Article

pubs.acs.org/EF

Modeling Low-Salinity Waterooding in Chalk and Limestone

Reservoirs
Changhe Qiao,* Russell Johns, and Li Li
Pennsylvania State University, University Park, Pennsylvania 16802, United States

ABSTRACT: The injection of low-salinity brines can improve oil recovery in carbonate reservoirs by changing the rock
wettability from being more oil-wet to being more water-wet. Existing models use an empirical dependence of wettability based
on variables including equivalent salinity and ionic strength. We recently developed a process-based model that mechanistically
includes the geochemical interactions between crude oil, brine, and the chalk surface that alter rock wettability. In this research,
we extend the previous model by including mineral dissolution reactions, therefore enabling the modeling of low-salinity ooding
in chalks and limestone cores with and without anhydrite, which is considered to be a key factor in controlling the extent of
improved oil recovery (IOR). We examine the role of mineralogy by including surface complexation, aqueous reactions, and
dissolution/precipitation of calcite and anhydrite in the extended model. These reactions, coupled with the equations of
multiphase ow and transport, are solved simultaneously using an in-house simulator, PennSim. Relative permeability functions
and residual oil saturation during ooding are adjusted dynamically according to the concentration of oil acids attached to the
mineral surface. Core ooding experiments from the Stevns Klint (SK) chalk and a Middle Eastern carbonate with a small
volume fraction of anhydrite are used to tune the reaction network and predict recovery. Simulation results agree with the
observed euent concentrations of SO42, Ca2+, and Mg2+ reported from chromatographic wettability tests and the measured
recoveries under diering compositions in chalk and limestone cores. For the SK chalk without anhydrite, lower Na+ and Cl
concentrations under constant SO42 conditions leads to IOR by as much as 6% OOIP. Lower salinity alone, however, does not
lead to IOR in limestones without anhydrite. Instead, anhydrite dissolution provides a natural source of sulfate and increases oil
recovery by 5% when injecting diluted formation water. Simulations of two-dimensional (2D) ve-spot patterns using tuned
reaction networks demonstrated that IORs from 5% to 20% OOIP can be obtained after two pore volumes are injected. These
IORs are greatly dependent on the aqueous chemistry of the injected uid and sweep. The results highlight the critical
importance of understanding the mineralogy and including a mechanistic reaction model in the simulation of low-salinity water
oods.

INTRODUCTION
Low-salinity water (LSW) has been reported in the literature to
improve oil recovery signicantly in sandstone and carbonate
core experiments.14 Here, we focus on the widely used term
low-salinity ooding, although both experimental data from
Austad et al.1,57 and our model8 suggest that improved oil
recovery (IOR) is not solely caused by low salinity (total
dissolved salt). Instead, it is the specic composition of the
injection waterin particular, the concentrations of the
wettability-altering species (SO42, Ca2+, and Mg2+)that
matters. The recoveries in core oods and imbibition tests vary
greatly, depending on the aqueous chemistry used, the pore
volumes injected (PVI), and the carbonate mineralogy.6,9
Improved recoveries were 5% to 40% OOIP for
spontaneous imbibition tests in the Stevns Klint chalk and
5% to 20% OOIP in core ooding experiments in both the
Stevns Klint chalk and a Middle Eastern limestone.6,2,10 Diluted
formation water without sulfate was found to improve oil
recovery by 5% OOIP.5 Diluted seawater was reported to
improve oil recovery by 17% to 19% OOIP in a limestone core
that contained anhydrite.2 A single well tracer test at eld scale
also exhibited decreased residual oil saturation by seven
saturation units from the injection of diluted seawater.11
One of the primary mechanisms proposed for IOR by LSW
ooding is wettability alteration from a more oil-wet state to a
more water-wet state.1,10 Chromatographic wettability tests
with chemically tuned water conrmed wettability alteration by
incremental sulfate adsorption onto the rock surface.6,12
Wettability alteration was also conrmed in contact angle
measurements on a at plane carbonate surface, where smaller
contact angles were reported with modied seawater.2
Furthermore, capillary pressure reduction was observed in
spontaneous imbibition tests when sulfate-containing seawater
was injected, compared to sulfate-free water.13 Shifts in relative
permeability and decreases in residual oil saturation were
demonstrated in core ooding experiments.10
Wettability alteration could be caused by mineral dissolution,
surface adsorption/desorption, and surface potential reduc-
tion.7,14,15 Austad et al.1 proposed that, for the Stevns Klint
chalk outcrop, the concentrations of potential determining ions
(PDIs) such as Mg2+, Ca2+ and SO42 greatly aected the oil
recovery in spontaneous imbibition tests. They explained that,
for mixed wet surfaces, both SO42 and carboxylic groups in the
oil adsorb onto the rock surface, altering the surface charge
from positive to negative. The negatively charged solid surface
then attracts cations such as Mg2+ and Ca2+ to react with the
adsorbed carboxylic group, which releases the carboxylic group
Received: October 18, 2015
Revised: January 11, 2016

XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.5b02456

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and causes the surface to become more water-wet. The notion
that carboxylic groups leave the chalk surface was inferred from
water vapor adsorption isotherms, where SO42 reduced the
surface concentrations of adsorbed fatty acids.16 Spontaneous
imbibition experiments with varied brine compositions support
such chemical mechanisms.6,7,9,12 In addition to SO42, BO32
and PO43 were also found to improve oil recovery.17
Experimental studies have revealed that the brine composi-
tion sucient for enhanced oil recovery in Stevns Klint chalk
was not necessarily eective for other carbonate minerals.
Instead, diluted formation water and seawater were found to
improve oil recovery the most for limestone and dolomites.2,18
Romanuka et al.18 performed spontaneous imbibition tests for
Stevns Klint chalk, limestone, and dolomite cores and
concluded that eective EOR uids are signicantly dependent
on the rock mineralogy. Screening Amott imbibition experi-
ments showed that additional SO42 did not lead to IOR for
limestone and dolomite, as well as for the Stevns Klint chalk
with diluted formation water. One possible reason for an
increase in oil recovery for sulfate-free injection uids in
limestone is the increased sulfate concentration from
dissolution of anhydrite in situ.5 In addition, SO42 and Mg2+
were reported to improve oil recovery incrementally in core
ooding experiments for limestone.19
The above-mentioned experimental evidences have shown
signicant promise of LSW for IOR; however, at the same time,
it has indicated the complexity of geochemical reactions
involved in low-salinity ooding in dierent types of carbonate
formations. Currently, there is no theory to quantify and
explain many of these dierences. Various modeling eorts
have tried to capture the wettability alteration process.
Wettability alteration has been modeled by interpolating
capillary pressure, relative permeability, and residual oil
saturation between two wetting states.20,21 Empirical relation-
ships between wettability and water chemistry parameters were
used including salinity, ionic strength, or total dissolved
salts.20,22 Contact angles were also used to represent surface
wettability.22 Although these relationships are valid under the
given experimental conditions, they do not take into account
complex surface reactions mechanistically and therefore cannot
be used to predict wettability alteration under conditions that
dier from where the empirical relationships are derived.23
Thus, a mechanistic model is needed to understand the
dominant processes and to accurately predict wettability under
varying mineralogical.
Qiao et al.8 developed a mechanistic model that coupled
multiphase ow and transport using a detailed surface and
aqueous multicomponent reaction network including adsorp-
tion/desorption that captures the competitive interactions
among oil, brine, and the surface of the Stevns Klint chalk.
Natural carbonate reservoirs, however, often contain minerals
including anhydrite, dolomite, and quartz. These minerals could
potentially aect surface reactions among rock, oil, and water,
and therefore inuence the oil recovery. For example, Austad et
al.5 reported that anhydrite can play an important role in
wettability alteration.
In this paper, we extend the multiphase reactive transport
model by Qiao et al.8 to include limestone surface complexation
and mineral dissolution/precipitation reactions. This extends
the model in our in-house simulator PennSim24 to provide a
unied model for low-salinity ooding in mineralogically
dierent carbonate reservoirs. The model was calibrated using
core experimental data from the Stevns Klint chalk and
B DOI: 10.1021/acs.energyfuels.5b02456
Article
limestones with anhydrite. We rst introduce the multiphase
reactive transport equations, and then we describe the
wettability alteration model and the mechanisms of altered
wettability and oil recovery in dierent cores. Lastly, we use the
new model to demonstrate the potential of LSW ooding at the
eld pattern scale.
METHODOLOGY
We consider isothermal recovery processes with immiscible oil/water
ow. Geochemical reactions occur in the aqueous phase and at the
crude oil/brine-mineral interfaces. Desorption of the carboxylic group
from the rock surface leads to more water-wet conditions, which
further changes the relative permeability and residual oil saturation
based on measured curves at two wettability end points. The major
extension from our previous model8 includes the addition of calcite
and anhydrite dissolution/precipitation reactions, surface complex-
ation with the surface site >CO3 , and additional aqueous complexation
such as CaCl+ and NaSO4. [Note that the prex > denotes the
species at the solid surface.] In this section, we describe the governing
equations that couple the ow, transport and reaction system, and the
inputs to setup a simulation.
Governing Equations. The equation set describes the mass
conservation of oil/water and chemical species, Darcy ow, and
reaction kinetics and equilibrium. The physical meanings and units of
the symbols are given in the Nomenclature section.
Immiscible Oil/Water Flow Equations. The mass conservation
equations for immiscible oil and water phases are as follows:
(S ) + ( u ) = 0 = o, w
(1)
t
Darcys law governs the ow rate of each phase,
kr
u = K(P gZ) = o, w
(2)
The subscript w represents the water phase and subscript o
represents the oil phase. Capillary pressure relates the pressure of oil
and water phases:
Pcow = Po Pw (3)
The saturation relation completes the set of equations:
So + Sw = 1 (4)
The primary unknowns for the multiphase ow system are Po and Sw.
Reactive Transport Equations. The mass conservation equation for
the primary species p is
Nsec Nsec
(M p + qpMq) + (Fp + qpFq) = 0 p = 1 , ..., Np
t q=1 q=1
(5)
where the rst term is the accumulation of total moles and the second
term is the total molar ux of a primary component p, the chemical
building blocks of the reaction systems. The equations are based on
the stoichiometric relationship among the species participating in
reactions and reaction kinetics. The derivation of the reactive transport
equations are given in Qiao et al.8 More details of reactive transport
equations can also be found in Yeh and Tripathi,25 Lichtner,28 Steefel
and Lasaga,26 and Walter et al.27 These equations solve for the
concentrations of primary species in the aqueous phase and at the
phase interfaces. Secondary species are solved using laws of mass
action based on the concentrations of primary species. Reactive
transport models have been widely used in subsurface biogeochemistry
in the past decades;2831 however, they are relatively new in
applications of interest to the oil and gas industry.24,3234
Multiphase Reaction Network. Reactions are either kinetically
controlled or at equilibrium, depending on the typical rates of the
specic geochemical reactions. According to the geochemical
convention, the reactions in the aqueous phase and surface
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Table 1. Multiphase Reaction Networka

number reaction log Keq(25 C) log Keq(110 C)
Oil/Water Interface Reactions
O1 COOH COO + H+ 5.00 5.00
O2 +
COOCa COO + Ca 2+ 1.20 1.20
O3 +
COOMg COO + Mg 2+ 1.00 1.30
Solid (Calcite)/Water Interface Reactions
C1 > CaOH + H+ >CaOH+2 11.80 11.80
C2 > CaOH+2 + SO24 > CaSO4 + H 2O 2.10 3.25

C3 > CaOH+2 + CO32 > CaCO3 + H 2O 6.00 6.00

C4 > CO3H > CO3 + H+ 5.10 5.10

C5 > CO3Ca + > CO3 + Ca 2 + 2.50 3.40

C6 > CO3Mg + > CO3 + Mg 2 + 2.50 3.40

CalciteWater/OilWater Interface Reaction

CO1 > CaOH+2 ( COO) >CaOH+2 + COO 5.90
Aqueous-Phase Reactions
A1 H 2O H+ + OH 13.99 12.24
A2 HCO3 H + +
CO32 10.33 10.27

A3 H 2CO3 H+ + HCO3 6.35 6.43

A4 MgSO4 Mg 2+
+ SO24 2.37 2.46

A5 NaSO4 Na + + SO24 0.70 0.77

A6 CaSO4 Ca 2+
+ SO24 2.30 2.61

A7 +
CaCl Ca 2+
+ Cl 0.70 0.54
A8 +
MgCl Mg 2+
+ Cl 0.15 0.74
Mineral Dissolution/Precipitation Reactions
M1 CaCO3(s) + H Ca 2 + + HCO3
+ 1.85 0.58

M2 CaSO4 (s) Ca 2 + + SO24 4.36 5.34

a
Keq values for oil/water interface reactions are taken from Brady and Krumhansl;47 Keq for calcite surface reactions are taken from Pokrovsky and
Schott42 and Brady et al.;40 Keq for aqueous and mineral reactions are taken from Wolery.37 KCO1 was xed at 5.9 obtained from reproducing initial
wettability of Fathi et al.6 The kinetic rate constant for reaction M1 is 106.19 mol/(m2 s);59 the kinetic rate constant for reaction M2 is 102.95 mol/
(m2 s).60 The new additions in the reactions, compared to the previous model,8 include reactions C3C6, A4A8, M1, and M2.

complexation on the rock and oil surfaces typically occur fast and are ai = iCi
assumed to be at equilibrium.35 In contrast, mineral dissolution and
precipitation are relatively slow and modeled with reaction kinetics.36 Activity coecients are determined using an extended DebyeHuckel
The reaction network, along with the thermodynamic and kinetic model.38
constants at 25 and 110 C, are listed in Table 1. The primary species High Na+ and Cl concentrations reduce surface adsorption in two
include aqueous ions HCO3 , Cl, SO2 2+ 2+ +
4 , SCN , Mg , Ca , Na , K ,
+
ways. First, higher concentrations lead to greater ionic strength and
H+, and surface species > CaOH+2 , > CO3 and COO, where the smaller activity coecients of aqueous species (and, therefore, less
prexes > and represent the species at the solid surface and oil surface adsorption). Second, Na+ and Cl form aqueous complexes
surface, respectively. The extension from Qiao et al.8 includes calcite with SO2 2+ 2+
4 , Mg , and Ca through reactions A5, A7, and A8, which
surface reactions (reactions C4C6), aqueous reactions (reactions reduces the corresponding free-ion concentration available for surface
A4A8) and mineral dissolution/precipitation reactions (reactions M1 adsorption. Therefore, reducing Na+ and Cl concentrations can
and M2). The equilibrium constants for aqueous and mineral promote surface adsorption, which causes wettability alteration.
dissolution reactions are taken from the EQ3/6 thermodynamic Mineral Surface Reactions. We considered the surface dissolution/
database.37 precipitation of calcite and anhydrite (reactions M1 and M2 in Table
Aqueous Complexation Reactions in Water. The aqueous species
1). The mineral reaction rates are written based on the transition state
include free ions HCO3 , Cl, SO2 2+ 2+ + +
4 , SCN , Mg , Ca , Na , K , H ,
+
theory (TST) rate laws.39 For example, calcite dissolution rate is
CO23 , OH , and H2CO3 and complex ions MgSO4, NaSO4 , CaSO4,
expressed as follows:
CaCl+, and MgCl+. An example, the equilibrium constant of reaction
A4 is
E aCa 2 +a HCO3
R CaCO3(s) = A CaCO3(s)k H+ exp a a H+1
Keqa H +
a Mg 2 +aSO24 RT
Keq,A4 =
a MgSO
4
The last term in the parentheses in the above equation indicates how
where the activities of the aqueous species (ai) are calculated by far away the reaction is from equilibrium. If the reaction is at

C DOI: 10.1021/acs.energyfuels.5b02456
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equilibrium, the rate is zero. The Damkohler number (D) for this
reaction is calculated as
R CaCO3(s)
Da ,CaCO3(s) =
vCCa 2 +,total
where v is the ow velocity and C Ca 2+,total is the total Ca 2+
concentration. The Damkohler number determines if the reaction is
modeled using an equilibrium law or a kinetic rate law. Calcite
dissolution provides a source for Ca2+ species and buers pH. The
calculated Damkohler number for anhydrite dissolution is more than
100 in the experimental cases studied later in this paper, indicating
much faster dissolution rates than transport. Therefore, the anhydrite
dissolution reaction is modeled at equilibrium. Anhydrite dissolution is
an important source or sink for sulfate and calcium.
In addition to the mineral dissolution reactions, we also consider
the surface adsorption/desorption reactions on a calcite surface.
Surface complexation models are typically used to describe the surface
reactions.4043 A calcite surface contains sites >CaOH and >CO3H
that can adsorb aqueous ions and carboxylic groups and form surface
species >CaOH2+, >CaSO4 , >CaCO3, >CO3, >CO3Ca+, and
>CO3Mg+.44 In this research, two models are used to describe the
surface reactions: the electrical diusive layer (EDL) and the
nonelectrical diusive layer (NEDL) model (the latter of which is
also called the constant capacitance model).43,45 We used the relatively
simple-to-implement NEDL model when the change of surface
potential does not have a signicant eect. The EDL model is used
when there are signicant surface potential changes, because of surface
adsorption. Thus, the EDL model also aects the surface adsorption
equilibrium. In the EDL model, the activity of an aqueous species is
corrected through a Boltzmann factor, so the equilibrium constant for
reaction C2 is expressed as follows:
2F
K C2 =
( )
exp RTs [>CaSO4 ]
[>CaOH+2 ]aSO24
Here [>CaSO4 ] and [>CaOH+2 ] are the surface concentrations (in
units of mol/m2). The surface potential (s) is calculated from the
GouyChapman theory,
F
s = 80mIRT sinh s
2RT
In the NEDL model, s is considered constant. The equilibrium
constant for reaction C2 can be written then as
[>CaSO4 ]
K C2 =
[>CaOH+2 ]aSO24
here the constant surface potential term is lumped into KC2. A
sensitivity analysis in Qiao et al.46 demonstrated the strong
dependency of the oil recovery on the equilibrium constants. For
aqueous reactions, the Keq values are well-documented for a large
range of temperature. For surface complexation, the Keq values are
empirical parameters related to intrinsic thermodynamic constants.45
The solid surface site densities for >CaOH and >CO3H are xed at 4.1
mol/m2, based on a previous simulation study.40
Oil/Water Interface Reactions. The active species on the oil/water
interface include COOH, COO, COOCa+, and COOMg+.
The NH4 oil surface sites are not included here because COO
dominates the interaction between oil and water surfaces.40 Oil surface
complexation reactions are described by either NEDL or EDL in a
similar way as mineral surface reactions. Temperature eects for
reactions on the oil surface are not considered to be as signicant.47
The surface oil site total concentrations are xed at 6 mol/m2.48
Interfacial Interactions and Wettability Alteration. The calcite-
water/oil interface reaction is represented by reaction CO1. The
species >CaOH+2 (COO) is the adsorbed carboxylic group on the
calcite surface. When the reaction goes from left to right,
>CaOH+2 (COO) desorbs and the system becomes more water-
Article
wet, as observed in low-salinity waterooding. If the reaction goes
from right to left, the system becomes more oil-wet, as observed
during the aging of crude oil. This reaction is reversible over the time
scale of core ooding, as shown in a recent experimental paper by
Hopkins et al.49 at a temperature of 50 C. Reaction CO1 happens fast
at high temperature but is much slower at room temperature.1,5052
This reaction is assumed to be reversible at high temperature (110
C). For simulation of the chromatographic wettability test at 25 C,
we assumed irreversibility during the duration of the experiments (3
h). The equilibrium constant of this reaction is not known in the
literature, so we used this parameter as a tuning parameter. In this
research, the value of KCO1 was xed at 5.9, as obtained from
reproducing the initial wettability of Fathi et al.,6 and this value was
used for all other simulations. Therefore, the surface concentration of
>CaOH2+(COO) is a wettability indicator: the higher this
concentration, the more oil-wet the solid surface. The wettability
indicator () is calculated from
c c ww
=
cow c ww (6)
where c, c ww , and c ow are the surface concentrations of
>CaOH+2 (COO) at the current state, the end-point water-wet
state, and the oil-wet state, respectively. Values of cww and cow are
obtained by speciation calculation at the initial and injection water
compositions.
For relative permeability values, we use the following linear
interpolation model:
* = (1 )k rw,ww
k rw * *
+ k rw,ow
* = (1 )k ro,ww
k ro * + k ro,ow
* (7)
* , krw,ow
where kro,ow * , kro,ww
* , and krw,ww
* are relative permeability values at
the end-point oil-wet (ow) and end-point water-wet states (ww).
These end-point states are not required to be completely oil-wet or
water-wet, but ideally should be measured under initial reservoir
conditions (mixed wet state) and at the most water-wet state possible.
The BrooksCorey model is used to calculate relative permeability at
any arbitrary saturation between the end points,53
* (S*)n w
k rw = k rw
*(1 S*)no
k ro = k ro
where the normalized water saturation (S*) is calculated as
Sw Swi
S* =
1 Swi Sor
Here, Swi is the irreducible water saturation and Sor is the residual oil
saturation. Alteration of the wettability can change the contact angle,
which reduces the capillary number and then the residual oil
saturation. Residual oil saturation has been shown to change during
low salinity waterooding, as shown in the works of Nasralla et al.10
and Morrow et al.54 Therefore, Sor is a function of wettability, as
follows:
Sor = (1 )Sorww + Sorow
Figure 1 shows two examples of relative permeability curves
measured or calculated under end-point wettability conditions.
Relative permeability end points under other wettability conditions
are determined using eq 7. Ideally, the relative permeability curves
should be measured at the end-point wettability states. Capillary
pressure is also important when the capillary number is large.
However, most of the coreooding experiments do not report the
relative permeability and capillary pressure curves. In this paper,
relative permeability curves at the end points were determined by the
best t to the measured oil recoveries, because data were not available.
The capillary pressure is assumed to be zero, since the relative
permeability curve is tuned, and we prefer not to have more tuning
parameters. The capillary pressure eects are specically studied for
D DOI: 10.1021/acs.energyfuels.5b02456
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Figure 1. Relative permeability curves at the end-point wetting states
used in the simulations of the core ooding experiments in (A) Fathi
et al.,6 with 100% volume fraction of calcite, and (B) Yousef et al.,2
with 3% anhydrite. In both cases, Swi remains constant when the
wettability changes. The Sor values decrease more in panel (B) than in
panel (A). The curves for panel (A) show signicantly less changes in
the relative permeability curves, compared to panel (B), because the
core in Fathi et al.6 is initially more water-wet than the core in Yousef
et al.2
spontaneous imbibition in a previous publication.8 Experimental
studies also shows that the change in Swi is negligible for high-salinity
water and LSW.55 The initial water saturation was assumed to be
constant. The water saturation remains high after alteration of the
wettability. Even Swi changes, the oil recovery will not be aected.
Simulation Cases. Table 2 lists the mineralogical compositions
and parameters for the limestone and chalk cores. The Stevns Klint
chalk in Fathi et al.6 and the Middle Eastern limestone in Strand et
al.56 contain pure calcite, with 100% volume fraction in the solid phase.
In contrast, the limestone cores from Austad et al.5 and Yousef et al.2
contain anhydrite. In these experiments, kr curves were not measured.
A practical workow for simulation of core ooding experiments
where relative permeability curves are not measured is given as follows.
(1) Tune kro, krw, and Sor at the original wetting state to match oil
recovery with injection of formation water where wettability
alteration does not occur.
(2) Tune Sor at the end-point water-wet case to match ultimate oil
recovery.
(3) Perform speciation calculations given the formation water
composition to obtain cow. Namely, solve the nonlinear
equation systems that describe the equilibrium condition of
all reactions and conservation of the total concentration as the
formation water. Perform speciation calculation given the LSW
that leads to the most water wettability to obtain cww. Select
either the NEDL or the EDL model so that cow > cww.
(4) Perform simulations using the end-point parameters obtained
in steps 1, 2, and 3.
Reaction equilibrium constants are xed for simulation of all
experiments. We conduct one-dimensional (1-D) simulations of core
ooding experiments in dierent carbonate rocks listed in Table 2.
The 1-D simulation domains were discretized uniformly into 100 grid
blocks, which is the minimum number of grid blocks needed to
reproduce the tracer breakthrough curves in the chromatographic
wettability test. Oil and water viscosities were xed at 1.0 and 0.476 cP,
respectively. We also used the reactions and tuned parameters from
the 1-D core oods to model two-dimensional (2-D) ve-spot
patterns.
RESULTS AND DISCUSSION
Stevns Klint Chalk Outcrop (No Anhydrite). The Stevns
Klint chalk is comprised of 55% (volume) calcite with 45% pore
space. The wettability can be altered by injection of ions that
causes the oil acids to desorb from the surface, changing the
rock to a more water-wet state. Austad et al.1 demonstrated this
in imbibition tests where a core plug was immersed by aqueous
solution containing SO42. Forced displacement experiments
(core oods) also show that chemically tuned seawater
injection leads to increased oil recovery in the same cores.6

Table 2. Input Parameters for Simulation of Core Flooding Experimentsa

Fathi et al.,6 Yousef et al.,2
SCC#1 Strand et al.,56 Core 2-21 Austad et al.,5 Core 5B 1st core ooding
core material Stevns Klint chalk Middle Eastern Limestone from the aqueous zone of an oil Middle Eastern limestone
limestone reservoir
mineral volume fraction 55% calcite 75% calcite 79% calcite, 3% anhydriteb 71% calcite, 3% anhydritec
porosity 0.45 0.25 0.18 0.25
permeability 1.0 mD 2.7 mD 1.2 mD 39.6 mD
specic surface area
calcited 1.00 m2/g 0.29 m2/g 0.29 m2/g 0.29 m2/g
anhydrite 1.0 m2/g 1.0 m2/g
dimensions
length, L 70.0 mm 49.0 mm 81.0 mm 40.6 mm
diameter, D 38.1 mm 37.8 mm 38.0 mm 38.0 mm
back pressure 145 psi 101.5 psi 145 psi 1000 psi
temperature 25 C 70 C 110 C 100 C
injection rate 0.20 mL/min 0.10 mL/min 0.01 mL/min 1.00 mL/min
surface complexation model NEDL NEDL NEDL EDL
cwwe 0.40 mol/m2 1.35 mol/m2 0.03 mol/m2
cowe 2.1 mol/m2 1.67 mol/m2 0.17 mol/m2
diusion/dispersion 0.0042 ft2/day 0.0020 ft2/day 0.0020 ft2/day 0.0020 ft2/day
coecientf

a
Values were taken from the reference listed in the rst row, unless otherwise specied. bThe 3% anhydrite was speculated, according to Austad et
al.5 cYousef et al.2 reported that the crushed powder is composed of 80% calcite, 13% dolomite, 6% anhydrite, and <1% quartz. The composition
used in simulations was calculated for the porous media and by lumping dolomite with calcite without dierentiating between the two. dThe specic
surface area for limestone was taken from Shariatpanahi et al.61 eThe end-point concentrations were obtained from speciation calculations with water
compositions at end-point oil-wet and water-wet states. fThe diusion/dispersion coecient was determined from tracer euent concentration
curves.

E DOI: 10.1021/acs.energyfuels.5b02456
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Table 3. Synthetic Brine Compositions Used in Experiments and Simulationsa

FWb SWb SW0NaClb SW0NaCl4SO4b SW1/2Mc NaCl-Mc FWd seawatere
ion concentration (mol/kg water)
HCO3 0.009 0.002 0.002 0.002 0.002 0.000 0.003 0.002
Cl 1.070 0.525 0.126 0.126 0.574 0.556 3.643 0.907
SO42 0 0.024 0.024 0.096 0.012 0.013 0 0.044
SCN 0 0 0 0 0.012
Mg2+ 0.008 0.045 0.045 0.045 0.045 0.013 0.076 0.088
Ca2+ 0.029 0.013 0.013 0.013 0.013 0.013 0.437 0.016
Na+ 1.000 0.450 0.050 0.194 0.475 0.504 2.620 0.796
K+ 0.005 0.010 0.010 0.010 0.022
pHf 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4
total ionic strength 1.116 0.658 0.258 0.474 0.682 0.608 4.159 1.149
a
Legend: FW, formation water; SW, seawater; SW0NaCl, seawater depleted in NaCl; SW0NaCl4SO4, SW0NaCl with four levels of sulfate; SW1/
2M, seawater that contains SCN and half the amount of SO42 in SW; and NaCl-M, NaCl solution with equal amounts of Ca2+, Mg2+, and SCN.
b
Data taken from Fathi et al.6 cData taken from Strand et al.56 dData taken from Austad et al.5 eData taken from Yousef et al.2 fThe pH was not given
in the original references; here, we used a pH value of 8.4, following the pH in the chemically tuned water in the work of Zhang et al.9

Chromatographic Wettability Test. In chromatographic
wettability tests, seawater with dierent compositions (SW1 in
Table 3) is injected into a formation-water-saturated core and a
core initially at residual oil saturation (here, Sor = 0.25). The
purpose of chromatographic wettability tests is to quantify the
adsorption of sulfate. Figure 2A shows the breakthrough curves
Figure 2. Breakthrough curves for seawater injection into water-wet
cores at room temperature: (A) SCN and SO42 breakthrough curves
(BTCs) from experiments6 and simulations without oil, (B) Ca2+ and
Mg2+ BTCs from simulations without oil, (C) SCN and SO42 BTCs
from experiments6 and simulations in the presence of residual oil, and
(D) Ca2+ and Mg2+ BTCs from simulations with oil. C0 is the injection
concentration of the corresponding species.
in a reference water-wet core without oil. The diusion/
dispersion coecients (0.0042 ft2/day) were determined by
reproducing the breakthrough curves (BTCs) of the non-
reactive tracer SCN. The area between the BTCs for SCN
and SO42 quanties the amount of adsorbed SO42, as
discussed in Zhang et al.,9 which essentially measures the
amount of surface sites available and the water-rock contact
surface area.
F DOI: 10.1021/acs.energyfuels.5b02456
We included all reactions in the simulations, except reaction
CO1, because, at room temperature, the oil surface reactions
were assumed to be inactive. Two simulations were performed
to reproduce the experimental breakthrough curves6 with and
without residual oil. The cores were lled with formation water
initially. Figure 2B shows the predicted Ca2+ and Mg2+
concentrations. Because the injected seawaterwater contains
more Mg2+ and less Ca2+ than the formation water does, more
Mg2+ adsorbed on the calcite surface, replacing adsorbed Ca2+
as the seawater contacted the rock surface, causing the Ca2+
concentration peak near 1.0 PVI. This is consistent with
experimental observations.6,9 Both concentrations eventually
returned to the injection concentrations.
Figure 2C shows the BTCs for cores at a residual oil
saturation of 0.25. The surface area that is in direct contact with
the aqueous phase is smaller than at the saturated conditions
without oil, leading to a smaller dierence between the SCN
and SO42 curves. The SCN and SO42 breakthrough earlier
than those in Figure 2A, because of the immobile residual oil
and less available pore space for ow and less surface area for
adsorption. The predicted Mg2+ and Ca2+ concentrations in
Figure 2D are similar to those depicted in Figure 2B, except
with an earlier and a smaller Ca2+ peak. The match of the BTCs
with and without oil shows the validity of the model and
parameters relevant to the physical processes when no oil
reactions are included.
Forced Displacement. Forced displacement experiments
were performed with successive injection of formation water
(FW), seawater (SW), and seawater depleted in NaCl
(SW0NaCl).6 The initial water saturation is 0.08.
Simulation studies are performed in two ways. Simulation A
injected FW, SW, and SW0NaCl successively in Table 3; in
simulation B, NaCl solution was injected with the same total
molality of FW, SW, and SW0NaCl. As shown in Figure 3A,
simulation A closely reproduced the experimental data. The oil
recovery for simulation B, however, indicates that without
SO42, Ca2+, and Mg2+, oil recovery was the same, even though
the injection water has increasingly lower salinity. This indicates
that, for the Stevns Klint chalk, it is the chemical composition
of the injected water that matters, not salinity. This is very
dierent from core ooding in limestones, where lower salinity
has been shown to improve oil recovery.2,10,19,52
Figure 3B shows the predicted BTCs of total SO42,
>CaSO4, and >CaOH2(COO), as well as the pH for
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Figure 3. (A) Oil recovery from experiments and simulations for
forced displacements with successive injection of FW, SW, and
SW0NaCl. The experimental data are taken from Fathi et al.6 (B) The
dimensionless concentration of total SO 4 2 , >CaSO 4 , and
>CaOH2(COO) for simulation A. C0 = 0.024 mol/kg water for
SO42, and 4.1 mol/m2 for surface species, >CaSO4, and
>CaOH2(COO).
simulation A. During the FW injection, >CaOH2(COO)
maintained a high concentration while no sulfate sorption
occurred (>CaSO4 = 0). During the SW injection, the euent
concentrations and oil recovery did not change much until the
seawater reached the outlet at 3.0 PVI, when the total
concentration of SO42 increased with increasing >CaSO4 and
decreasing >CaOH2(COO). The high anity of sulfate to the
calcite surface, indicated by higher surface concentrations of
>CaSO4 than >CaOH2(COO), leads to increased oil
recovery between 3.0 PVI and 4.0 PVI. From 4.0 PVI to 6.0
PVI, SW0NaCl was injected with the same SO42 concentration
as in the SW case, but without NaCl. With the decrease in ionic
strength, SO42 activity increased so that the surface
concentration of >CaSO4 increased further while the aqueous
total SO42 decreased. With continued SO42 injection, the
total concentration eventually increased back to the inlet
concentration at 5.0 PVI. The increased sulfate adsorption
reduces >CaOH2(COO), which causes the observed change
in wettability toward a more water-wet state and the increased
in oil recovery. The predicted SO42 and >CaOH2(COO)
concentrations are consistent with the chemical mechanism
proposed by Austad et al.1 The pH of the euent solution
changes between 6.5 and 9.5 and is responsive to the changes in
injection water composition. Euent pH increased during the
SW slug and decreased during the SW0NaCl slug. After 3
PVI, the pH change mirrored the change in >CaSO4, indicating
the dominant control of SO42 sorption on the pH of the
system.
Limestone without Anhydrite from Strand et al.56 The
selected limestone core was composed of 75% calcite and 25%
pore space by volume. Thus, most of the reactions are the same
as those for the SK chalk. The limestone has a lower specic
surface area (0.29 m2/g), compared to that of chalk (1.00 m2/
g).
Chromatographic Wettability Tests. To explore the anity
of SO42 toward the limestone surface, a chromatographic
wettability test for a completely water-wet core is simulated. In
the test, seawater that contains SCN and half of SO42 of SW
(SW1/2M) was injected (Table 3). A smaller diusion/
dispersion coecient (0.002 ft2/day) than the SK chalk was
obtained by reproducing the BTC of SCN. As shown in
Figure 4A, the predicted SO42 concentration agrees well with
the concentration data. The similarity between Figure 4A and
Figure 2A indicates that the same equilibrium constants can be
G DOI: 10.1021/acs.energyfuels.5b02456
Article
Figure 4. Breakthrough curves (BTCs) of chromatographic wettability
tests in limestone cores:56 (A) SCN and SO24 at 25 C and (B)
SCN, Ca2+, and Mg2+ at 70 C.
used to describe sulfate adsorption in limestone and in SK
chalk.
Surface Adsorption Test for Ca2+ and Mg2+. A NaCl
solution with equal amounts of Ca2+, Mg2+ and SCN (NaCl-
M, see Table 3) was injected to test the calcite surface
adsorption of Ca2+ and Mg2+ in a similar chromatographic
wettability test.56 As shown in Figure 4B, the breakthrough
times of Ca2+ and Mg2+ are longer than SCN, indicating that
Ca2+ and Mg2+are adsorbed on the surface. The adsorption
reactions are independent from SO42 adsorption and the
carboxylic group, as the adsorption is observed without SO42
and oil acids. Figure 4B shows the comparison of experimental
and predicted BTCs for SCN, Ca2+, and Mg2+ at 70 C. The
BTCs were matched with tuned KC5 and KC6 (2.1 for both
reactions), because of the increased temperature using the
NEDL model, while other reaction parameters are the same as
that in the simulation of Fathi et al.6
The two simulations of the chromatographic wettability tests
indicated no signicant dierence between chalk and limestone,
regarding the surface reactivity behaviors of Ca2+, Mg2+, and
SO42. The dierence in adsorption is a result of dierent
porosity and specic surface area. That is, we can use the same
reaction network listed in Table 1 to describe the surface
complexations on the Stevns Klint chalk6 and the Middle
Eastern limestone surfaces.56
Limestone with Anhydrite. Anhydrite dissolution was
reported in some low-salinity core oods and was regarded as
the cause of the alteration in wettability when the injection
uids do not contain sulfate. Here, we examine our model
results for two cases.
Forced Displacement in Limestone Core with Anhydrite
from Austad et al.5 Diluted formation water was found to
improve oil recovery in limestone cores.5,2,10 Austad et al.5
observed tertiary IORs of 5% OOIP in limestone rocks with
diluted formation water containing no sulfate. Sulfate was
detected in the euent when the core was ooded with
deionized water, conrming the presence of anhydrite. The
increased SO42 concentration from dissolved anhydrite likely
led to the wettability alteration and increased IOR. To test this
hypothesis, we simulated the forced displacement experiments
in Austad et al.,5 where formation water (FW) and 100-times-
diluted formation water (100 diluted FW) were injected
successively.
Figure 5A shows that simulation A with anhydrite dissolution
reproduced the incremental oil recovery with 100 diluted FW.
In simulation B, where anhydrite dissolution was removed,
Figure 5A indicates that the diluted FW does not lead to IOR.
Figure 5B shows the predicted total euent concentration of
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Figure 5. (A) Oil recovery for forced displacements in cores with
anhydrite dissolution (simulation A) and without anhydrite dissolution
(simulation B). (B) Breakthrough curves of Ca2+, total Ca2+, SO42,
and total SO42 from simulation.
Ca2+ and SO42 for simulation A. Upon the injection of 100
diluted FW, Ca2+ concentrations decreased while SO42
concentrations increased. Since the injection water does not
contain SO42, the total SO42 concentration indicates how
much anhydrite is dissolved. As shown in Figure 5B, total
SO42 did not change much when the injection uid
composition was changed at 6.0 PVI. This is because the
lower Ca2+ concentration in the injection water increased
anhydrite dissolution while a smaller ionic strength decreased
anhydrite dissolution. The net result is that anhydrite
dissolution remained almost the same as that indicated by the
almost-constant total SO42 concentration. The concentration
of free SO42, however, increased by more than one order of
magnitude, because Na+ and Ca2+ concentrations decreased
with the 100 diluted FW, so that less aqueous complexation
of NaSO4 and CaSO4(aq) were formed. Thus, additional free
SO42 was available to adsorb onto the solid surface to replace
adsorbed oil acids, leading to an increased oil recovery of 5%
OOIP.
Forced Displacement in Composite Limestone with
Anhydrite in Yousef et al.2 Yousef et al.2 observed 20%
OOIP incremental oil recovery with successive injection of
seawater, 2 diluted seawater, and 10 diluted seawater into
composite limestone cores. Anhydrite dissolution was veried
in their experiments using nuclear magnetic resonance (NMR)
measurements. The cores were originally oil-wet. The NEDL
model failed to predict any alteration of wettability in our rst
attempt. An EDL model, however, reproduced the data,
indicating the importance of including the surface potential
changes in simulations with brines of dierent ionic strength.
Figure 6A shows that the model reproduced oil recovery
data. Figure 6B shows the predicted breakthrough curves
Figure 6. (A) Oil recovery for forced displacement from core oods
(Yousef et al.2) and simulation. (B) Euent concentration of chemical
species. The units for Na+, total SO42 and free SO42 concentration
are mol/kg water. The units for >CaOH2(COO) concentration are
mol/m2.
H DOI: 10.1021/acs.energyfuels.5b02456
Article
(BTCs) of Na + , SO 4 2 , and the concentration of
>CaOH2(COO) and >CaSO4. Stepwise decreases in Na+
concentration are due to the slug injection of diluted seawater.
The concentration of >CaOH2(COO) also decreased
stepwise, demonstrating the change in wettability to more
water-wet states. Because the concentration of >CaSO4 also
decreased, the reason for the decrease in >CaOH2(COO) is
not due to the competition by SO2 4 adsorption. A lower ionic
strength leads to a smaller solid surface potential and less
adsorption of the negatively charged carboxylic group.
Comparison of Chalk and Limestones. Using the same
input parameters for the previously discussed cases, we
compare predicted oil recoveries for the dierent cores with
the same injection water composition. The core oods for
dierent mineralogies were modeled with the same parameters
in NEDL as shown in Figures 3A and 5A; core oods for
dierent mineralogies with the same parameters in EDL were
modeled as shown in Figure 6A.
Figure 7A compares the oil recovery of chalk6 from limestone
A (Austad et al.5) and limestone B (Yousef et al.2), both
Figure 7. (A) Oil recovery for chalk, limestone A, and limestone B
when seawater, 2 diluted seawater, and 10 diluted seawater were
injected. (B) The ratio of the breakthrough concentration of adsorbed
carboxylic acids >CaOH2(COO), with respect to its initial
concentration for each case in panel (A). (C) Oil recovery for chalk,
limestone A, and limestone B; formation water (FW) and 100
diluted FW were injected. (D) The ratio of the breakthrough
concentration of adsorbed carboxylic acids >CaOH2(COO), with
respect to its initial concentration at the condition of panel (C).
Simulation input parameters are the same as those in Figure 3A for
chalk, Figure 5A for limestone A, and Figure 6A for limestone B.
containing anhydrite. The same injection sequence as that
reported by Yousef et al.2 was used. Unlike limestone B, chalk
and limestone A show little IOR with the injection of diluted
seawater. Figure 7B shows the predicted adsorbed carboxylic
acid at the euent point. All three cores have decreased
>CaOH2(COO) at 1.0 PVI with seawater injected. With 2
and 10 diluted seawater injection, limestone B shows
decreased >CaOH2(COO), indicating a more water-wet
state. Chalk and limestone A have an increased concentration
of >CaOH2(COO), indicating a more oil-wet rock because
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the sulfate concentration decreased as seawater was diluted
(even after anhydrite was dissolved). Limestone A and
limestone B show signicantly dierent behavior. The dierent
IOR for limestone A and limestone B results from the use of
NEDL for limestone A, while EDL is used for limestone B.
Figure 7C compares the oil recovery of the three cores with
FW and 100 diluted FW injected. Both limestone A and
limestone B show increased oil recovery, although the extent of
the increase is much smaller in limestone A. The dierences in
IOR might be caused by shifts in relative permeability curves,
which should be measured for each core. In contrast, no IOR is
observed for chalk. The >CaOH2(COO) concentrations in
Figure 7D indicate that wettability alteration occurs for
limestones but does not occur for chalk, because of the lack
of anhydrite dissolution. The dierent responses of the chalk
and limestones to the same injection water indicate the
importance of anhydrite dissolution.
Extension to the Field Scale Injection. One concern in
the core ood using LSW is the large pore volumes that are
injected (for example, 30 PVIs in Yousef et al.2) to achieve a
signicant increase in oil recovery. To examine this, we
simulated a quarter of a ve-spot pattern using PennSim with
the reaction network and parameters that reproduced core
ood experiments (see Tables 1 and 2). Two homogeneous
models and one heterogeneous model were simulated. The
pattern size of 300 ft 300 ft for all three models was
discretized into uniform 20 20 grid blocks. No gravity is
included. The rst two homogeneous models used the input
parameters of core ood experiments of Austad et al.5 and
Yousef et al.,2 respectively. The heterogeneous model used the
same porosity, mineral composition, and end-point relative
permeability of Yousef et al.2 and the permeability eld was
taken from an upscaling of the 41th layer of the permeability
eld in a SPE10 comparative solution project.57 The original
permeability was for 60 220 grid blocks and was coarsened
into 20 20 grid blocks. The grid coarsening was done by
combining 3 11 ne grid blocks into one coarse grid block.
The permeability was calculated by using an arithmetic mean.
PennSim results for the 2-D ve-spot pattern cases matched
exactly with simulations using Eclipse for FW injection without
wettability alteration.
Figure 8A compares the oil recovery curves for the 1-D
homogeneous core oods and 2-D homogeneous ve-spot
patterns. Breakthrough in the 1-D simulations is delayed
slightly compared to the 2-D model for both FW and 100
diluted FW injection water. Breakthrough is somewhat quicker
in the 2-D homogeneous model, because of poorer sweep.
Figure 8. Oil recoveries for 1-D core oods and 2-D ve-spot patterns
in a homogeneous limestone reservoir, using (A) parameters of core
ood experiments from Austad et al.5 and (B) parameters of core
oods from Yousef et al.2
I DOI: 10.1021/acs.energyfuels.5b02456
Article
Sweep is excellent in the 2-D models, however, so that ultimate
oil recovery quickly approaches the 1-D values. This is expected
since the mobility ratio is favorable in these oods (end-point
mobility ratios are 0.5). For both the 1-D and 2-D cases, the
injection of 100 diluted FW produces 5% OOIP more oil
recovery than injection of FW at 2.0 PVI. This increase is
signicant and demonstrates that recovery can be enhanced
with a realistic volume of water being injected.
Figure 8B shows the oil recovery of SW and 10 diluted SW
injection for the same 1-D core and 2-D ve-spot models. For
both injection uids, the 2-D ve-spot patterns exhibits smaller
oil recovery at 2.0 PVI than the 1-D core oods. For both 1-D
and 2-D cases, injection of 10 diluted SW leads to 20%
OOIP more oil recovery at 2.0 PVI than the injection of SW
alone.
Figure 9A shows the permeability eld for a heterogeneous
2-D reservoir. The permeability eld contains a high-
Figure 9. Simulations for 2-D heterogeneous ve-spot pattern: (A)
permeability eld and (B) oil recoveries for 2-D ve-spot patterns
(obtained using the same parameters as those in Figure 6B).
permeability channel and therefore injection water break-
throughs occur much faster. Figure 9B shows a signicantly
decreased oil recovery and earlier breakthrough, compared to
the homogeneous case, because of poor sweep eciency,
although the benet of using LSW remains large (6% OOIP).
The CPU time for the entire simulation on a MacBook Pro
(Intel i5 2.3 GHz, 2011 version) was 307 s.
Comparison with Previous Model. The reaction network
used in this paper is extended from a previous model.8 With
more reactions, the current model is compared with the
previous model for the case of ow in chalk and a series of
injection brine compositions including formation water (FW),
seawater (SW), SW depleted in NaCl (SW0NaCl), and
SW0NaCl with four levels of sulfate (SW0NaCl4SO4). The
brine composition is shown in Table 3. As is shown in Figure
10 for the current model with and without calcite dissolution,
the simulations reproduce the decrease of >CaOH2(COO)
concentration on the rock surface. This indicates that the
current model and the previous model predict the same trend
of wettability alteration with the tested brine compositions. The
eect of calcite dissolution is also tested, since calcite
dissolution was regarded as being important during seawater
injection processes.58 Figure 10 also indicates that although
calcite dissolution is important when FW is injected, it does not
aect the trend of wettability alteration.
Model Limitations and Potential Improvements. The
model developed here oers a promising pathway to move
forward with regard to understanding the chemical mechanisms
for wettability alteration during low-salinity waterooding. The
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Figure 10. Comparison of the calculated surface fraction of
>CaOH2(COO) for chalk from extended and previous models.46
Blue bars represent the values calculated by the previous model; red
bars represent the values calculated by the current model; and green
bars represent the values calculated by the current model, but without
calcite dissolution.
current model does have some limitations that may aect the
predictive capability of this model.
Four mechanisms of interaction between crude oil, brine, and
solid surfaces have been reported in the literature, including
polar, surface precipitation, acid/base and divalent/multivalent
ion binding.23 Here, we focus on the acid/base mechanism. We
did not include ion binding because there is a lack of
experimental and thermodynamic data for ion-bridging
interaction. Moreover, it is challenging to study those
mechanisms independently.
The use of EDL and NEDL models to reproduce the
experiments for limestone A5 and limestone B2 is not desirable.
This indicates that the key dierence between dierent forms of
CaCO3, limestone and chalk, should be identied. Collection of
detailed aqueous geochemical data, including Ca2+, Mg2+, and
SO42 concentrations, and pH at the euent, as well as
measuring zeta potential at the oil and rock surface at high
pressure and high temperature, will also allow further
constraints on the geochemical reaction network.
CONCLUSIONS
In this research, we extended a previous mechanistic wettability
alteration model to understand and predict the improved oil
recovery (IOR) from low-salinity waterooding for dierent
cases, including seawater injection in the Stevns Klint chalk, and
diluted formation water and seawater injection in limestone
cores containing anhydrite. The extension of the reactions
include adding calcite and anhydrite dissolution, the sorption of
Ca2+ and Mg2+ on the calcite surface, and aqueous complex-
ation. The new model was incorporated into an in-house
simulator PennSim, providing a unifying explanation of the
recoveries observed under low-salinity waterooding conditions
in carbonate reservoirs.
The results show that, with little tuning, the new model can
capture the role of mineral reactions in buering the aqueous
composition and could accurately predict wettability alteration
and recoveries, because of surface reactions. The main overall
conclusions are as follows:
(i) The 1-D chromatographic wettability tests for the SK
chalk and limestone cores were simulated. The predicted
J DOI: 10.1021/acs.energyfuels.5b02456
Article
euent concentration matched well with the experimental
measurements.
(ii) Forced displacement experiments for the SK chalk and
limestone cores were also simulated. The predicted oil
recoveries also matched the experimental measurements well.
The predicted euent concentrations were consistent with
experimental measurements.
(iii) Simulation of secondary recoveries for the 1-D core
ooding models and 2-D ve-spot models ranged from 5% to
20% OOIP at 2.0 PVI, using diluted formation water or diluted
seawater. More importantly, the 2-D models demonstrated that
LSW can yield excellent increases in recovery at realistic pore
volumes injected (PVI).
Additional important conclusions include the following:
The same set of reactions can be used for the wettability
alteration model.
The prediction of wettability alteration using the
mechanistic model is accurate for the demonstrated
experimental studies.
Coreooding experiments are lacking all data needed to
predict recovery. Relative permeability curves should be
measured at two wettability states.
The nonelectrical double layer (NEDL) model cannot
capture wettability alteration in the core oods of Yousef
et al.2 The electrical double layer (EDL) model was
required instead.
In limestone cores with anhydrite,5 diluted water reduces
ion strength and aqueous complexation of sulfate with
cations. This enhances anhydrite dissolution and the
availability of free SO42, thereby improving the oil
recovery. The simulation for the same limestone core but
without anhydrite does not show IOR.
The IOR at 2.0 PVI for 1-D core oods and 2D ve-spot
models is dependent on the rock mineralogy.
This is the rst mechanistic model for carbonate rocks that
considers the coupling of mineral dissolution and surface
complexation reactions to predict low-salinity waterooding
recoveries and wettability changes for both chalk and limestone
cores, with and without anhydrite. Other minerals could be
added as needed in the reaction network for reservoir
formations with dierent type of lithology.
AUTHOR INFORMATION
Corresponding Author
*E-mail: changheqiao@gmail.com.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
The authors gratefully thank the member companies of the Gas
Flooding JIP in the EMS Energy Institute at The Pennsylvania
State University at University Park, PA for their nancial
support. Russell T. Johns holds the Victor and Anna Mae
Beghini Faculty Fellowship in Petroleum and Natural Gas
Engineering at The Pennsylvania State University.
NOMENCLATURE
ai = activity of species i (dimensionless)
A, B = temperature-dependent parameters for the Debye
Huckel model (kg water1/2/mol1/2)
d = temperature-dependent parameter for the Debye
Huckel model (kg water/mol)
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As = bulk surface area of mineral species s (m2)
D = diusion/dispersion coecient tensor (ft2/day or m2/s)
Ea = activation energy (Btu/lb-mol or J/mol)
F = Faradays constant; F = 9.648 104 C/mol
Fp = molar rate of the primary species p (mol/(m day))
Fq = molar rate of the secondary species q (mol/(m day))
g = standard gravitational constant (ft/day2 or m/s2)
I = ionic strength of water (mol/kg water)
Keq,r = equilibrium constant of reaction r
K = permeability (md or m2)
ks = reaction rate constant (mol/m2s)
krj = relative permeability of phase j
Mp = molar density of the primary species p (mol/m3)
Mq = molar density of the secondary species q (mol/m3)
Np = number of primary species
Ntot = total number of species
Nsec = number of secondary reactions
Pj = pressure of phase j (psi or Pa)
Pcj = capillary pressure between phase j and a reference phase
(psi or Pa)
Qp = total molar rate of primary species p (lb-mol/day or
mol/s)
R = universal gas constant; R = 8.31 J/(mol K) or 10.73 ft3
psi/(R lb-mol)
Sj = saturation of phase j (dimensionless)
T = temperature (R or K)
Z = depth (ft or m)
zi = charge carried by species i
Greek Symbols
0 = dielectric constant of water; 0 = 55.3 (dimensionless)
m = permittivity of free space; m = 8.854 1013 C V1
dm1
o = charge density at the oil surface (C/m2)
o = oil/water interface charge potential (mV)
s = solid/water interface potential (mV)
j = molar density of phase j (lb-mol/ft3 or mol/m3)
i = activity coecient of species i (kg water/mol)
ip = the (i, p) entry in the stoichiometry matrix for the
reactions in canonical form
= porosity (dimensionless)
= density (lb/ft3 or kg/m3)
j = viscosity of phase j (cP)
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(1) Austad, T.; Strand, S.; Madland, M. V.; Puntervold, T.; Korsnes,
R. I. Seawater in Chalk: An EOR and Compaction Fluid. SPE J. 2008,
11 (4), 648 (DOI: 10.2118/118431-PA).
(2) Yousef, A.; Al-Saleh, S.; Al-Kaabi, A.; Al-Jawfi, M. S. Laboratory
Investigation of the Impact of Injection-Water Salinity and Ionic
Content on Oil Recovery from Carbonate Reservoirs. SPE Reservoir
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(3) Lager, A.; Webb, K. J.; Black, C. J. J.; Singleton, M.; Sorbie, K. S.
Low Salinity Oil RecoveryAn Experimental Investigation 1.
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