Finally, we show that a comparison between the mass
transfer and interfacial tensions between crude oil and water allows for better insight into the interactions between synthetic and
natural surfactants in alkaline surfactant ooding processes.

INTRODUCTION

The eect of synthetic surfactants on mass transfer for

reactive crude oils has never been previously studied to our
knowledge. In this work, we have measured the nal pH (pHf)
of the aqueous phase after contact with the reactive crude oil.
We used sodium dodecyl benzenesulfonate (SDBS) as a
synthetic surfactant at dierent concentrations below and above
its critical micellar concentration (cmc). In previous works, we
have reported a strong decrease of the IFT for the SDBS
concentration above the cmc (0.005 wt %) and ultralow
values (<0.001 mN/m) at basic pH.16,18 In the absence of a
surfactant, Poteau et al.20 have also reported a decrease of IFT
at basic pH but much more limited. In part 2, we propose a
model quantifying the inuence of SDBS on mass transfer and
discuss the inuence of the transfer on the IFT.

In part 1 (10.1021/ef501751b), it was shown that mass transfer

of natural amphiphilic species from oil to water is responsible
for variations of the water pH. These changes depend upon
crude oil characteristics, such as global acidity and basicity of oil
and pKa of natural species.16 The experiments revealed that
reactive crude oils behave as acido-basic oils, with the acid
character being stronger. The establishment of a model
demonstrated that the partition coecients of each species
play an important role in determining the nal water pH. The
transfer of acidic species is about 1000 times more important
than the transfer of basic species, explaining the global acid
behavior of reactive crude oils.5,7,8 The model allows for the
description of the mass transfer of natural surfactants in the
alkaline ooding process for enhanced oil recovery (EOR).911
One of the main limitations in oil recovery is the high
interfacial tension (IFT) between crude oil and reservoir brine.
In EOR processes, a combination of synthetic surfactants and
alkali (called alkaline surfactant ooding) can be used to
decrease IFT to ultralow values (<0.01 mN/m).8,12,14 The
added alkali reacts with the acidic groups of molecules within
the crude oil to generate in situ surfactants that accumulate at
the oil/water interface6,15,17 and interact with added synthetic
surfactants.12,13,16,18,19 A signicant decrease of IFT has been
observed16 and can be attributed to a synergistic eect between
natural and synthetic surfactants. The eciency of a surfactant
formulation can be studied by following the time evolution of
the IFT. The transfer of natural species from crude oil to water
can also be studied by observing the coloring of the water and
measuring the pH evolution after contacting water and crude
oil.
XXXX American Chemical Society

MATERIALS AND METHODS

Crude Oil. Samples of crude oil were prepared from a 9 American

Petroleum Institute (API) gravity Venezuelan heavy crude oil. The
saturate, aromatic, resin, and asphaltene (SARA) analysis gave 12%
saturates, 37% aromatics, 33% resins, and 17% asphaltenes (obtained
by precipitation using pentane). The acidity of the crude oil is given by
the total acid number (TAN). The TAN is determined by the ASTM
D664-01 method revisited by Buckley and Fan and corresponds to the
amount of potassium hydroxide that is needed to neutralize the acids
in oil. The crude oil used in this study has a TAN of 4.2 0.2 mg of
KOH/g. The basicity of the oil is given by the total base number
(TBN). The TBN is measured by the Dubey and Doe method21 and
corresponds to the amount of perchloric acid that is needed to
neutralize the bases in oil. The TBN of the oil is 2.7 0.4 mg of
Received: August 4, 2014
Revised: November 13, 2014

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KOH/g. The TAN and TBN can be also related to molar

concentrations in mol/L (see the Appendix). A diluted heavy oil has
been prepared by dilution of the Venezuelan heavy oil in toluene (3.4
weight dilution, i.e., 2.4 g of toluene/g of heavy oil) to obtain a crude
oil containing 5% asphaltenes with a TAN of 1.25 mg of KOH/g and a
TBN of 0.8 mg of KOH/g. Before dilution, the heavy oil was heated
for 30 min at 60 C to ensure homogenization. Dodecanoic acid from
Sigma (99%), naphthenic acids from Aldrich with an acid number
(AN) of 230 mg of KOH/g, and octadecylamine from Merck were
diluted in Rectapure xylene (99.9%) to mimic crude oil behavior.
Water Phase. Ultrapure water from a Millipore Milli-Q UV system
(resistivity of 18.2 M cm) was used. We added 5 g/L NaCl (Fisher
Scientic) to increase the ionic strength of the aqueous phase.
Ultrapure water was degassed prior to measurements, to remove CO2
molecules, which inuence the water pH. We noticed indeed a
buering eect for pH between 5 and 8 because of carbonic acid
(H2CO3) formed by the dissolution of CO2 into water. The pKa of the
couple H2CO3/HCO3 is about 6.4, explaining why the equilibrated
water pH converges to this value for pH between 5 and 8. For low pH
(pH < 4) and high pH (pH > 9), there is a slight but non-negligible
eect of the H2CO3/HCO3 equilibrium on the water pH. To avoid
this phenomenon, we decided to remove most of the CO2 molecules
from the water. For this purpose, the water was heated at 60 C to
facilitate the extraction of gases by a vacuum pump for at least 3 h. pH
of the aqueous phase was then adjusted to the desired value by adding
an aqueous solution of 0.1 mol/L sodium hydroxide (VWR Prolabo)
or 0.1 mol/L hydrochloric acid (Titripur Merck).
Oil in Water Emulsions. Oil and water at pHi were mixed with a
magnetic stirrer for at least 2 h. After this period, pH reaches an
equilibrium value pHf. The pH measurements were made with an
InlabScience electrode connected to a pH meter (Seven Easy, Mettler
Toledo). When large amounts of oil were used, we separated the oil
and water phases before measuring pHf. For this purpose, we waited
for 10 min to let the oil droplets cream before measuring pH in the
water phase. In most cases, only 5% or less oil was dispersed in water,
and the pH measurements were performed in the emulsion thanks to
the InlabScience electrode, which was insensitive to the presence of oil.
The electrode was cleaned between each measurement and
recalibrated after 10 measurements. All pH measurements were
performed at room temperature, 24 1 C. The error bars correspond
to the spread of the measurements (at least three for each data point).
IFTs. The IFT was measured with an automated drop tensiometer
(Tracker, Teclis) and a spinning drop tensiometer (SITE 100, Kruss).
We used the drop tensiometer for IFT larger than 2 mN/m and the
spinning drop tensiometer for IFT smaller than 2 mN/m. The use of
the spinning drop technique does not allow for the measurement of
the IFT at times less than 1 min.
For all of the IFT measurements, the initial time (t = 0 s)
corresponds to the time at which the oil drop is rst contacted with
the aqueous phase. All IFT measurements were performed at room
temperature, 23 1 C.
Let us recall that the IFT time evolution reects the kinetics of
adsorption at the interface.
The error bars for pH and IFT correspond to the spread of the
measurements (at least three for each data point).

Figure 1. Eect of SDBS on nal pH (pHf) for crude oil in contact

with water at dierent initial pH (pHi). Input parameters of the
models are pKaA = 5, TAN = 1.25, Xa = 104, pKaB = 9, TBN = 0.8, and
Xw = 0.95.

presence of SDBS (about two units for pHi values of 4 and 5

with respect to pHf without SDBS). This results in a higher
value for the plateau region. For pHi above 10, the increase
because of the surfactant is less signicant. Clearly, the presence
of SDBS enhances the transfer of basic species from the oil
phase to the water phase.
The model developed in part 1 (10.1021/ef501751b)
without a synthetic surfactant gave the values of partition
coecients for the fatty acids and fatty bases. In the case of our
reactive crude oil, the partition coecient for the acids22 is 3
orders of magnitude smaller than the partition coecient for
the bases (Xb). When tting the results in the presence of
SDBS using the same model, it was found that Xb decreases,
whereas Xa is unchanged; as a result, the presence of SDBS
signicantly increases the transfer of bases from oil to water.
With 0.1 wt % SDBS, the nal concentration of fatty bases
dissolved in water is increased by a factor of 1000 with respect
to the SDBS-free systems. For the sake of comparison, we
measured the evolution of pHf for naphthenic acids dissolved in
xylene at the same concentration (acidity AN 1.25) as the
diluted crude oil.
As seen in Figure 2, there is only a slight eect of SDBS on
pHf of this system compared to the crude oil system. SDBS
seems, therefore, to interact mainly with the fatty bases. We
investigated the eect of the SDBS concentration on pHf
(Figure 3). For a given pHi, pHf increases with the
concentration of SDBS. This increase is especially important
above the cmc for low pH. These results could imply a role of
micelles in the transfer of fatty basic species.
The evolution of the water phase color after mass transfer is
in line with pH measurements (Figures 1 and 4). In the
absence of SDBS (Figure 4a), the transfer is important only at
pH 10. The water remains clear for all other pH values. No
transfer of bases at low pH is therefore seen, conrming the
pHf results. In the presence of 0.1 wt % SDBS (Figure 4b),
mass transfer is important for both basic and acidic pH and
more limited for intermediate pH values. To quantify the acidobasic behavior of the reactive crude oil, we extended the model
developed in part 1 (10.1021/ef501751b) for the exchanges
between oil and water.

RESULTS AND DISCUSSION

Inuence of SDBS Concentration on Mass Transfer for
Heavy Crude Oil. In part 1 (10.1021/ef501751b), we
described the evolution of nal pH (pHf) versus initial pH
(pHi) of the water phase in the presence of the diluted heavy
crude oil (Figure 1). We showed that the oil behaves as an
acido-basic oil with a dominant acid behavior. At pHi < 5, we
observed a low increase of pHf as a result of a limited transfer
of fatty bases.
We present in Figure 1 the evolution of the nal pH (pHf)
versus initial pH (pHi) in the presence of 0.1 wt % SDBS in the
water phase. For 3 < pHi < 10, pHf is much higher in the
B

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interactions between the dierent aromatic rings. They lead to

a decrease of the partition coecient Xb when increasing the
SDBS concentration. We can write a new coecient Xb as
follows:
Xb =

[Bo]
[Bw ]

(1)

This coecient is the ratio between the equilibrium

concentration of bases in oil [Bo] and in water [Bw]. [Bw]
can be written as the sum of the concentration of bases
transferred in water in the absence of SDBS and the
concentration of bases that have been transferred by the
presence of surfactant, f([SDBS]).
[Bw ] = [Bw ] + f ([SDBS])

(2)

The concentration of bases in water increases as the

concentration of SDBS increases. If we assume that this is
due to a complexation between one base and n surfactant
molecules, we can write f(SDBS) as a power law of [SDBS]i,
the initial concentration of SDBS

Figure 2. Comparison between crude oil and naphthenic acids

dissolved in xylene without and with 0.1 wt % SDBS.

f ([SDBS]) = A[SDBS]ni

(3)

where A is the equilibrium constant of the complexation

process. We will assume that the equilibrium relative to noncomplexed oil molecules is not aected by the presence of
SDBS and that Xb does not change. Thus, from eqs 2 and 3,
[Bw ] is expressed as
[Bw ] = [Bw ] + A[SDBS]ni = [Bw ](1 + a[SDBS]ni )

(4)

with a = A/[Bw] This leads (Figure 5) to

Xb =

Xb
1 + a[SDBS]ni

(5)

Figure 3. Inuence of the SDBS concentration on pHf for crude oil at

dierent pHi.

Figure 5. Simplied system of the base exchanges between oil and

water.

Figure 4. Color change of water that has been contacted with crude oil
for dierent pHi without and with 0.1 wt % SDBS.

Then, we can build a model based on the partitioning of acidobasic species between the aqueous solution and oil in the
presence of SDBS and their dissociation in the aqueous
solution (Figure 6). In this model, we assume that Xa is not
modied by the presence of the surfactant, as seen
experimentally.
Details of the calculations for this new model can be found in
the Appendix.

Model for Mass Transfers between Oil and Water in

the Presence of SDBS. We started from the model
established in part 1 (10.1021/ef501751b). The interaction
between the fatty bases and SDBS have already been shown to
be associated with the transfer of these bases into water (Figure
3 and 4). These interactions are either electrostatic or
C

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Figure 6. Simplied system of the acidbase exchanges between oil

and water in the presence of SDBS: transfer of a fatty acid and a fatty
base.

Validation of the Model in Relation to the Experimental Results. The evolution of pHf for dierent SDBS
concentrations is presented in Figure 7.

Figure 8. Evolution of Xb as a function of the SDBS concentration.

103 wt %), which shows that the inuence of SDBS micelles

in the mass transfer seems, therefore, not as dominant as could
have been expected.
Link between Interfacial and Mass Transfer Phenomena. In previous papers,16,18 we reported the evolution of IFT
for the same system at alkaline pH. In Figure 9, we compare the
behavior at the interface (IFT) and in the bulk (pHf) for initial
pH of the water phase between 3 and 11 without SDBS. Three
zones can be identied in Figure 9.

Figure 7. Fit of pHf as a function of pHi for dierent SDBS

concentrations by varying the value of Xb. Input parameters of the
models are pKaA = 5, TAN = 1.25, Xa = 104, pKaB = 9, TBN = 0.8, Xb =
107, and Xw = 0.95.

We used the parameters of the system determined for the

surfactant-free system in part 1 (10.1021/ef501751b): pKaA = 5,
TAN = 1.25, Xa = 104, pKaB = 9, TBN = 0.8, Xb = 107, and Xw =
0.95 (Xw is the volume fraction of water). Xb is therefore the
only adjustable parameter. We found that, when the SDBS
concentration Si is below 104 wt %, Xb Xb and that Xb
decreases signicantly at larger Si. The curve tting with eq 5 of
the evolution of Xb as a function of the SDBS concentration on
Figure 8 allows for the determination of the values of a and n.
For Si > 104 wt %, Xb 103/Si. Because Xb = 107, one
obtains a 104 and n = 1. The complete expression for Xb is
Xb
Xb =
1 + 104[SDBS]i

Figure 9. Evolution of the equilibrated IFT and nal pH as a function

of initial pH in the case of crude oil in contact with an aqueous phase
without added surfactant.

In zone 1, for pHi 5, the IFT increases only slightly when

pHi increases. It is slightly lower than the values measured at
neutral pHi because of the ionization of the basic functions at
the interface with the water phase that increases their interfacial
activity. This behavior is also visible with pHf, which is slightly
higher than pHi in this zone. In zone 2, for 5 < pHi < 9, we are
in the buer zone (or plateau zone), where pHf varies little
and the IFT is at a maximum. The concentration of ionizable
species is low; thus, there are less interfacially active molecules
able to occupy the interface. In zone 3, for pHi > 8, the IFT
decreases by 1 order of magnitude; pHf is also much lower than
pHi. The fatty acids react with alkali at the interface, leading to
ionized species that are much more interfacially active than the

This expression ts the data well, except the point for Si = 104
wt %, which is slightly above the line (Figure 8). One sees that,
for concentrations lower than 104 wt %, there is no detectable
eect of SDBS; pHf is equal to that without SDBS. The fact
that n = 1 suggests that the interactions between SDBS and oil
bases are electrostatic interactions between ion pairs. The curve
does not show any inection point around the cmc of SDSB (5
D

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with SDBS, a sulfonated surfactant, showed an increase of the

transfer of fatty bases between oil and water. This unexpected
phenomenon may be explained by an interaction between the
fatty bases and the synthetic surfactant. The higher the SDBS
concentration, the higher the anity of the bases toward the
water phase. This is conrmed by a strong coloration of the
water. We modeled the partitioning of fatty bases in the
presence of SDBS assuming that the partition coecient for
bases varies as a power law of the initial SDBS concentration.
The exponent n is the number of molecules of SDBS that react
with one base. The data analysis lead to n = 1, indicating that
the transport involves ion pairs rather than a surfactant micelle.
The transfer aects the time evolution of the IFT. At neutral
pH, the transfer is limited and the IFT rapidly reaches an
equilibrium value slightly lower than with pure toluene,
suggesting that crude oil species are co-adsorbed with SDBS
molecules at the oilwater interface.
The transfer is very important at acidic and basic pH. As a
result, the IFT decreases to very low values that become nonmeasurable after tens of minutes. When the transfer is
completed, the IFT might increase and reach larger equilibrium
values. However, because transfer is slow, the transient ultralow
IFT could be of importance for EOR.

other natural surfactants. The increasing concentration of these

species at the interface therefore causes a decrease in the IFT.
In the presence of 0.1 wt % SDBS, the IFT is lowered
because of the presence of SDBS and natural surfactants at the
interface. At acid and basic pH, the IFT varies slowly with time,
and at long times, it falls below measurable values16,18 (oil
drops break, and water becomes opaque). We show three
curves for the time evolution of the IFT at pHi of 3, 7, and 10
(Figure 10). In the neutral pH zone 2, the IFT reaches an

APPENDIX
In the case where the alkaline agent is NaOH and the acid
agent is HCl in the aqueous phase with SDBS, relationships to
be considered for both acidbase pairs are the same as for the
model used in part 1 (10.1021/ef501751b), where we replaced
Bw by Bw and Xb by Xb . The model is based on reactions of
transfer between oil and water (Figure 6). Acids and bases are
distributed between the oil and water phase according to

Figure 10. Evolution of IFT as a function of time at pHi of 3, 7, and

11 for 0.1 wt % SDBS.

equilibrium value, 2 orders of magnitude lower than the value

measured without SDBS (Figure 9). This dierence in IFT can
be explained mostly by the presence of SDBS at the interface
but also by the presence of crude oil species. The equilibrium
IFT for toluene in contact with an aqueous solution at pH 7 is
about 0.8 mN/m with 0.1 wt % SDBS,16 while it is about 0.1
mN/m in the case of crude oil. Therefore, for this zone of pH,
the decrease in equilibrium IFT is due to both SDBS and crude
oil molecules. The pHf curves are also dierent; the plateau
value is higher in the presence of the surfactant (Figure 1). The
enhanced transfer leads to accumulation of more crude oil
species at the interface.
At acidic pH (zone 1) and without SDBS, there is little fatty
base transfer (Figure 9). In the presence of SDBS, the fatty base
transfer is favored, which results in a signicant increase of pHf
(Figure 1). The concentration of bases complexed with SDBS
in water increases as well as the amount of active species at the
interface (Figure 3). The transfer results in a slow IFT decrease.
At basic pH (zone 3), the IFT reaches ultralow values rather
fast, possibly because the ionized acidic molecules transferred
are more surface-active and accumulate at the interface.

AHo AH w
Bo Bw
where AHo, AHw, Bo, and Bw are the undissociated acid and
base in the oil and water phases, respectively. These equilibria
can be described with their oil/water partition coecients

Xa =

[AHo]
[AH w ]

(6)

Xb =

[Bo]
[Bw ]

(7)

where [AHo], [Bo], [Aw], and [Bw ] are the undissociated acid
and base concentrations in the oil and water phases,
respectively.
Acid and base will dissociate in the water phase according to
AH w + H 2O H3O+ + A w

Bw + H 2O HO + B+w

CONCLUSION
In chemical EOR, the eect of an added synthetic surfactant is
sought to reduce the IFT between brine and crude oil.
However, there are some constraints in surfactant ooding:
specic formulations of surfactants must be adapted to the
reservoir and crude oil to maximize the production of oil and
minimize side eects, such as adsorption of surfactants on
rocks, etc. Predicting and controlling the pH of the aqueous
phase in the reservoir is essential to allow for a continuous
activation of natural surfactants. The experiments performed

depending upon their equilibrium constants KaA (eq 8) and KaB

(eq 9)

K aA =

[A w ][H3O+]
[AH w ]

(8)

KbB =

[B+w ][HO]
[Bw ]

(9)

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Exponents i and f refer to initial and nal state of the

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basicity of oil (TBN) is only given by Bo; therefore, the
dierent equations are as follows:
Mass balance for the two acid/base pairs

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(1 X w )[AHo]i = (1 X w )[AHo]f
+ X w ([AH w ]f + [A w ]f )

(10)

(1 X w )[Bo]i = (1 X w )[Bo]f + X w ([Bw ]f + [B+w ]f )

(11)

with [AHo]f = Xa[AHw]f and [Bo]f = Xb[Bw]f.

Acid/base chemical reactions in water
[AH w ]f =

[Bw ]f =

(1 X w )[AHo]i
(1 X w )Xa + X w (1 + 10 pHf pKaA )

(12)

(1 X w )[Bo]i
(1 X w )Xb + X w (1 + 10 pKaB pHf )

(13)

with Xb = Xb/(1 +
Electroneultrality of the aqueous phase at the nal state
a[SDBS]ni ).

[OHw ]i + [Bw ]f 10 pKaB pHf + [H3O+]f

= [H3O+]i + [AH w ]f 10 pHf pKaA + [OHw ]f

(14)

The solution of the eqs 1014 gives us pHi according to pHf.

In this model, Xa and Xb will be adjusted to nd the good mimic
of the evolution of pHf.
The initial acid concentration [AHo]i (mol/L) and initial
base concentration [Bo]i (mol/L) in the oil are directly linked
to the TAN and TBN of oil, respectively, through
[AHo]i = 103

[Bo]i = 103

TANdoil
MKOH

TBNdoil
MKOH

(15)

(16)

where doil is the density of oil (g/L) and MKOH is the molecular
weight of KOH (g/mol).

AUTHOR INFORMATION

Corresponding Author

*E-mail: anthony.hutin@teclis-instruments.com.
Present Address

Anthony Hutin: Teclis, Parc de Chancolan, 69770 Longessaigne, France.

Notes

The authors declare no competing nancial interest.

REFERENCES

(1) Hurtevent, C.; Rousseau, G.; Bourrel, M.; Brocart, B. Production

issues of acidic petroleum crude oils. In Emulsions and Emulsion
Stability, 2nd ed.; Sjoblom, J., Ed.; CRC Press (Taylor & Francis
Group): Boca Raton, FL, 2006; pp 493516.
(2) Havre, T. E.; Sjoblom, J.; Vindstad, J. E. Oil/water-partitioning
and interfacial behavior of naphthenic acids. J. Dispersion Sci. Technol.
2003, 24 (6), 789801.
F

dx.doi.org/10.1021/ef5017522 | Energy Fuels XXXX, XXX, XXXXXX