J170966 DOI: 10.
2118/170966-PA Date: 6-August-15 Stage: Page: 767
A Mechanistic Model for Wettability
Alteration by Chemically Tuned
Waterflooding in Carbonate Reservoirs
C. Qiao, L. Li, R.T. Johns, and J. Xu, Pennsylvania State University
Summary
Injection of chemically tuned brines into carbonate reservoirs
has been reported to enhance oil recovery by 5–30% original oil
in place (OOIP) in coreflooding experiments and field tests. One
proposed mechanism for this improved oil recovery (IOR) is
wettability alteration of rock from oil-wet or mixed-wet to more-
water-wet conditions. Modeling of wettability-alteration experi-
ments, however, is challenging because of the complex interac-
tions among ions in the brine and crude oil on the solid surface.
In this research, we developed a multiphase and multicomponent
reactive transport model that explicitly takes into account wett-
ability alteration from these geochemical interactions in carbon-
ate reservoirs.
Published experimental data suggest that desorption of acidic-
oil components from rock surfaces make carbonate rocks more
water-wet. One widely accepted mechanism is that sulfate (SO2 4 )
replaces the adsorbed carboxylic group from the rock surface,
whereas cations (Ca2þ, Mg2þ) decrease the oil-surface potential.
In the proposed mechanistic model, we used a reaction network
that captures the competitive surface reactions among carboxylic
groups, cations, and sulfate. These reactions control the wetting
fractions and contact angles, which subsequently determine the cap-
illary pressure, relative permeabilities, and residual oil saturations.
The developed model was first tuned with experimental data
from the Stevns Klint chalk and then used to predict oil recovery
for additional untuned experiments under a variety of conditions
where IOR increased by as much as 30% OOIP, depending on sa-
linity and oil acidity. The numerical results showed that an
increase in sulfate concentration can lead to an IOR of more than
40% OOIP, whereas cations such as Ca2þ have a relatively minor
effect on recovery (approximately 5% OOIP). Physical parame-
ters, including the total surface area of the rock and the diffusion
coefficients, control the rate of recovery, but not the final oil re-
covery. The simulation results further demonstrate that the opti-
mum brine formulations for chalk are those with relatively
abundant SO2 4 (0.096 mol/kg water), moderate concentrations of
cations, and low salinity (total ionic strength of less than 0.2 mol/
kg water). These findings are consistent with the experimental
data reported in the literature. The new model provides a powerful
tool to predict the IOR potential of chemically tuned waterflood-
ing in carbonate reservoirs under different scenarios. To the best
of our knowledge, this is the first model that explicitly and mecha-
nistically couples multiphase flow and multicomponent surface
complexation with wettability alteration and oil recovery for car-
bonate rocks specifically.
Introduction
Changing the ionic composition of injection water during water-
flooding has been reported to lead to improved oil recovery (IOR)
in recent years (Yildiz and Morrow 1996; Lager et al. 2006; You-
sef et al. 2010). Increases in oil recovery between 5 and 38% orig-
inal oil in place (OOIP) have been observed in sandstone-
Copyright V
C 2015 Society of Petroleum Engineers
This paper (SPE 170966) was accepted for presentation at the SPE Annual Technical
Conference and Exhibition, Amsterdam, 27–29 October 2014, and revised for publication.
Original manuscript received for review 4 August 2014. Revised manuscript received for
review 25 November 2014. Paper peer approved 11 February 2015.
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Total Pages: 17
coreflooding experiments (Webb et al. 2004; McGuire et al. 2005;
Lager et al. 2006). Incremental-oil recovery by up to 40% OOIP
has been demonstrated in carbonate cores (Zhang et al. 2007;
Yousef et al. 2010). Incremental-oil recoveries from field tests,
however, are generally smaller than those from corefloods.
Increases of 15% OOIP have been reported in sandstone reser-
voirs (Webb et al. 2004). Oil recovery of 50% OOIP by use of
seawater injection in carbonate reservoirs, such as in the Ekofisk
field in the North Sea reservoir, have been reported (Hallenbeck
et al. 1991; Austad et al. 2008; Yousef et al. 2012c).
Wettability alteration of the rock from oil-wet to water-wet
has been suggested as the primary mechanism for increased oil re-
covery during low-salinity waterflooding in carbonates (Morrow
1990; Buckley and Liu 1998; Austad et al. 2012). Oil recovery is
generally greater in water-wet reservoirs because of the higher oil
mobility owing to its lower affinity to rock surfaces. Water break-
through is typically slower in water-wet rocks compared with oil-
wet reservoirs. In addition, in fractured rocks, a water-wet matrix
allows for water imbibition and countercurrent flow of oil. Most
carbonate reservoirs are not completely oil-wet; instead, the rocks
usually have mixed wettability depending on the nature of the
mineral surface, oil properties, and fluid/rock interactions (Ander-
son 1987; Morrow 1990; Peters 2012). The relative proportion of
oil-wet and water-wet surfaces determines the overall capillary
pressure, relative permeability, and residual oil saturation (ROS),
which ultimately control oil recovery (Anderson 1987; Ustohal
et al. 1998; Delshad et al. 2003; O’Carroll et al. 2005). Low-salin-
ity seawater has been found to increase the proportion of the
water-wet surface during spontaneous imbibition experiments in
the Stevns chalk (Strand et al. 2006a, 2006b; Puntervold and Aus-
tad 2008; Strand et al. 2008; Puntervold et al. 2009). Favorable
contact-angle hysteresis was observed during injection of low-sa-
linity brine containing sulfate (Alotaibi et al. 2010; Yousef et al.
2010; Gupta and Mohanty 2011; Yousef et al. 2011; Yousef et al.
2012a, 2012b, 2012c). Incremental-oil recovery differed signifi-
cantly from 0 to 40% OOIP under various experimental condi-
tions (Fathi et al. 2010).
Possible mechanisms for the observed wettability alteration
include fine-particle migration (Tang and Morrow 1999), ion
exchange (Lager et al. 2006), mineral dissolution (Hiorth et al.
2010), and sorption and desorption of carboxylic groups (Zhang
et al. 2007). For Stevns chalk, spontaneous imbibition and chro-
matographic wettability tests verified that SO2 2þ 2þ
4 , Ca , and Mg
ions actively participate in surface reactions that alter wettability
(Strand et al. 2003, 2006a; Zhang et al. 2007). Austad et al.
(2008) suggest that sulfate adsorption on positively charged chalk
surfaces and desorption of the carboxylic group from the surface
reduces the affinity of the surface to oil (RezaeiDoust et al. 2009).
According to this mechanism, experimental studies reported the
optimal ionic composition for IOR in carbonates (Fathi et al.
2011). Other factors, including temperature, oil composition, and
water-phase composition, are also observed to play an important
role in determining oil recovery (Hjelmeland and Larrondo 1986;
Strand et al. 2006b; Zhang et al. 2007; Puntervold and Austad
2008; Strand et al. 2008; Puntervold et al. 2009; Fathi et al. 2011).
Significant advances have been made in recent years to predict
wettability alteration and oil recovery (Høgnesen et al. 2006; Jer-
auld et al. 2008; Yu et al. 2009; Evje and Hiorth 2011; Andersen
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 J170966 DOI: 10.2118/170966-PA Date: 6-August-15
Multiphase Flow
+ · = 0
+ · = 0
Wettability, relative
Solute transport permeability, and capillary
,→ pressure alteration
, ,
Reactive Transport
+ + · + =0
Fig. 1—Schematic of the governing equations for multiphase
flow (oil and water) and multicomponent reactive transport. The
two processes interact by means of solute transport and wett-
ability alteration.
et al. 2012). Jerauld et al. (2008) proposed a fully compositional
model that included the transport of salts in the aqueous phase as
an additional single-lumped component. They determined the
relationship between the relative permeability and ROS, but from
linear interpolation of the wetting state by use of the salinity with-
out tracking individual species. Yu et al. (2009) and Andersen
et al. (2012) assumed a single wetting agent that modified the
rock wettability through adsorption. The simplification of wett-
ability alteration by including one or two chemical species is not
sufficient to capture the complex interactions among multiple
components in water, oil, and solid surfaces. Brady et al. (2012)
used a surface complexation model with reaction networks rele-
vant to carbonate rocks and sandstones (Brady and Krumhansl
2012; Brady et al. 2012). However, their reaction approach has
not been coupled with multiphase flow to understand dynamic
effects on wettability alteration. Other models with multiple
chemical reactions either assumed that mineral dissolution modi-
fies wettability (Evje and Hiorth 2011; Andersen et al. 2012), or
were designed only for sandstones where cation exchange was
believed to be the mechanism of wettability alteration (Dang et al.
2013). In general, there is currently a lack of a detailed representa-
tion of the surface-geochemical reactions and the corresponding
wettability alterations in multiphase-flow models. No existing
models can be used to quantitatively link water and surface reac-
tions, wettability, capillary pressure, relative permeability, and
(eventually) oil recovery, or to predict oil recovery under different
injection-water compositions and conditions for carbonate rocks.
In the geochemistry community, multicomponent reactive-
transport models have been developed since the 1980s (Lichtner
1985; Steefel et al. 2005) and have been extensively used to
understand and predict subsurface reactive-transport processes in
many applications (Davis et al. 2004; Li et al. 2010, 2011). Appli-
cations of these complex surface reactions in IOR processes,
although promising from a geochemistry point of view, have not
yet been made to the best of our knowledge.
In this research, we develop a model that couples multiphase
flow with detailed, mechanistic understanding of surface reactions
to systematically investigate the complex interactions among mul-
ticomponent surface reactions, wettability, and oil recovery. We
propose a reaction network for carbonates based on a double sur-
face complexation model (Brady et al. 2012a, 2012b). The new
model was tuned with data from a low-salinity seawater-imbibi-
tion experiment, where both porous-media properties (porosity,
permeability, capillary pressure, and relative permeability) and
geochemical reactions (aqueous- and surface-complexation reac-
tions) play important roles. Simulations were carried out with this
new model under an array of conditions to understand the control-
ling parameters during the chemically tuned waterfloods. By
chemically tuned waterflooding, we refer to the injection of water
that is adjusted in the ionic composition.
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This paper is organized as follows. We first introduce the gen-
eral multiphase-flow and reactive-transport equations, and then
present the reaction network and the relationships between
chemical concentrations, capillary pressure, and relative perme-
ability. We then focus on the model validation with the base-
case experimental data and sensitivity analysis of the important
parameters and processes in determining wettability and the oil-
recovery factor.
Methodology
In this section, we introduce the general multiphase-flow and re-
active-transport equations, the reaction network, and the wettabil-
ity-alteration model. The finite-difference-solution approach is
presented at the end of this section.
Low-salinity flooding involves both multiphase flow and geo-
chemical reactions. The injected brine has ionic compositions dif-
ferent from the formation water. This difference perturbs the
original thermodynamic equilibrium and leads to surface-geo-
chemical reactions, which alters the concentrations of surface spe-
cies and potentially the wettability. The wettability controls
capillary pressure and relative permeability, which in turn affect
multiphase flow and recovery.
We have developed an implicit-pressure/explicit-concentration-
formulated code (PennSim Toolkit 2013) to solve the coupled mul-
tiphase-transport and chemical-reaction equations in this research
(Fig. 1). The mass-conservation equations for oil and water phases
are solved for the pressure and saturation sequentially. The water-
saturation and water-phase flux from the solutions of the multi-
phase-flow equations are used in the reactive-transport equations.
Reactive-transport equations are then solved sequentially for the
spatial/temporal evolution of the concentrations of aqueous and
surface species. The multiphase flow and reactive transport are
linked through the interactions among surface reactions, wettabil-
ity, relatively permeability, and capillary pressure.
Multiphase-Flow Equations. The mass-conservation equations
of the immiscible oil- and water-fluid phases are as follows:
@
ð/Sa qa Þ þ r  ðqa~
u a Þ ¼ 0; a ¼ o; w; . . . . . . . . . . ð1Þ
@t
where / is porosity (dimensionless) and S, q, and ~u are the satura-
tion (dimensionless), fluid density (kg/m3), and volumetric flow
rates (m3/s), respectively, for the oil and water phases. The sub-
script w is for the water phase, and the subscript o is for the oil
phase. Darcy’s law governs the flow rate of different phases:
kkra
ua ¼
~ rðPa  qa gZÞ; . . . . . . . . . . . . . . . . . . . . . ð2Þ
la
where k is absolute permeability (m2); Z is the depth (m); and l,
g, and P are the viscosity (cp), gravitational constant (m/s2), and
the pressure of the fluid phase (Pa), respectively. The pressure dif-
ference between oil and water phases is the capillary pressure:
Pcow ¼ Po  Pw : . . . . . . . . . . . . . . . . . . . . . . . . . . . ð3Þ
The capillary pressure Pcow and the relative permeabilities krw
and kro depend on water saturation, pore structure, and rock wett-
ability. The saturation relation completes the set of equations:
So þ Sw ¼ 1: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð4Þ
The unknowns for the multiphase-flow system are the pressure
and saturation of the different fluid phases.
Reactive-Transport Equations. Reactive-transport equations
describe the coupled process of solute transport and reactions.
Compared with standard reactive-transport models for water-satu-
rated porous media (Steefel and Lasaga 1994), PennSim has vary-
ing water saturation and three interfaces (oil/water, oil/solid, and
August 2015 SPE Journal
 J170966 DOI: 10.2118/170966-PA Date: 6-August-15
(a) (c)
O
w
(b) Oil
Water
Solid
Carboxylic group or other surface active components
Surfate
Divalent Cation like Ca2+ and Mg2+
Fig. 2—Illustration of the multiphase reaction network in a pore of mixed wettability. (a) A mixed-wet pore by use of a triangle
model; o 5 oil; w 5 water. (b) The ion-species distribution on a water-wet surface. (c) The chemical-ion species at the interfaces
between crude oil, water, and solid.
water/solid interfaces). The species are partitioned into primary
and secondary species. The partition is determined in such a way
that the concentrations of the secondary species can be explicitly
expressed by those of the primary species through the mass-action
law (Lichtner et al. 1996). The mass-conservation equation for the
primary species p is
! !
@ XNsec X
Nsec
Mp þ qp Mq þ r  Fp þ qp Fq ¼ 0;
@t q¼1 q¼1
p ¼ 1; …; Np ;                       ð5Þ
where subscripts p and q represent the primary species p and sec-
ondary species q and qp represents the ðq; pÞ entry of the stoichi-
ometry coefficient matrix. The number of primary species Np equals
Ntot  Nsec , where Ntot is the total number of species and Nsec is the
number of secondary species. The definition of molar density M,
flux F, and the derivation of Eq. 5 are in Appendix A. The set of
unknowns for the reactive-transport equations includes the aqueous-
species concentration Ciw , the solid-surface-species concentration
Cis , and the oil-surface-species concentration Cio , where the sub-
script i represents a species. Details of the reactive-transport-model-
ing formulation can be found in Yeh and Tripathi (1991), Steefel
and Lasaga (1994), and Walter et al. (1994). The system of general
equations is coupled with the mass-action law discussed later.
Multiphase Reaction Network. As illustrated in Fig. 2, the
reaction network includes the interactions among Ca2þ, Mg2þ,
SO2
4 , and absorbed-oil species. The reaction network includes
aqueous reactions and surface-complexation reactions at the oil/
water, solid/oil, and solid/water interfaces (Brady and Krumhansl
2012; Brady et al. 2012). The reactions on the solid/water inter-
face include the adsorption of sulfate and the carboxylic group.
The reactions on the oil/water interface include the dissociation
of carboxylic acids and reactions between the carboxylic group
and multivalent cations. All aqueous reactions are fast reactions
and are assumed to be at equilibrium and are controlled by reac-
tion thermodynamics (Lichtner et al. 1996; Langmuir 1997).
The concentrations of the polar components in crude oil
largely affect the initial wettability and the wettability alteration
by seawater (Strand et al. 2003; Fathi et al. 2011). For refined oil
where polar components are removed, no low-salinity-water or
seawater improved-oil-recovery (IOR) effect has been observed
(Hirasaki and Zhang 2004; Robertson 2007). The acid number
(AN) quantifies the abundance of polar components in crude oil
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Water
Solid
and has been shown to be crucial in low-salinity flooding (Zhang
and Austad 2005a). Here we use AN to quantify the amount of
carboxylic acids in the oleic phase.
The carboxylic acids represent the polar oil components. As
shown in Reactions 1 through 3 in Table 1, the carboxylic acids
dissociate at the oil/water interface and react with ions in the water
phase. The species at the oil/water interface occupies an oil-sur-
face site, following Brady et al. (2012). A diffusive-layer model is
used to quantify the activity of the surface species and the electro-
static forces (Dzombak and Morel 1990). The expression for the
equilibrium constant of Reaction 2 is shown as an example:
 
Fwo
exp ½COOCaþ aHþ
RT
K2;eq ¼ ;
½COOHaCa2þ
where ½COOH and ½COOCaþ  are the surface concentrations
(mol/m2) of carboxylic acid and the surface complex of carbox-
ylic calcium, respectively; aHþ is the activity of Hþ in aqueous
phase (dimensionless); F is Faraday’s constant (9.648 104 C/
mol); wo is the oil/water-interface charge potential (mV); R is the
gas constant (8.314 J/Kmol); and T is the absolute temperature
(Kelvin). The surface potential is calculated by use of the Gouy-
Chapman theory that relates the surface-charge density to surface
potential in the following form (Gouy 1910; Chapman 1913):
 
p Fw
ro ¼  8e0 em IRTsinh  o ; . . . . . . . . . . . . . . . ð6Þ
2RT
where ro is the charge 2
Xdensity at the oil/water interface (C/m )
calculated from ro ¼ z C , where zi is the charge carried by
i i i;o
ion species i; e0 is the dielectric constant of water (55.3,
dimensionless); em is the permittivity of free space (8.8541013
C V 1 dm1 ); and I is the ionic strength of water (mol/kg water).
The solid-surface potential can be calculated in a similar manner.
The calculation follows the same method of Hiorth et al. (2010).
This surface-complexation model integrates the effects of surface
charge, solution ionic strength, temperature, and surface potential.
The reactions between brine and the calcite surface are repre-
sented by Reactions 4 and 5 in Table 1. The species > CaOH rep-
resents the reactive site on the calcite surface because > CaOHþ 2
was found to sorb strongly on the oil surface (Brady et al. 2012).
Reaction 4 describes the hydration of the calcite-surface site. The
equilibrium constant is known to highly depend on temperature
(Austad et al. 2008; Fathi et al. 2010). Here we use the data
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 J170966 DOI: 10.2118/170966-PA Date: 6-August-15
Table 1—The reaction network and equilibrium constants. Here, “–”
means species at the oil/water interface and “>” means species on
the solid surface. All other species are in the aqueous phase. All
reactions are assumed at equilibrium.
interpolated from Evje and Hiorth (2011). Similar to the oil/
water-interface reactions, the equilibrium constants of Reaction 5
can be written as
 
Fw
exp  s ½> CaSO 4
RT
K5 ¼ ; face concentrations on the interface. We model the contact angle
½> CaOHþ 2 aSO2
4 as a linear function of surface concentration for the oil-wet and
where ws is the solid/water-interface potential (mV), which can
be calculated similarly to wo . Experimental results show that
Ca2þ, Mg2þ, and SO2 4 control surface potential, but Ca2þ or
Mg2þ alone without SO2 4 cannot alter wettability (Zhang et al.
2007). SO2 alone, however, cannot alter wettability either
4 ½> Ca; total
(Strand et al. 2006a; Zhang et al. 2007). Reactions 1 through 5
show that SO2 4 determines the potential at the solid surface,
whereas Mg2þ and Ca2þ complex with desorbed carboxylic acids
from the solid/fluid interface, which allows sufficient change to
occur. These reactions describe the different roles of aqueous spe-
cies. Reaction 6 in Table 1 represents the acid/base interactions
between oil/water interface and solid surface. Ion binding is not
included here because on calcite surfaces a positive surface
charge dominates below a pH of 9.4 (Buckley and Liu 1998),
whereas the experiment in Fathi et al. (2010) used a pH value of
8.4. The equilibrium constant for Reaction 6 was obtained by his-
tory matching of the base-case scenario.
Reactions 1 through 6 account for the electrostatic interactions
between the oil/water interface and the solid surface. The crude-
oil/brine interface is known to carry a negative charge, as repre-
sented in Reaction 1, whereas a chalk surface is known to be posi-
tively charged, as shown in Reaction 4 (Hiorth et al. 2010). The
electrostatic attraction between opposite charges leads to the oil
sorption on the solid surface (Nasralla and Nasr-El-Din 2012).
Those reactions represent the competitive adsorption of carbox-
ylic acids and SO2
4 on the chalk/water interface and the competi-
tive compounding of Ca2þ, Mg2þ, and >CaOH 2 on the oil/water
interface. Reactions 7 through 9 are aqueous-speciation reactions
that are also important in determining pH.
For all aqueous species (Ca2þ, Mg2þ, Hþ, and others), the ac-
tivity was calculated from
ai ¼ ci Ci ;
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where the activity coefficients were calculated according to the
extended Debye-Hückel model (Helgeson et al. 1970):
pffiffi
Az2i I
lnci ¼  pffiffi þ bI;
1 þ a0i B I
where the parameters A, B, and b are temperature-dependent pa-
rameters taken from the EQ3 database (Wolery et al. 1990). The
parameter a0i is the ion size, and I is the ionic strength of the brine.
Note that with higher ionic strength, the activity coefficients are
smaller, which leads to lower activity of specific species.
Wettability-Alteration Model. Most carbonate reservoirs are
classified to have mixed wettability (Buckley et al. 1996; Helland
and Skjaeveland 2006). Here, the rock surface is considered as
containing both water-wet and oil-wet surfaces. Different surfaces
can have different contact angles. Both receding-contact angles
(altered, water-wet) and advancing-contact angles (unaltered, oil-
wet) varied in core experiments (Buckley et al. 1996; Drummond
and Israelachvili 2004; Zhang and Austad 2005a; Alotaibi et al.
2010). According to Young’s equation, the contact angle has the
following relation derived from the force balance:
cos  cws
cosh ¼ ; . . . . . . . . . . . . . . . . . . . . . . . . . . ð7Þ
cow
where cws , cos , and cow are the interfacial tension (IFT) (mN/m)
between water and solid, between oil and solid, and between oil
and water, respectively. The contact angle describes how much a
mineral surface prefers one phase to another and is a result of the
three-phase (brine/oil/surface) interaction. The IFTs are deter-
mined by the surface concentration of ion species through Gibbs
equation (Gibbs 1948). The contact angle is then a function of sur-
water-wet surfaces of carbonates, which is justified in Appendix
B, where the derivation is modeled after the Gibbs isotherm. The
linear interpolation is shown in Eqs. 8 and 9:
½> CaSO 4
coshw ¼ coshw;0 þ ðcoshw; 1  coshw; 0 Þ;
                   ð8Þ
½> CaOHþ 
2 ðCOO Þ
cosho ¼ cosho;0 þ ðcosho;1  cosho;0 Þ;
½> Ca; total
                   ð9Þ
where ½> Ca; total represents the total concentration of the sur-
face site on the carbonate surface. The contact angle hw on the
water-wet surface (receding-contact angle) is interpolated by the
concentration of the water-wet agent (sulfate). The oil-wet contact
angle ho (advancing-contact angle) is interpolated by the oil-wet
agent (carboxylic group). The contact angles hw; 0 ; hw; 1 ; ho ;0 , and
ho;1 are input values representing the extreme cases (0 and 90 for
water-wet, 90 and 150 for oil-wet).
The surface concentration also determines the oil-wet and
water-wet surface fractions. The water-wet fraction (WWF) is cal-
culated as a linear function of the surface-site concentration as
½> CaOHþ2 ðCOO Þ

WWF ¼ 1  :
½> Ca; total
The change in relative permeability and capillary pressure
functions have typically been determined by linear interpolation
with respect to a wettability index (Delshad et al. 2009; Yu et al.
2009). Our model uses an experimentally verified wettability
index as well as theoretical support from equations by Gibbs
(1948) and Cassie (1948). The capillary pressure function fol-
lows the Leveret-Cassie equation (O’Carroll et al. 2005):
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10 1
krowater-wet

0.8
5 kroWWF = 0.5

Relative Permeability
Capillary Pressure water-wet

WWF = 0.52 0.6

0 krooil-wet oil-wet
krw
WWF = 0.82 WWF = 0.5
0.4 krw

–5
0.2 water-wet
krw
oil-wet

–10 0
0 0.5 1
0 0.2 0.4 0.6 0.8
(a) Water Saturation (b) Water Saturation

Fig. 3—Illustration of wettability-dependent capillary pressure and relative permeability. (a) Relative permeability for oil-wet
(WWF 5 0), water-wet (WWF 5 1), and intermediate-wettability (WWF 5 0.5) state. (b) Imbibition capillary pressure for oil-wet, water-
wet, and two intermediate states with different WWF values: 0.52 and 0.82. Note that the equilibrium water saturation under capil-
lary pressure is the x-axis intercept. As the rock becomes more water-wet, larger water saturation can be achieved by spontaneous
imbibition.

Pc ðSw ; WWFÞ ¼ WWFcoshw Pww
c ðSw Þ
þ ð1  WWFÞcosho Pow
c ðSw Þ;
where and Pww
c ðSw Þ Pow
c ðSw Þ
are the capillary pressure functions
for completely water-wet and oil-wet surfaces. Eq. 10 has been
experimentally verified to provide excellent predictions of the
capillary pressure as a function of saturation (Ustohal et al. 1998;
O’Carroll et al. 2005). Surface roughness has been included in the
completely oil-wet and completely water-wet capillary pressures.
One example of the capillary pressure for mixed wettability is
shown in Fig. 3a, where the oil-wet and water-wet data are from
Webb et al. (2005). The curves for intermediate wetting state
were obtained by use of Eq. 10. In Fig. 3b, the x-intercept repre-
sents the maximum water saturation that can be achieved by spon-
taneous imbibition. Our model captures the fact that the residual
oil saturation (ROS) depends on wettability.
The Brooks-Corey formulation was used here to describe the
relative permeability as a function of normalized fluid saturation
and water-wet fraction (Anderson 1987; Delshad et al. 2009). The
relative permeability was assumed to depend on the endpoint rela-
tive permeability and relative saturation using the following
equations:

krw ¼ krw ðS Þnw ;

kro ¼ kro ð1  S Þno
where the normalized water saturation S was calculated as
So  Sor
S ¼ ; effects of various brine compositions on wettability and recovery.
1  Swi  Sor
where Swi is the initial water saturation and Sor is the ROS. For
the mixed and fractional wettability, the fluids were assumed to
flow in parallel in both oil-wet and water-wet pore networks.
Therefore, WWF was also used to linearly interpolate the relative
permeability between completely water-wet and oil-wet cases, as
follows:
       ð10Þ
  
krw ¼ WWF krw;ww þ ð1  WWFÞkrw;ow ;

kro 
¼ WWF kro;ww 
þ ð1  WWFÞkro;ow ;

where kro;ww 
, krw;ww 
, kro;ww 
, and kwo;ow are the oil and water end-
point relative permeability for the oil-wet or water-wet case. One
set of relative permeability curves is shown in Fig. 3b, with the
corresponding parameters (endpoint relative permeability and
Corey exponent) in Table 2. In Fig. 3b, the oil-wet relative per-
meability function was adapted from Høgnesen et al. 2006.
Increasing water wettability shifts the curves to the right, which
favors oil-phase flow. The treatment is consistent with experimen-
tal findings (Owens and Archer 1971).
The simulation code PennSim was used to solve the multi-
phase-flow equations. PennSim uses a finite-volume discretization
(Fung et al. 1992) and a noniterative implicit-pressure/explicit-
concentration method (Coats 2000) to solve the governing equa-
tions. We sequentially obtained the immiscible multiphase-flow
solution and then a chemical reactive-transport solution. The pro-
cedure uses an operator-splitting technique with a strict restriction
on timestep size (Zysset et al. 1994). The calculation procedure
for one timestep is shown in Fig. 4.
Results and Discussion
This section presents a validation of the model by use of the base-
case scenario, sensitivity analyses of key parameters, and the
The ultimate recovery in this paper refers to the recovery factor at
the end of 40 days, when the oil-production rate is very low. The
discussion provides a mechanistic and quantitative understanding
of processes involved in low-salinity flooding and identifies the
most-important parameters.

Table 2—Corey’s relative permeability model parameters.

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Begin one timestep calculation

Pressure Solver
Calculate Jacobian for implicit-pressure solution
Multigrid-preconditioned iterative linear solver

Transport Solver
Calculate flux between blocks using the new pressure and old transmissibility
Explicitly calculate moles of components and ion species in each block

Reaction Solver
Update mole fraction of aqueous species
Perform chemical-equilibrium calculation

Property Update
Calculate contact angle, water-wet fraction, and change wettability-affected functions

End one timestep

Fig. 4—Illustration of the flow chart for one timestep in the implicit-pressure/explicit-saturation solution.

Base-Case Simulations. Various core experiments have been
performed to understand the mechanism and identify the optimal
conditions for chemically tuned waterflooding (Austad et al.
2008; Fathi et al. 2010; Yousef et al. 2010, 2012a, 2012b). We
used the data from Fathi et al. (2010) to validate our model and to
obtain key parameters. We selected this data set because their
experiments were consistently carried out at 110 C with different
brine compositions while maintaining all other conditions, which
allows easy comparison among different cases.
The experiments used homogeneous Stevns Klint chalk cores
(3.8 cm in diameter and 7.0 cm in length) with porosity of approx-
imately 45% and permeability between 1 and 2 md (1015 m2).
The cores were first cleaned with distilled water. After the drying
process, the cores were saturated with formation brine and then
flooded with oil to establish the initial water saturation. The oil
used was diluted from acid-reservoir-stabilized oil with n-heptane
to an equivalent acid number of 1.9 mg-KOH/g. The cores were
aged at 90 C for 4 weeks to restore to the reservoir condition,
where mixed wettability has been established. The cores were
then immersed in synthetic brine at 110 C, after which spontane-
ous imbibition began. The produced oil was collected over time,
after which chromatographic wettability tests were performed to
determine the water-wet fraction. Three different synthetic brines
were used, including formation water (FW), seawater (SW), and
seawater depleted in NaCl (SW0NaCl), as listed in Table 3. The
comparison among cases allows identification of the important
ions during the low-salinity-imbibition process.
During the spontaneous imbibition, the ions in the immersing
brine were transported and diffused into the core. The chemical
reactions altered the wettability and improved imbibition. Sponta-
neous imbibition causes countercurrent flow, during which the
volumetric flow rate of oil and water were equal, but in opposite
directions. Spontaneous imbibition is simulated by solving Eqs. 1
through 5 with Dirichlet boundary conditions. The boundary pres-
sure for both phases was set to be the backpressure; the boundary
saturation for water was 1.0; and the brine concentration on the
boundary was set to be the same as the imbibing fluid. The initial
oil saturation determined from the experiments was used and the
water-phase pressure was the same as the backpressure, whereas
the oil-phase pressure was calculated from the capillary pressure
relation in Eq. 3. The fluid initial water composition was the same
as the formation water.
We performed 2D simulations by use of the radial symmetry
of the core, where the core was discretized into 30  100 grid-
blocks in the r, z coordinates, as shown in Fig. 5. Fig. 6 compares
the oil-recovery data and the modeling output. The reaction-equi-
librium K6 value was tuned to match the base case. Here, we com-
pare three methods of different levels of complexity in
reproducing the oil recovery by use of brines of different compo-
sition. Method A was modeled after Høgnesen et al. 2006, where
fixed capillary pressure and relative permeability functions were
used, as is typically the case for multiphase-flow simulations. Oil-
wet functions were used for FW; water-wet functions were used
for SW0NaCl; and intermediate-wet functions were used for SW.
These functions were chosen on the basis of our understanding of
the wettability with respect to different water compositions.
Method B includes the transport and adsorption reaction of SO2 4
as the single reacting solute and calculates the wettability as a
function of the adsorbed sulfate mass (Yu et al. 2009). The capil-
lary pressure and relative permeability functions were obtained by
interpolation by use of the equations kr ¼ WWF krww þ ð1 
WWFÞkrow and Pc ¼ WWF Pww ow
c þ ð1  WWFÞPc , where WWF is
calculated from the solid-surface fraction of sulfate ions (i.e.,
CSO24 ;s
=Ctotal;s ). The sulfate-adsorption reaction was modeled with
the Langmuir isotherm without the effect of salinity. Method C is
our mechanistic method with PennSim, as discussed in the Method-
ology section. The reaction system explicitly included the effects
of different ions on the reaction-driven wettability alteration.
The comparison of oil-recovery curves shown in Fig. 6 shows
the necessity of including the geochemistry details. In the FW
case, with fixed wettability, Method A reproduced the countercur-
rent flow and the subsequent oil production for the FW case.
However, it overestimated the oil-production rates for SW and
SW0NaCl when wettability alteration occurred. Method B cannot
distinguish between the SW and SW0NaCl cases, as indicated by
their overlapping oil-recovery curves. This is because of the over-
simplified representation by use of a single component and single
reaction. PennSim accurately matched the oil-recovery curves for
the FW and SW0NaCl cases, and predicted approximately the re-
covery curve for SW (Fig. 6c). Our model reproduced the oil-

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Table 3—Synthetic-brine compositions used in experiments (Fathi et al. 2010) and simulations. We use
the same notation for different types of brine as those used in Fathi et al. (2010). FW denotes formation
water; SW denotes seawater; SW0NaCl denotes seawater with no NaCl; SW0NaCl0SO4 denotes
seawater with no NaCl or SO2 4 ; SW0NaCl4SO4 denotes seawater with no NaCl and with the sulfate
concentration adjusted to four times that of seawater; and SW0NaCl4Ca denotes seawater with no
NaCl but with the calcium concentration adjusted to four times that in seawater.

recovery decrease with increasing NaCl concentration for SW and
SW0NaCl. Moreover, our model reproduced the measured wetting-
area fraction in all experiments. The final water-wet fractions simu-
lated for FW (0.52), SW (0.67), and SW0NaCl (0.83) were within
5% of the experimentally measured values through chromato-
graphic wettability tests (Strand et al. 2006a; Fathi et al. 2010).
Fig. 7 shows the profile evolution for the base-case scenario
with SW0NaCl. The core was originally saturated with oil,
whereas the SW0NaCl solution was at the outside boundary of the
core. Sulfate diffused into the core from the boundary. Over time,
zones of high sulfate concentration expanded. Correspondingly,
the water-wet fraction of the core also expanded into the core and
oil was produced from the boundary because of increasing sponta-
neous imbibition. Oil saturation decreased from the initial
80–90% to a range of 30–50% on Day 20. The change occurred
faster in the first 10 days, with the oil saturation reduced to
approximately 36% at the boundary and up to 70% at the center.
At later times, the oil was produced more slowly, primarily
because of the decreasing positive capillary pressure. Naþ con-
centration was high at early time because of the high initial water
salinity. The brine inside the core became diluted during the imbi-
3.8 cm
bition process because seawater was depleted with sodium chlo-
ride. In this scenario, Naþ did not participate in sorption and
acted as a tracer, the spatial evolution of which was a result of the
transport process only. Compared with Naþ, the SO2 4 propaga-
tion was slower because the transport was delayed by adsorption.
The order of the propagation rate (So < WWF < CSO2 4
< CNaþ )
reflects the driving force of the system: the solute diffusion per-
turbed the original surface-chemical equilibrium, followed by
altered wettability by the sulfate adsorption, and later by water
imbibition with a positive capillary pressure and oil production.
The coherent profiles among different variables underscore the
tightly coupled multiphase and reactive-transport processes.
Fig. 8 shows the sulfate, water-wet fraction, and oil-saturation
profiles for SW. SW has seawater levels of sodium chloride,
whereas SW0NaCl has no sodium chloride. At any particular
time, the water-wet fraction at the altered locations was larger for
SW0NaCl than for SW, because there was more SO2 4 adsorbed
on the surface in the SW0NaCl case than in the SW case. Accord-
ing to the extended Debye-Hückel model, the activity coefficients
of the aqueous species in SW0NaCl were larger because of its
low total ionic strength. The activity coefficients varied with mix-
ing of the formation water and the imbibing fluid. Before mixing,
the activity coefficient of sulfate was 0.57 in SW0NaCl and 0.38
in SW. With the same concentration in SW0NaCl and SW, the ac-
tivity of sulfate was 1.5 times greater in SW0NaCl than in SW.
Therefore, more SO2 4 was adsorbed in the SW0NaCl case and
the surface became more water-wet. Comparison between Fig. 8c
and Figs. 7m through 7p shows that the oil saturation for
SW0NaCl is larger than that with SW. That is, high salinity leads
to less wettability alteration and less oil-recovery improvement.

Sensitivity Analysis. The multiple processes involve a large

7.0 cm
Fig. 5—Geometry of the model used in the experiments and
simulations. The radial symmetry of the core allows for 2D sim-
ulations instead of 3D ones. The computational domain has 30
blocks in the radial r-direction and 100 gridblocks in the vertical
z-direction. The gray blocks are boundary blocks with Dirichlet
boundary conditions.
number of parameters. A sensitivity analysis was performed to
understand the importance of different processes and parameters
in the SW0NaCl case, and the most-effective fluid in improving
oil recovery was compared with other types of brines in this
research. As shown in Table 4, the tested parameters include spe-
cific surface area and surface-site density of the chalk, diffusion
coefficient, equilibrium constants, and the crude-oil acid number.
Surface-reaction-equilibrium constants are important in deter-
mining the chemical-equilibrium state and thus the surface wett-
ability. The reported equilibrium constants of Reactions 2, 3, 5,
and 6 in the literature vary by orders of magnitude (Zhang and
Sparks 1990; Hiorth et al. 2010; Brady and Krumhansl 2012).
These reaction equilibrium constants are chosen to vary by one to
two orders of magnitude in our sensitivity analysis. Fig. 9a com-
pares the oil-recovery curves generated by use of different equi-
librium constants. A larger K5 means larger affinity of sulfate to
the surface so that more sulfate can adsorb onto the solid surface.
With the same surface-site density, this will lead to a larger por-
tion of sulfate-occupying surface sites, which therefore alters the

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0.6
0.5
Oil Recovery
0.4
0.3
0.2
0.1
0
0 10 20
Time (days)
Fig. 6—Comparison between experimental oil recovery and simulation results for FW, SW, and SW0NaCl by use of three different
simulation methods. The experimental data are the same for all cases and are represented by use of the symbols. Simulation A
used fixed-wettability functions adapted from Høgnesen et al. 2006. Simulation B used a single adsorption reaction adapted from
Yu et al. (2009). Simulation C used the model developed in this paper. Note that with Simulation B, the curve for SW overlaps with
the curves for SW0NaCl. Only (c) matches the trend in the experimental recovery curve for seawater.
rock surface to a more water-wet state. As such, a larger capillary
pressure is expected with a faster and greater oil recovery. Fig. 9a
shows that with a K5 value one order of magnitude larger, the ulti-
mate oil recovery increased by 5% original oil in place (OOIP). In
addition, the recovery rate was faster because the increased water
wettability increased the capillary pressure to larger positive val-
ues. When the K5 value is one magnitude smaller than the base
case, wettability alteration was negligible, which leads to zero
incremental-oil recovery.
Larger equilibrium constants typically correspond to those
under high-temperature conditions. Our results here are consistent
with the findings of the experimental results that low-salinity sea-
water is more effective under high-temperature conditions (Zhang
et al. 2006; Strand et al. 2008; RezaeiDoust et al. 2009).
The strength of the oil/rock bond was represented by K6
because Reaction 6 represents the interaction between the carbox-
ylic group and chalk surface. A large K6 value means a larger
tendency for oil to attach onto the solid. Fig. 9b shows that
smaller K6 values lead to much-greater oil recovery. The close-
ness between curves for the small and medium cases indicates
that when the K6 is small enough (less than 2.5104), the recov-
ery is not sensitive to the K6 value.
Figs. 9c and 9d compare the oil recovery with different K2 and
K3 values. The cations Ca2þ and Mg2þ compound with the car-
boxylic group on the oil surface and make the oil-surface charge
more neutral. The decrease of the negative charge enhances the
oil release from the positively charged rock surface. Larger K2
and K3 values result in a stronger tendency of Ca2þ and Mg2þ to
attach onto the oil surface. Figs. 9c and 9d show negligible effects
of K2 and K3. Ca2þand Mg2þ have similar roles in the reaction
system. Because there are sufficient divalent cations in the sea-
water, the cation-compounding reaction is unlikely to be a limit-
ing reaction. Therefore, Reactions 2 and 3 play a relatively minor
role compared with Reactions 5 and 6.
Fig. 10 shows the effect of the total number of surface sites
(TSS) on oil recovery. TSS was calculated as the product of
chalk-specific-surface area (SSA, in units of m2/g) and surface
site density (SSD, which represents the number of sites/m2). Fig.
10 was obtained by varying the SSA with the same SSD. Varying
SSD with the same SSA produces exactly the same curve. As
observed from Fig. 10, although the ultimate oil recovery is the
same for all cases, a smaller TSS leads to faster oil recovery
whereas a larger TSS leads to slower oil recovery. This is because
of the difference in sulfate adsorption and transport. A larger TSS
value means a larger number of surface sites to be occupied by
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Experimental FW
FW simulation A
FW simulation B
FW simulation C
Experimental SW
SW simulation A
SW simulation B
SW simulation C
Experimental SW0NaCl
SW0NaCl simulation A
SW0NaCl simulation B
SW0NaCl simulation C
30 40
sulfate for the same proportion of the water-wet fraction. To reach
the same wettability, more sulfate needs to be adsorbed, which
takes a longer time. TSS, however, only controls the quantity of
adsorbed mass and has no effect on the reaction equilibrium. The
extent of wettability alteration is the same with different TSS val-
ues, which leads to the same ultimate oil recovery.
The oil contains the carboxylic group (COOH); larger acid
numbers (ANs) mean more COOH to react with Ca2þ and
Mg2þ and other aqueous species. The literature reports a range of
surface-density values between 3.1/nm2 and 0.3/nm2, correspond-
ing to acid numbers between 2.07 and 0.17 mg-KOH/g. Fig. 11a
shows greater recovery with the smaller AN. Fig. 11b shows the
water-wet fraction along the core radius for different ANs in Fig.
11a. For the small AN, the core was altered to almost completely
water-wet (water-wet fraction equals 1) at the end of 20 days. For
the large-AN case, the water-wet fraction was approximately
0.82. This difference leads to increases in oil recovery. Such dif-
ferences can be explained by use of Reactions 1 and 6. Reaction 1
shows that larger COOH concentration leads to larger Hþ and
–COO concentrations, which results in an oil surface that is
more negatively charged. With Reaction 6, the increased –COO
concentration leads to more > CaOH2 (COO), which results in a
more oil-wet chalk surface and less oil recovery. Therefore, a
smaller AN leads to a higher oil recovery (68% OOIP) than a
larger AN (59% OOIP). This is consistent with experimental
observations in the literature (Zhang and Austad 2005a; Strand et
al. 2006a). If the oil does not contain acid at all, the rock is com-
pletely water-wet and the spontaneous imbibition has the best re-
covery. However, in this case the salinity of water does not affect
the oil recovery. To our knowledge, the dependence on oil acidity
was not included in any other low-salinity models.
The impact of diffusion coefficient is shown in Fig. 12a. All
diffusion coefficients lead to the same oil recovery on Day 80.
The diffusion coefficient is important because diffusion controls
the transport rate of the ions into the rock. Fig. 12b shows the cor-
responding sulfate-concentration profile on Day 10. Sulfate was
transported faster with a larger diffusion coefficient, which led to
more adsorbed sulfate earlier, and faster wettability alteration and
oil recovery. However, the diffusion coefficient does not affect
the ultimate wettability and oil recovery at 40 days.
From the sensitivity analysis, the parameters are classified into
Type I and Type II according to their role in controlling the oil-
recovery curve. Type I parameters control the ultimate amount of
oil recovery. These include the chemical-equilibrium constants
and crude-oil AN. Type II parameters, including the solid-
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SO42– Solid-Surface Concentration (μmol/m2)

(a) 0.5 days (b) 5 days 10 days (c) 20 days (d)
mm mm mm mm
2.5
10 10 10 10
20 20 20 20 2
30 30 30 30 1.5
40 40 40 40
1
50 50 50 50
60 60 60 60 0.5

70 70 70 70 0
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Na+ Aqueous Concentration (mol/kg water)

(e) 0.5 days (f) 5 days 10 days (g) 20 days (h) 1

mm mm mm mm
10 10 10 10 0.8
20 20 20 20
30 30 30 30 0.6
40 40 40 40
50 50 50 50 0.4

60 60 60 60
0.2
70 70 70 70
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Water-Wet Fraction
(i) 0.5 days (j) 5 days 10 days (k) 20 days (l)
mm mm mm mm 0.8
10 10 10 10
0.75
20 20 20 20
0.7
30 30 30 30
40 40 40 40 0.65

50 50 50 50 0.6
60 60 60 60
0.55
70 70 70 70
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Oil Saturation
0.9
(m) 0.5 days (n) 5 days 10 days (o) 20 days (p)
mm mm mm mm
0.8
10 10 10 10
20 20 20 20 0.7

30 30 30 30 0.6
40 40 40 40
50 50 50 50 0.5

60 60 60 60 0.4
70 70 70 70
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Fig. 7—Spatial and temporal evolution of the SO22 1

4 , Na concentrations, water-wet fraction, and oil saturation for the imbibition of
SW0NaCl. The horizontal axis is the radial distance from the center of the cylinder core, and the vertical axis is the vertical distance
from the base.
2þ
surface-site density and diffusion coefficient, control the rate of with different SO2
4 and Ca concentrations for the same core
oil recovery. Most of these controlling variables (equilibrium con- and crude oil. Fig. 13 shows oil-recovery curves for all cases.
stants, oil acidity, and the diffusion coefficient) are temperature- Among these five cases, the SW0NaCl4SO4 case has the greatest
dependent, indicating the importance of temperature in the effec- oil recovery of approximately 65% OOIP.
tiveness of the chemically tuned waterfloods in carbonates. The SW0NaCl0SO4 case behaves the same as formation
water, indicating no improved oil recovery without the pres-
Effect of Brine Composition. Here we use the parameters from ence of sulfate. Without sulfate, the carboxylic group is stable
the calibrated base case and compare predictions for five cases on the rock surfaces and the system remains oil-wet. With more

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SO42– Solid-Surface Concentraion (μmol/m2)

(a)
0.5 days 5 days 10 days 20 days
mm mm mm mm
2.5
10 10 10 10
20 20 20 20 2
30 30 30 30 1.5
40 40 40 40
1
50 50 50 50
0.5
60 60 60 60
70 70 70 70 0
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Water-Wet Fraction
(b)
0.5 days 5 days 10 days 20 days
mm mm mm mm 0.8
10 10 10 10
0.75
20 20 20 20
0.7
30 30 30 30
40 40 40 40 0.65

50 50 50 50 0.6
60 60 60 60 0.55
70 70 70 70
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Oil Saturation
(c) 0.9
0.5 days 5 days 10 days 20 days
mm mm mm mm
0.8
10 10 10 10
20 20 20 20 0.7
30 30 30 30
0.6
40 40 40 40
50 50 50 50 0.5

60 60 60 60 0.4
70 70 70 70
0 10 mm 0 10 mm 0 10 mm 0 10 mm

Fig. 8—Spatial and temporal evolution of the SO22

4 surface concentration, water-wet fraction, and oil saturation for the imbibition
of SW. The corresponding oil-recovery curve is shown in Fig. 6c. The comparison of this figure with Fig. 7 explains the recovery
differences.

sulfate in the seawater, the ultimate oil recovery increased ent with multiple experimental observations (Zhang et al. 2006;
(SW0NaCl4SO4) by 5% OOIP and the rate of the oil produc- Fathi et al. 2011).
tion was also faster. These results demonstrate the importance A decrease in oil recovery is observed with increased aqueous
of sulfate in the wettability-alteration process and are consist- salinity, which is consistent with Fig. 7 and with experimental

Table 4—Parameters used in sensitivity analysis. The value for K6 was selected from the match of the base case because no such data
were found in the literature. Other values selected are within the range from the literature.

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(a) (b)
0.8 0.8

0.6 0.6 log K6 = 4.4

Oil Recovery log K5 = 4.4

Oil Recovery
log K5 = 3.4 log K6 = 5.4
0.4 0.4

log K5 = 2.4
0.2 log K6 = 6.4
0.2

0 0
0 10 20 30 40 0 10 20 30 40
Time (days) Time (days)
(c) (d)
0.8 0.8

0.6 0.6 log K3 = –1.5

Oil Recovery

Oil Recovery
0.4 log K3 = –2.5
0.4
log K3 = –3.5
log K2 : –2.2
0.2 log K2 : –1.2 0.2

log K2 : –3.2
0 0
0 10 20 30 40 0 10 20 30 40
Time (days) Time (days)

Fig. 9—Oil-recovery curves for different reaction-equilibrium-constant parameters for Reactions 5 (a), 6 (b), 2 (c), and 3 (d). With
the same brine compositions, the significant difference in the oil recovery illustrates that the solid/water interface reactions (5 and
6) are very important. The specific values of these parameters can be found in Table 4.

observations (Fathi et al. 2011). Increasing Ca2þ concentration
has a negligible effect, suggesting that Ca2þ concentration is not a
limiting quantity for SW0NaCl and there are abundant divalent
cations in seawater. Similar marginal effects of Ca2þ were also
observed in experiments (Fathi et al. 2011).
Limitations and Potential Improvements. In the model valida-
tion in Fig. 6, the oil-recovery curves were matched for FW and
0.8
Chalk TSS = 0.6 x 109/g
0.6
Oil Recovery
SW0NaCl, whereas the oil recovery for SW was predicted. There
are two main differences between the model prediction and exper-
imental data. First, the predicted oil recovery for SW is larger
than the experimental data in the first 5 days. There are multiple
reasons that could have caused the discrepancy. The lack of the
measured specific imbibition capillary pressure function for limit-
ing wettability cases could be one reason for the discrepancy.
Another possible factor is numerical diffusion introduced by the
low-order finite-volume discretization. Numerical diffusion
causes additional mixing between the imbibing and connate fluids
and may overestimate the rates of wettability alteration. In addi-
tion, the ions were assumed to have the same diffusion coefficient.
However, small ions such as Naþ can diffuse faster than large
ions such as SO2 4 . Surface adsorption/desorption reactions could
also be dominated by kinetic effects, which violates the reaction-

equilibrium assumption (Bruemmer et al. 1988; Fuller et al.

1993). All these factors could lead to the mismatch of the oil-re-
0.4 Chalk TSS = 6 x 109/g covery rate in the first 5 days.
Second, the final oil-recovery factor for SW is underestimated.
Chalk TSS = 14.4 x 109/g
This can be because of the lack of accurate surface-chemistry
0.2 data. Reaction 6 used in this model was not validated by experi-
ments, but instead was tuned to provide a good match of the simu-
lated data to the experiments. Whether the acidic-oil-component
0 adsorption obeys the mass-action law is not clear. The diffusive-
0 10 20 30 40 layer model used to predict the effect of surface potential on car-
Time (days)
boxylic-group adsorption could also be a constraint of the model.
An independent measurement of the key reaction-equilibrium
Fig. 10—Oil recovery as a function of the total number of sur- constant K6 could allow a conclusive validation of the model.
face sites. A difference in the recovery rate is apparent at Also, the relative permeability and capillary pressure data specific
approximately Day 2. The ultimate recovery is the same, how- to the core experiments (at the initial wettability and final wett-
ever. The adsorbing capacity, represented by TSS, affects the ability) will lead to a complete validation of this model and better
recovery rate. understanding of the system.

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0.8
1
Oil AN: 0.17
Oil AN: 0.17
0.6

Water-Wet Fraction
Oil Recovery

0.9
0.4 Oil AN: 1.90

Oil AN: 2.07 Oil AN: 1.90

0.8
0.2
Oil AN: 2.07

0 0.7
0 10 20 30 40 0 5 10 15
(a) Time (days) (b) Distance to Core Center (mm)

Fig. 11—(a) Oil recovery as a function of the AN. (b) Water-wet fraction profile along the radial direction at Day 10. Crude-oil acidity
affects the wettability alteration and oil recovery.

0.8
mm mm
D: 2.4x10–10 m2/s
0.6 10 10 0.02
Oil Recovery

20 20
D: 1.4x10–10 m2/s 0.015
Height

Height
0.4 30 30
D: 5.1 x10–11 m2/s 40 40 0.01

0.2 50 50
0.005
60 60
70 70 0
0 0 10 mm 0 10 mm
0 20 40 60 80
Radius Radius
(a) Time (days) (b) (c)

Fig. 12—(a) Predicted oil recovery with different values of diffusion coefficients. (b) The sulfate concentration in the aqueous
phase (mol/kg water) profile on Day 10 for diffusion coefficient 1:43310210 m2/s. (c) The sulfate concentration in the aqueous phase
(mol/kg water) profile on Day 10 for diffusion coefficient 0:51310211 m2/s. The oil-recovery rate (a) is very sensitive to the diffusion
coefficient because the diffusion process dominates the solute transport (b) in these experiments.

Conclusion waterflooding in mixed-wet carbonate reservoirs. The simulation

We developed a model to understand and predict wettability alter- results of spontaneous-imbibition experiments demonstrated that
ation and improved oil recovery (IOR) for chemically tuned our model can be used to describe the complex interactions
among different phases and species involved in chemically tuned
water IOR. The model captured the interplay among aqueous spe-
0.7 cies (Ca2þ, Mg2þ, SO2 4 ), crude-oil acidity, and solid-surface
SW0NaCl4SO4 properties. The coupled mixed-wettability and reactive-transport
0.6 model was capable of predicting the wettability-alteration effects
owing to chemical reactions. The oil-recovery curves predicted
0.5 SW0NaCl for different brine compositions showed good consistency with
experimental observations.
Oil Recovery

SW0NaCl4Ca
0.4 Our model improves the understanding of and provides a
powerful tool for chemically tuned waterflooding. The findings
SW include
0.3
• The surface-complexation reactions control the wettability-
0.2 alteration process. The chemically tuned brine should be
designed to promote oil-component desorption from the
SW0NaCl0SO4
0.1
rock. Moreover, because the oil recovery is sensitive to the
equilibrium constants, the specific reservoir condition
should be used in both experiments and simulation.
0 • There are two types of parameters. Type I controls the final
0 10 20 30 40
wettability and ultimate oil recovery, whereas Type II con-
Time (days) trols the rate of wettability alteration and rate of oil recov-
ery. Type I includes the reaction-equilibrium constants and
Fig. 13—Oil-recovery prediction for five chemically tuned crude-oil acid number. Type II includes total surface sites of
brines, where brine is the imbibing fluid at 110º C. A description
solid and the diffusion coefficient.
of the abbreviations is shown in Table 3. Generally, the oil re-
covery at 40 days increases with the sulfate concentration and • The concentrations of ionic species, ionic strength, and oil
decreases with the total ionic strength. This is because there acidity are important in the IOR process. The salinity should
are adequate Ca21 and Mg21 in seawater so that adding those not be the single factor that is used to assess the effective-
cations only has a marginal effect in such cases. ness of the chemically tuned water.

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 J170966 DOI: 10.2118/170966-PA Date: 6-August-15
Nomenclature
ai ¼ the activity of species i, dimensionless
a0i ¼ the ion-size parameter for Debye-Hückel model
A, b, B ¼ temperature-dependent parameters for the Debye-
Hückel model
Aos ¼ area of the oil/solid interface, m2
Aow ¼ area of the oil/solid interface, m2
Aws ¼ area of the water/solid interface, m2
Cio ¼ the concentration for the species io on the oil surface,
mol/m2
Cis ¼ the concentration for the species is on the solid surface,
mol/m2
Ciw ¼ the concentration for the species iw in the aqueous
phase, mol/m3
D ¼ diffusion coefficient, m2/s
F ¼ Faraday’s constant, 9.648104 C/mol
Fp ¼ molar rate of the primary species p, mol/md
Fq ¼ molar rate of the secondary species q, mol/md
g ¼ gravity factor, m/s2
I ¼ the ionic strength of water, mol/kg water
k ¼ permeability, md
kr ¼ relative permeability
Kn;eq ¼ the equilibrium constant for the nth reaction, unitless
Mp ¼ molar density of the primary species p, mol/m3
Mq ¼ molar density of the secondary species q, mol/m3
Np ¼ the number of the primary species
Nsec ¼ the number of secondary reactions
Ntot ¼ the total number of species
P ¼ pressure, Pa
Pc ¼ the oil/water capillary pressure
R ¼ the gas constant, J/Kmol
Ri ¼ reaction rate for the species i, mol/m3s
S ¼ saturation, dimensionless
T ¼ the absolute temperature, K
u ¼ fluid-volume flow rate, m3/d
~ Buckley, J. S., Bousseau, C. and Liu, Y. 1996. Wetting Alteration by Brine
zi ¼ the charge carried by the species i
a ¼ phase subscript, w representing water phase and o rep-
resenting oil phase
ci ¼ the activity coefficient of species i, kg water/mol
cos ¼ the interfacial tension (IFT) of the oil/solid interface,
dynes/cm
cow ¼ the IFT of the oil/water interface, dynes/cm
cws ¼ the IFT of the water/solid interface, dynes/cm
e0 ¼ the dielectric constant of water, 55.3, dimensionless
em ¼ the permittivity of free space, 8.854  1013 C
V 1 dm1
h ¼ the contact angle, degrees
l ¼ viscosity, poise
li ¼ chemical potential of species i, J/mol
pq ¼ the (q; p) entry in the stoichiometry matrix
q ¼ density, kg/m3
ro ¼ the charge density at the oil surface, C/m2
/ ¼ porosity, dimensionless
wo ¼ the oil/water-interface-charge potential, mV
ws ¼ the solid/water-interface-charge potential, mV
Acknowledgments
The authors gratefully thank the member companies of the
Enhanced Oil Recovery JIP in the EMS Energy Institute at Penn-
sylvania State University at University Park, Pennsylvania, for
their financial support.
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Appendix A: Mass Conservation for Multiphase
Reactive Transport System
This appendix derives the multiphase reactive-transport equation,
Eq. 5. For the aqueous species, the mass-conservation equation
for the primary species iw is
@
ð/Sw qw Ciw Þ þ r  ½Ciw qw~
u w  DrðSw qw Ciw Þ
@t
¼ Req kinetic
iw þ Riw ; iw ¼ 1; …; nw : . . . . . . . . . . . . . ðA-1Þ
For the water/solid-interface species iws and the oil/solid-inter-
face species ios , the mass-conservation equation is
@
½ð1  /Þqs Aws Ciws  ¼ Req kinetic
iws þ Riws ; iws ¼ 1; …; nws ;
@t
                   ðA-2Þ
@
½ð1  /Þqs Aos Cios  ¼ Req kinetic
ios þ Rios ; ios ¼ 1; …; nos :
@t
                   ðA-3Þ
For the oil/water-interface species iow , the mass-conservation
equation is
@
½ð1  /Þqs Aow Ciow  ¼ Req kinetic
iow þ Riow ; iow ¼ 1; …; now ;
@t
                   ðA-4Þ
781
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where Ciw is the concentration of species iw in aqueous phase where all the reactions are assumed to be at equilibrium and the
(mol/kg water); Ciws is the concentration of species iws on water/ kinetic rates vanish. We followed the typical reactive-transport
solid interface (mol/m2); Cios is the concentration of species ios on formulation to partition the reactive species into primary and sec-
oil/solid surface (mol/m2); Ciow is the concentration of species iow ondary species. The rate of production of a primary species p
on oil/water interface (mol/m2); D is the diffusion/dispersion from the equilibrium reactions can be written as the total rates of
coefficient (m2/s); Aws is the water/solid-interface area (m2/g production of secondary species:
solid); Aos is the oil/solid-interface area (m2/g solid); and Aow is XNsec
the oil/brine-interface area (m2/g solid). In Eq. A-1, the first term Req
p ¼  qp Rq ;
is for mass accumulation; the second term is a transport term, q¼1
which includes convection and diffusion; and the right-hand side where qp represents the (q, p) entry of the stoichiometry coeffi-
is the reaction term. The reaction rates are classified into equilib- cient matrix. Here the primary species p or secondary species q
rium-controlled reaction rates and kinetically controlled reaction can represent aqueous species, solid-surface species, or species on
rates, denoted as Req and Rkinetic (mol/s-kg water). These two the oil/water interface. We can eliminate the reaction rates from
terms can be the summation of multiple reaction-rate terms, Eqs. A-1, A-5, and A-6 for Eq. 5:
depending on the number of reactions that involve this species.
! !
Eqs. A-2, A-3, and A-4 do not have the transport term because the @ X
Nsec X
Nsec
interfaces are not mobile in our model. Mp þ qp Mq þ r  Fp þ qp Fq ¼ 0;
The interface between brine and oil contains surface-active @t q¼1 q¼1
sites as the polar components in crude-oil hydrate, whereas the p ¼ 1; …; np :                       ð5Þ
interface between brine and solid contains solid-surface sites that
contain polar ions (Buckley 1994; Buckley and Liu 1998; Hira-
saki and Zhang 2004). The interface between the solid and oil Appendix B: Relation Between Surface
phase is regarded as the part of the solid surface that is fully occu- Concentration and Contact Angle
pied with organic ion-containing sites. At the solid surface, the One crucial step in our model is to relate surface geochemistry to
competition between the oil and water species for the solid sur- surface-contact angles. That relation was built by estimating inter-
face determines the proportion of the solid surface that is occu- facial tension (IFT) from a Gibbs isotherm. The contact angle was
pied by water and oil. This occupancy of solid-surface sites then estimated from Eq. 7. The change in IFT can be quantified
determines the wettability. by the Gibbs adsorption equation (Gibbs 1948),
The total solid-surface area (Aos þ Aws ) represents the total X
available surface area and is a constant calculated on the basis of dcws ¼  Ci dli;ws ; . . . . . . . . . . . . . . . . . . . . . . ðB-1Þ
the specific surface area (SSA) of the rock. The total oil-surface i
area (Aos þ Aow ) may vary depending on oil saturation. We define where dcws is the differential change of the water and surface IFT,
the solid-surface concentration (Ci;s ) as Ci is the surface-excess concentration of species i (mol/m2), and
8A dli;ws is the differential change of the chemical potential of spe-
>
<
ws
Ciws ; when i ¼ iws : cies i on the surface (mJ/mol). For surface-active species, the sur-
Ci;s ¼ AAs face-excess concentration Ci can be considered to be equal to the
>
: os Cios ; when i ¼ ios : actual surface concentration without significant error (Rosen and
As Kunjappu 2012); namely, Ci ¼ ½i, where ½i is the surface concen-
tration of species i in mol/m2. The chemical potential of surface-
The oil/water-surface concentration can be defined similarly. species i can be calculated from
Eqs. A-2 through A-4 can be rewritten as the mass conservation
on the total solid surface and total oil surface: li;ws ¼ l0i;ws þ RTlnai;ws ¼ l0i;ws þ RTlnðci ½iÞ;
@
½ð1  /Þqs As Cis  ¼ Req kinetic
is þ Ris ; . . . . . . . . . . . . ðA-5Þ where l0i;ws is the chemical potential of surface-species i at a refer-
@t ence state. If we assume the activity-coefficient ci has a weak de-
@ pendence on the surface concentration ½i, then
½ð1  /Þqs Ao Cio  ¼ Req
i þ Ri
kinetic
; . . . . . . . . . . . . ðA-6Þ
@t RT
dli;ws ¼ d½RTlnðci ½iÞ ¼ RTdðln½ci  þ ln½iÞ ¼ d½i:
where Cis is the solid-surface concentration that includes the oil/ ½i
solid and water/solid species; Cio is the oil-surface concentration
that includes the oil/water species; and As and Ao are the total sur- Substitution of dli;ws into Eq. B-1 gives
face areas of solid and oil, respectively. In this research, As is the X X
RT
total surface area and is calculated on the basis of the specific sur- dcws ¼  ½i d½i ¼ RT i d½i: . . . . . . . . . . ðB-2Þ
face area of the carbonate rocks, whereas Ao is a linear function of
i ½i
oil saturation.
Eq. B-2 indicates that the surface tension is linear with respect to
We define the molar density of species i as
the surface concentration. The derivation is also valid for an oil/
8 solid interface. In the low-salinity-flooding scenario, the change
< /Sw qw Ciw ; for i ¼ iw
Mi ¼ ð1  /Þqs As Cis ; for i ¼ is ; in cow is not considered significant (Zhang et al. 2006). Therefore,
:   X
ð1  /Þqs Ao Cio ; for i ¼ io cos  cws dcos  dcws RT i d½i
dcoshw ¼ d ¼ ¼ :
and the molar-flow rate of species i as cow cow cow
8                    ðB-3Þ
u w  DrðSw Ciw Þ; for i ¼ iw
< Ci;aq qw~ Eq. B-3 indicates that for an ideal system, cosh is a linear function
Fi ¼ 0; for i ¼ is : of the surface concentration of sulfate. A linear interpolation can
: be used when we know extreme values of the contact angles.
0; for i ¼ io
With h ¼ h0 for fresh water and h ¼ h1 for a sulfate-surface con-
From these definitions, we can write a general equation for the centration > Ca; total, at surface concentration of > CaSO 4 the
transport of chemical species: effective contact angle is estimated by Eq. 8:
@ ½> CaSO 4
Mi þ r  Fi ¼ Req
i ;
coshw ¼ cosh0 þ ðcosh1  cosh0 Þ: . . . . . . ð8Þ
@t ½> Ca; total

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 J170966 DOI: 10.2118/170966-PA Date: 6-August-15
Changhe Qiao is a PhD degree candidate in the Department
of Mathematics at the Pennsylvania State University. Qiao’s
research interest includes compositional simulation, reactive-
transport models, fast and robust linear solvers, and parallel
computing. He holds a bachelor’s degree in computational
mathematics from Peking University, China.
Li Li is an assistant professor in the Department of Energy and
Mineral Engineering at Pennsylvania State University. She has
worked for more than 10 years in understanding and predicting
physical-, chemical-, and biological-process coupling in spa-
tially heterogeneous subsurface. In addition to low-salinity flood-
ing, Li has worked on a range of topics at the water/energy
nexus, including geological carbon sequestration, microbe
enhanced oil recovery, reservoir souring, and bioremediation.
Russell T. Johns is the Chair of the Petroleum and Natural Gas
Engineering Program within the Department of Energy and
Mineral Engineering at Pennsylvania State University. He also
holds the Victor and Anna Mae Beghini Professorship of Petro-
leum and Natural Gas Engineering and the CMG Foundation
Chair in fluid behavior and rock interactions. Before his current
position, Johns served on the petroleum engineering faculty
at the University of Texas at Austin from 1995 to 2010. He also
has 9 years of industrial experience as a petrophysical engi-
neer with Shell Oil and as a consulting engineer for Colenco
Power Consulting, Baden, Switzerland. Johns has more than
200 publications in enhanced oil recovery, thermodynamics
August 2015 SPE Journal
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Stage: Page: 783 Total Pages: 17
and phase behavior, unconventional gas engineering, multi-
phase flow in porous media, and well testing. He received the
SPE Ferguson Medal in 1993 and served as coexecutive editor
for SPE Reservoir Evaluation and Engineering from 2002 to
2004. In 2009, Johns was awarded the SPE Distinguished Mem-
ber Award and in 2013 the SPE Faculty Pipeline Award. He is
currently director of the Enhanced Oil Recovery Consortium
and codirector of the Unconventional Natural Resources Con-
sortium in the EMS Energy Institute at Pennsylvania State
University. Johns holds a bachelor’s degree in electrical engi-
neering from Northwestern University and master’s and PhD
degrees in petroleum engineering from Stanford University.
Jinchao Xu is the Verne M. Willaman Professor of Mathematics,
the Francis R. and Helen M. Pentz Professor of Science, and
Director of the Center for Computational Mathematics and
Applications at Pennsylvania State University. His research
interests are in the design, analysis, and application of numeri-
cal methods, especially multilevel and adaptive finite-element
methods, for systems of partial-differential equations and
problems with direct applications to physics, biology, and en-
gineering. Xu was a plenary speaker at the International Con-
gress for Industrial and Applied Mathematics in 2007 and an
invited speaker at the International Congress for Mathemati-
cians in 2010. He is a fellow of the Society for Industrial and
Applied Mathematics and the American Mathematical Soci-
ety in the inaugural class.
783