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Alkaline/Surfactant/Polymer Flooding With Sodium Hydroxide in Indiana

Limestone: Analysis of Water/Rock Interactions and Surfactant Adsorption
Article in SPE Journal · October 2018

DOI: 10.2118/191146-PA
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Alkaline/Surfactant/Polymer Flooding With

Sodium Hydroxide in Indiana Limestone:
Analysis of Water/Rock Interactions and
Surfactant Adsorption
M. Tagavifar, H. Sharma, D. Wang, S. H. Jang, and G. A. Pope, University of Texas at Austin
Summary
We recently used sodium hydroxide (NaOH) in Indiana limestone coreflood experiments to lower anionic-surfactant adsorption. This
study presents analysis of the limestone geochemistry and the surfactant adsorption under static and dynamic conditions. Analysis of
the effluent ionic composition using ion chromatography and inductively coupled plasma showed the presence of sulfate (SO2 4 ) alumi-
num (Al), and iron (Fe), as well as calcium (Ca) and magnesium (Mg). To determine the likely source of each geochemical species and
to characterize how the dissolution kinetics changes the slug chemistry, PHREEQC was used to inverse-model Indiana limestone rock
using the bulk X-ray-diffraction (XRD) mineralogical composition and the influent and effluent water chemistry. Results showed that
all Indiana limestone cores contained anhydrite, which was not detected by XRD. The effluent concentration of Al increased with pH to
approximately 15 mg/L, whereas Fe concentration remained fairly independent of pH at 0.04 6 0.02 mg/L. These trends suggest the
likely source of Al and Fe to be either clay dissolution or the release of natural clay colloids with NaOH. Simulations suggested that in
Fe-bearing carbonates, alkali consumption is fast but limited with NaOH, which is observed as pH-front delay, whereas alkali consump-
tion is slow but severe with sodium carbonate (Na2CO3) resulting in minimal pH-front delay but lower effluent pH compared with influ-
ent pH for prolonged injection times. Using the PHREEQC calculations, the ionic composition of the chemical slug in subsequent
alkali/surfactant/polymer (ASP) experiments was adjusted. In addition, the coupled adsorption/transport of anionic surfactants in car-
bonate rocks was also investigated using surface-complexation-model adsorption under static and dynamic conditions. Model predic-
tions agree with the single-phase-adsorption coreflood results and suggest that the adsorption on the metal oxides or clay could be
comparable with that on calcite. This arises from the higher surface area and the point of zero charge of pH (pHpzc) of metal oxides.
Introduction
The retention of anionic surfactants in carbonate rocks has been high, and numbers in the range of 0.5 to 1.5 mg/g in low-permeability
reservoir cores are not uncommon (Chevallier et al. 2013; Levitt et al. 2016). The high retention is partly because of the adsorption of
anionic surfactants, which could be significant on carbonates (Ahmadall et al. 1993; Ma et al. 2013; ShamsiJazeyi et al. 2014) because
unlike sandstones, the calcite/dolomite surface is positively charged at or near neutral-pH values. A simple treatment for better surfac-
tant transport is to raise the surfactant-solution pH. In practice, however, this treatment can be ineffective or difficult to sustain because
of geochemical interactions (precipitation in hard water, mineral dissolution, alkali consumption by clays, redox reactions and natural
colloid release, and others) driven by the rock mineralogy and water chemistry (ionic composition, ionic strength, and pH). Understand-
ing these interactions requires the characterization of the rock composition (XRD, scanning electron microscopy, energy dispersive
AQ1 spectroscopy, TS); the effluent ion concentrations; and the main source of major elements such as Fe and Al. Here, the results of these
characterizations are presented for Indiana limestone flooded with an ASP slug that contains NaOH. Subsequently, their relevance to
surfactant adsorption is discussed.
Na2CO3 is typically used to raise the pH and reduce surfactant adsorption (Liu et al. 2008), with additional benefits for wettability
alteration (Hirasaki et al. 2011) and optimization of emulsion type and viscosity (Aminzadeh et al. 2016). However, carbonate rocks of-
ten contain anhydrite/gypsum, which prohibits the use of Na2CO3 because of incongruent dissolution of anhydrite, and traces of metal
[Fe, Al, silicon (Si)] oxides with high specific surface areas that facilitate surfactant adsorption (Levitt et al. 2015). The pH increase
by Na2CO3 (pH of approximately 10) may not be high enough to sufficiently reduce surfactant adsorption on these oxyhydroxides.
Maubert et al. (2018) and Wang et al. (In Press) used NaOH to lower the surfactant retention in Indiana limestone cores. The reasons
for NaOH selection were no or minimal alkali consumption by calcite, dolomite, and quartz (Ehrlich and Wygal 1977); suppressing and
slowing down the dissolution of calcite at high pH values (Arvidson et al. 2003); and low concentrations of NaOH that increase the pH
to approximately 12, which is well beyond the point of zero charge (pHpzc) of most Fe or Al oxides (Table 1).
Mineral Description Salt pH

–2 –3
Al2O3 α 3×10 mol dm NaCl 9
–2 –3
γ 3×10 mol dm NaCl 9.3–9.8
–3 –1 –3
Al(OH)3 Gibbsite 10 to 10 mol dm NaCl 8.35–9.6
–3 –1 –3
Fe2O3 Hematite 10 to 10 mol dm NaCl 8.8
–3
FeOOH Goethite 0.1–0.7 mol dm NaCl 8.5
º
Table 1—Isoelectric point of common Fe/Al oxides at 25 C (Kosmulski 2002).
Copyright V
C 2018 Society of Petroleum Engineers
Original SPE manuscript received for review 7 July 2017. Revised manuscript received for review 31 January 2018. Paper (SPE 191146) peer approved 19 March 2018.
2018 SPE Journal 1
ID: jaganm Time: 18:53 I Path: S:/J###/Vol00000/180055/Comp/APPFile/SA-J###180055

At such high pH values with NaOH, there can be issues, such as precipitation of calcium hydroxide [Ca(OH)2] or magnesium
hydroxide [Mg(OH)2] (often evident by core plugging) and clay dissolution. To mediate these effects and optimize the performance of
NaOH, geochemical calculations were performed using PHREEQC (Parkhurst and Appelo 1999). An inverse-modeling approach that
combined kinetic dissolution of primary minerals (detected by XRD) and effluent composition was used to infer the main source of
major elements in Indiana limestone. The rock surface was also modeled, using a surface-complexation model from the literature. To
quantify surfactant interactions with the rock surface, a surface-complexation model for surfactant adsorption (Tagavifar et al. 2018)
was used and results were compared with dynamic adsorption corefloods.
Effluent Ion Measurements and Geochemical Calculations

This section describes the analysis of effluent ion concentrations vs. effluent pH in an ASP flood with NaOH. A PHREEQC model is
presented that in a quantitative way describes the mineralogy and dissolution kinetics in Indiana limestone. The model was used in the
geochemical calculations to identify soft-brine compositions that minimize the precipitation of Ca(OH)2 or Mg(OH)2 in ASP corefloods
with NaOH.
Effluent Ion Concentrations in Indiana Limestone. Fig. 1 shows the effluent compositions for Ca, Mg, Fe, and Al as pH changes
during the flood. It is worth noting that these elements are absent in the influent. Table 2 provides the mineralogy of the Indiana lime-
stone rock as determined by XRD. The flooding involved injecting a high-pH slug at frontal velocity of 1 ft/D while monitoring the
effluent composition. The summary of data for flooding is given in Table 3. The effluent concentrations of Ca, Mg, Fe, and Al were
measured by inductively coupled plasma (ICP) spectroscopy and that of SO2 4 by ion chromatography (IC). To minimize polymer inter-
ference, the effluent samples that contained polymer were diluted by a factor of two with sodium hypochlorite (5 wt%) and mixed for
1 hour at 78 C to degrade the polymer. Subsequently, nitric acid in deionized water (10 wt%) was added to samples to prevent metal
oxide precipitation and to decompose any organic compounds that may be present. More details on the ICP and IC procedures can be
found in Wang (2018). Even though XRD did not detect anhydrite, effluent contained SO2 4 (76.3 6 10 mg/L) when the cores were
flushed with sodium chloride (NaCl).
100 10
Ca Concentration (mg/L) Mg
Concentration (ppm)
10
Coreflood 1 0.1 Coreflood 1

Coreflood 2 Coreflood 2
Model Model
1 0.01
7 9 11 13 7 9 11 13
pH pH
100 1
Al Fe
Concentration (mg/L)
10
0.1
Coreflood 1 0.01 Coreflood 1

0.1 Coreflood 2 Coreflood 2
Model Model
0.01 0.001
7 9 11 13 7 9 11 13
pH pH
Fig. 1—Effluent ion concentration in ASP corefloods. Table 3 provides legend. Points show the data, and lines are calculations.
Mineral Composition (wt%)

Quartz 0.9
Calcite 97.7
Fe-dolomite 0.2
Halite 0.6
Illite and mica 0.6
Table 2—Mineralogy of Indiana limestone core by XRD.
The notable features of Fig. 1 include the strong dependence of effluent composition on pH and the lack of clear correlation with the
salinity of either in-situ brine or the ASP slug. The effluent concentration of Al increased nearly linearly with pH, from approximately
0.7 to approximately 15 mg/L, whereas the Fe concentration remained fairly independent of or increased slightly with pH, with an
average value of 0.04 mg/L. The increasing Al and Fe concentrations with pH must be considered when developing surfactant formula-
tions. The broader significance of these results is that because under certain conditions metal ions may cause or contribute to
2 2018 SPE Journal

polyacrylamide-polymer degradation and/or reduction of its intrinsic viscosity (Levitt et al. 2011; Seright and Skjevrak 2015), adding
reducing and protective agents to polymer drive (Gaillard et al. 2010) or using functionalized/alternative polymers (Vermolen et al.
2011; Gaillard et al. 2014; Chapman et al. 2015; Dwarakanath et al. 2016; Jouenne et al. 2016) might be necessary to minimize adverse
effects of clay dissolution at high pH on polymer transport. It is worth noting that at pH of 10 and higher, Al mainly exists as AlðOHÞ
4
species and Fe as FeðOHÞ 4 and FeðOHÞ3 . The Ca and Mg effluent concentrations in Fig. 1 are as expected for carbonates. The curves
are calculated using PHREEQC, as described in the following subsection. Fig. 2 shows the effluent ionic composition and pH vs. pore
volume (PV) of flow for the three corefloods.
Coreflood 1 Coreflood 2 Coreflood 3

Temperature (°C) 83 78 78
Rock
Porosity 0.162 0.185 0.15
3
Bulk density (g/cm ) 2.216 2.17 2.263
Diameter (cm) 3.76 3.76 5.07
Length (cm) 30.48 30.48 29.97
In-Situ Brine
NaCl (mg/L) 75 000 102 500 65 000
Na2SO4 (mg/L) – 7500 –
ASP Slug
pH (at 24°C) 12.5 12.7 12.4
NaOH (mg/L) 3000 3000 3000
NaCl (mg/L) 35 000 35 000 401 50
Na2SO4 (mg/L) 20 000 7500 20 000
Na2CO3 (mg/L) – 20 000 –
Surfactant (wt%) 0.50 wt% C28-PO35-EO40-COONa Same as Flood 1 0.65 wt% C24-PO45-EO30-COONa
0.20 wt% C15–18IOS – 0.35 wt% C15–18IOS
0.30 wt% C19–28IOS – 0.50 wt% C19–23IOS
Cosolvent (wt%) 1.00 wt% IBA-3EO 0.5 wt% phenol-5EO 0.25 wt% phenol-4EO
Polymer Drive
NaOH (mg/L) 3000 3000 3000
NaCl (mg/L) 9550 9550 9550
Na2SO4 (mg/L) 20 000 20 000 20 000
Table 3—Summary of data for flooding in Indiana limestone cores. Floods are tertiary oil recovery with a frontal velocity of 1 ft/D. Slug
contained 0.35 wt% Flopaam-3330S hydrolyzed polyacrylamide (HPAM). The corresponding effluent composition is given in Fig. 1.
100 14
10
12
1
pH
0.1 10
0.01 Coreflood 1
8
Coreflood 1 - Ca Coreflood 2 - Ca Coreflood 3 - Ca Coreflood 2
0.001 Coreflood 1 - Mg Coreflood 2 - Mg Coreflood 3 - Mg
Coreflood 1 - Al Coreflood 2 - Al Coreflood 3 - Al Coreflood 3
Coreflood 1 - Fe Coreflood 2 - Fe Coreflood 3 - Fe
0.0001 6
0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5
PV PV
(a) (b)
Fig. 2—Effluent (a) ion concentration and (b) pH during the ASP corefloods. pH is measured at room temperature. Lines guide
the eye.
Inverse Modeling of Indiana Limestone With PHREEQC. The measured effluent concentrations pose several questions:
• What is the likely source of Al, Fe, and SO24 ?
• Do the dissolution kinetics play a role in the evolution of the slug chemistry and the propagation of the pH front?
• Are precipitation and alkali consumption key concerns?
To answer these questions, PHREEQC was used to inverse model Indiana limestone rock by treating the influent and effluent water
chemistry as known data and the rock composition as the unknown. The bulk mineralogical composition, determined by XRD, was
2018 SPE Journal 3

used as the initial guess for the unknown and the dissolution kinetics were modeled using the general expression for the specific dissolu-
tion rate (Appelo and Postma 2004),
Ea1 Ea2 Ea3 Ea4
r ¼ rk1 anH1þ e RT þ rk2 anH22 O e RT þ rk3 anCO
3
2
e RT þ rk4 anOH
4
e RT ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð1Þ
where r is the specific dissolution rate (in molm2s1), rk is the rate constant, T is the temperature (in K), R is the gas constant
(8.3145 103 kJK1mol1), aHþ is the activity of the proton (dimensionless), Ea is the activation energy, and a and n are the activity
and reaction order for hydron (Hþ), water (H2O), carbon dioxide (CO2), or hydroxide (OH). The details of rate expressions are given
in an example PHREEQC input file (Appendix A). The calculated specific dissolution rate of the minerals vs. pH is shown in Fig. 3.
The dissolution rate for minerals (except calcite) was calculated by (Morse and Arvidson 2002)

dm As m n
¼ rm0 ð1 XÞ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð2Þ
dt V m0
where As is the mineral specific surface area (in m2mol1), m0 is the initial moles of mineral per solution amount V [1 L, or kg water
(kgw) here], m is the current moles of mineral per solution volume ðm=m0 Þn , n ¼ 0.67 is a correction factor to account for changes in
As =V during dissolution of the mineral, and X is the saturation state defined as the ratio of the ion-activity product to the solubility prod-
uct (ksp ) for the solid. The initial mole of mineral, m0 , for a coreflood was calculated by
xð1 /ÞqV
m0 ¼ ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð3Þ
/Mw
AQ2 where x is the mass fraction of the mineral in bulk mineralogy, / ( ¼ 0.185) is porosity, q ( ¼ 2.2 g/cm3) is the rock bulk density, Mw is
the mineral molecular weight, and V ( ¼ 1 L) is the solution volume (equivalent to PV). Table 4 lists the As and x values for the miner-
als along with their dissolution rate at pH value of 8, for example. Because dissolution rates are dependent on pH, Fig. 3 shows the rates
over a wide range of pH values (please refer to Appendix A for the rate expressions used in generating Fig. 3). For the static adsorption
case, m0 ¼ xM; where M is the total mass of the rock calculated by the experimental solid/water ratio of unity. In surface-complexation
reactions, the number of available adsorption sites was calculated using the rock surface mineralogy, surface area, and site-density
details given in Table 5. The total number of reactive surface functional groups, c (in mol/L), is related to the surface-site density, Ns
(in site/nm2), by
1018 SBET mads Ns

c¼ ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ð4Þ
VNA
where SBET (in m2/g) is the (Brunauer-Emmett-Teller (BET) surface area, mads (in g) is the mass of the adsorbent, V (in L) is the volume
of the aqueous solution, and NA is Avogadro’s number. The total site density for the calcite surface in Table 5 corresponds to 4 sites/nm2.
–3
Calcite (25°C)
–4
Anhydrite/gypsum
–5
Dolomite (25°C)
–6
log10 rk (mol/m2/s)
Ankerite (25°C)
–7
Muscovite (70°C)
–8
Biotite (25°C)
–9
–10
–11
–12
–13
–14
1 3 5 7 9 11 13
pH
Fig. 3—Dissolution rate for minerals found in Indiana limestone. Muscovite and biotite data are taken from Marini (2006); calcite
and magnesite/ankerite [Mg0.965Ca0.020Fe0.015CO3] are taken from Chou et al. (1989); dolomite data are from Pokrovsky and Schott
(2001); anhydrite/gypsum rates are for gypsum at 198C (Jeschke et al. 2001) and 258C (Raines and Dewers 1997) and anhydrite at
1208C (Bildstein et al. 2001). Lines are calculated by PHREEQC.
Specific Rate, rk (mol/m /s)

2
Surface Area Initial Amount Surface Area
2 2
Mineral (m /g) (wt%) (78°C and pH = 8) (m /mol)
–7
Calcite 1.1 99.1985 8.58×10 110.1
–10
Ankerite/Fe-dolomite 0.78 0.1 3.58×10 146.3
–9
Dolomite 1.0 0.1 3.09×10 184.4
–13
Biotite 1.2 0.1 1.24×10 576.4
–13
Muscovite (K-mica) 35 0.5 2.03×10 13 941
–5
Anhydrite 0.7 0.0015 2.05×10 95.3
Table 4—Simulated composition and dissolution kinetics of Indiana limestone.
4 2018 SPE Journal

Surface Area Site Density

Solid (m 2 /g) Site Types (µmol/m2 )
+
Calcite 1.1* >CO3OH>CaOH2 3.323.32
Hydrous ferric oxide (HFO) 600** >Fe(w)OH>Fe(s)OH 3.740.09
* from Tagavifar et al. (2018)
** from Dzombak and Morel (1990)
Table 5—Surface areas, surface-site types, and site densities used in diffuse-layer-model calculations.
To determine the source of Fe, Al, and SO2 4 , PHREEQC calculations were performed assuming that the rock contains traces
of ankerite/ferroan-dolomite [Ca(Fe,Mg)(CO3)2], siderite, dolomite, mica as biotite [K(Mg,Fe)3AlSi3O10(OH)2] and K-mica
[KAl3Si3O10(OH)2], and alunite [KAl3(SO4)2(OH)6]. A sensitivity analysis was performed by varying the amount of each mineral and
comparing the simulated and experimental effluent ionic compositions for Corefloods 1 through 3 (Table 3). The sensitivity analysis
using the dissolution kinetics for ankerite and siderite showed that neither could be the primary source of Fe. Biotite (mica) dissolution,
however, describes the effluent Fe reasonably well. Thus, clay is considered to be the major source of Fe even though the exact compo-
sition and amount of mica and other clay minerals is unknown. Similar to Fe, it was determined that alunite cannot be the main source
of Al, whereas the Al from the dissolution of K-mica describes the trend of Al reasonably well. This suggests that the surface area of 35
m2/g used for the K-mica clay is reasonable (Table 4). The primary source of SO2 4 is likely to be anhydrite because the kinetic dissolu-
tion of other SO2
4 -containing minerals, such as jarosite and alunite, cannot simultaneously describe the observed Fe, Al, and SO2
4 con-
2
centrations, although the latter (i.e., alunite being a source of Al and SO4 ) seems to be appropriate from a stoichiometric point of
view. The low level of anhydrite in the simulation model and its absence from XRD data is consistent with previous observations that
reported that low anhydrite concentrations fell below the detection limit of XRD (Lopez-Salinas et al. 2011; Levitt and Bourrel 2016).
The absence of reliable measurements of potassium and Si concentrations prevent us from drawing further conclusions. The final com-
position of Indiana limestone, determined
X by simulations, along with dissolution kinetic parameters are given in Table 4. The average
compositional surface area, S ¼ xi si (x being mass fraction and s being mineral surface area) is 1.27 m2/g, which agrees with the
measured BET surface area of 1.25 m2/g (Tagavifar et al. 2018). We may note that although pressure and temperature are constant in
our study, their variations could significantly change geochemical interactions (Tavassoli et al. 2016; Abouie et al. 2017).
Limit of NaOH With Anhydrite Dissolution. Anhydrite or gypsum is common in carbonate reservoirs and introduces a high concen-
tration of Ca ions in aqueous solutions. The dissolved Ca from anhydrite can deteriorate the transport and performance of surfactants
and polymers, and react with conventional alkali such as Na2CO3 and NaOH and precipitate calcium carbonate and hydroxide with the
former and latter, respectively. One approach to resolve the anhydrite problem at high pH is to use alternative alkali such as organic
alkali (Berger and Lee 2006) and ammonia (Sharma et al. 2015; Southwick et al. 2015), and another is optimizing the injected-brine
composition (Kazempour et al. 2013). We considered the addition of sodium sulfate (Na2SO4) to NaOH to prevent or minimize the
anhydrite dissolution and thus the precipitation of divalent hydroxides, Mg(OH)2 and Ca(OH)2, under our coreflood conditions. First,
the slug stability (i.e., lack of precipitation) was determined to be up to 0.16 wt% NaOH without NaSO4 and 0.3 wt% NaOH with
Na2SO4. Second, mixing of the in-situ brine (6.5 wt% NaCl) and the high-pH slug was simulated to investigate precipitation in the mix-
ing zone between the two solutions inside the limestone rock that contains anhydrite. Fig. 4 shows the batch-mixing results and the
amount of dissolution/precipitation; positive amounts reflect precipitation, and negative amounts reflect dissolution. The “net” depicts
the sum of dissolution/precipitation or, equivalently, the Ca pickup by the water. The in-situ brine buffered by the rock corresponds to
the lowest pH value, and the slug corresponds to the highest pH value. The in-between brines were created by mixing the two to mimic
the dynamic mixing in the flood. The slug alkali concentration is given at the bottom-left corner of each graph in Fig. 4. Slug salinity
was kept constant at 6.5 wt% by adding NaCl. Fig. 4 shows the in-situ brine picked up approximately 0.03 mol of CaSO4 upon equilib-
rium with the rock, with corresponds to a Ca concentration of 1202.1 mg/L. Subsequent precipitation as CaCO3 is evident when
Na2CO3 is used, whereas with NaOH and Na2SO4, minor precipitation occurs at a narrow pH band. Maubert et al. (2018) and Wang
et al. (In Press) observed good pH propagation with 0.3 wt% NaOH alkali and 2 wt% Na2SO4 in Indiana limestone cores.
0.05 0.05
Net Net
CaCO3 CaCO3
0.03 0.03
Dissolution (–) (mol)
Ca(OH)2 Ca(OH)2
Precipitation (+)
Dissolution (–) (mol)
CaSO4 CaSO4
Precipitation (+)
0.01 0.01
–0.01 8 9 10 11 –0.01 8 9 10 11
pH
pH
–0.03 –0.03
–0.05 –0.05
0.5 wt% Na2CO3 0.3 wt% NaOH + 2.5 wt% Na2SO4
–0.07 –0.07
Fig. 4—Mixing of in-situ brine (the lowest pH in each graph) and slug (highest pH in each graph) in equilibrium with a limestone
rock that contains 1 wt% anhydrite at 788C. Negative moles show dissolution and positives are precipitation. “Net” is the sum of
precipitation and dissolution and shows the Ca concentration in brines. Precipitation of CaCO3 with Na2CO3 is severe (top). Add-
ing Na2SO4 to the slug significantly reduces the precipitation of Ca(OH)2 (bottom).
Kinetics of Dolomite-Bearing Limestones. Dolomite dissolution and simultaneous precipitation of calcium carbonate and Mg(OH)2
can be severe with NaOH. This dedolomitization reaction under alkali conditions can be written as (Garcı́a et al. 2003)
CaMgðCO2 þ 2
3 Þ2 þ NaOH ¼ CaCO3ðsÞ þ MgðOHÞ2ðsÞ þ Na þ ðCO3 : HCO3 Þ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð5Þ
2018 SPE Journal 5

where ðCO2 2
3 : HCO3 Þ represent the distribution of CO3 and HCO3 , which is pH dependent. Our batch equilibrium calculations
showed that this reaction is complete and results in considerable alkali consumption. However, the assumption of equilibrium is not
valid because the dissolution kinetics of dolomite is approximately 100 times slower than calcite because magnesite and ankerite
kinetics are slower than dolomite (Pokrovsky et al. 1999). Invoking the dissolution kinetics of calcite and dolomite at low and high pH,
the evolution of dolomite dissolution was investigated in a limestone rock with 1 wt% dolomite in contact with brines of 6.5 wt% total
dissolved solids (TDS). These results suggest that the dedolomitization reaction is slow but complete with NaOH, leading to significant
alkali consumption. Unlike the complete dedolomitization with NaOH, Na2CO3 suppresses the dedolomitization reaction because of
the common-ion effect of carbonate ions. Indeed, Cheng (1986) observed minimal alkali consumption by dolomite when using
Na2CO3, whereas, with NaOH, alkali loss by mineral dissolution was considerable. Considering these results, we tested using
PHREEQC whether the addition of Na2CO3 could suppress the dedolomitization by NaOH. The calculations show that using Na2CO3
offers no significant benefits in slowing the dedolomitization kinetics when NaOH is used as alkali; therefore, a prospective experimen-
tal study is needed to clarify this issue.
pH Propagation With NaOH vs. Na2CO3 in Fe-Bearing Carbonates. Anhydrite can cause consumption of alkali and retardation of
high-pH front (French and Burchfield 1990; Hirasaki and Zhang 2004; Korrani et al. 2016). Another less-obvious cause of pH retarda-
tion is the interactions of the infilling solution with charged/sorption surfaces, often accompanied by release of natural colloids. Bunn
et al. (2002) injected NaOH in ferric oxyhydroxide-coated aquifer sediments to assess the effect of elevated pH on the mobilization of
natural colloids. The field and laboratory experiments both showed that the total mass of colloid release increased with increasing pH;
that significant colloid release was observed only at pH greater than approximately 10 to 11, approximately two pH units greater than
the pHpzc of goethite of approximately 8 to 9.2; and the retardation of pH front and the colloid breakthrough compared with a bromide
tracer. Similarly, Scheidegger et al. (1994) provided experimental and theoretical evidence for pH-front retardation caused by surface
charges, especially when the sediment contains goethite.
To determine how the presence of ferrihydrite would alter the pH propagation with either NaOH or Na2CO3, a surface-complexation
model was used to represent the charged sorption surfaces in Indiana limestone. It was assumed that Indiana limestone contains 99.8
wt% calcite and 0.2 wt% ferrihydrite. Note that this composition is used in calculating the rock surface interactions with ions and is dif-
ferent from the bulk mineralogy composition. Table 5 provides the surface properties (a complete description is given in the next sec-
tion). Fig. 5 shows the effluent pH with and without ferrihydrite when the column is flushed with 2.5 wt% NaCl and 2 wt% of either
NaOH or Na2CO3. Even though ferrihydrite retards the elevated-pH advance with NaOH, the pH plateau is the same with or without
ferrihydrite, which is similar to the observations of Bunn et al. (2002) and Scheidegger et al. (1994). Unlike with NaOH, pH-front lag is
minimal with Na2CO3 in the presence of ferrihydrite. However, the pH plateau is approximately 9.9 after 2 PV, which is lower than the
influent pH. In other words, in carbonate rocks that contain ankerite, effluent pH would be lower than that of the influent Na2CO3 solu-
tion for a prolonged injection time.
14
NaOH and no ferrihydrite
Na2CO3 and no ferrihydrite
13
NaOH and ferrihydrite
Na2CO3 and ferrihydrite
12
pH
11
10
8
0 0.5 1 1.5 2
PV
Fig. 5—Effect of ferrihydrite on pH propagation with NaOH vs. Na2CO3 at 788C. The rock surface is given in Table 5.
Surfactant Adsorption by Surface-Complexation Modeling

Surfactant adsorption/desorption is the key in transport of anionic surfactant in carbonate rocks. Various empirical approaches, such as
the distribution coefficient and Freundlich and Langmuir isotherm equations, have been used to represent adsorption (Davis and Kent
1990). However, these empirical approaches are not capable of accounting for the effects of variable chemical conditions, such as pH
and salinity, on surfactant-adsorption reactions. This can be performed using chemical models such as surface-complexation models.
These models define specific surface species, chemical reactions, equilibrium constants, mass balances, and charge balances, and their
molecular features can be given thermodynamic significance. Here, we investigate surfactant adsorption by a surface-complexation
model (Tagavifar et al. 2018) that incorporates both hydrated cation and anion surface sites of minerals, and accounts for surfactant
adsorption on these sites. The model uses a two-surface multisite diffuse-layer model to simulate the mineral surfaces and the attach-
ment of surfactant on these surfaces. The two surfaces represent the calcite (i.e., the major mineral) and the oxide-like sites on the edges
AQ3 of clay platelets (i.e., the trace mineral) as ferrihydrite (hydrous ferric oxide, or HFO). It was assumed that the rock contains 0.1 wt%
HFO in all surface-complexation calculations throughout the paper. The calcite and ferrihydrite surface models were adopted from Van
Cappellen et al. (1993) and Dzombak and Morel (1990), respectively. The calcite surface model has two primary hydration sites,
>CaOH and >CO3OH, which have a 1:1 stoichiometry on the surface. Surface sites for HFO are the typical weak >Fe(w)OH and
strong > Fe(s)OH sites. Available adsorption sites were calculated using the surface area and site density given in Table 5. The amount
of solid, or surface, sites was calculated using the water/rock ratio for dispersions (i.e., static adsorption) and using a rock bulk density
6 2018 SPE Journal

of 2.22 g/cm3 and porosity of 0.18 for dynamic adsorption (i.e., coreflood) experiments. The reactions describing the surfactant adsorp-
tion on calcite and HFO and the corresponding equilibrium constants are given in Table 6. The equilibrium constants were estimated
using the typical experimental observation that static surfactant adsorption is approximately 2 mg/g on calcite and approximately 3 mg/g
on limestone at or near neutral-pH values (Ahmadall et al. 1993; Ma et al. 2013; ShamsiJazeyi et al. 2014; Tagavifar et al. 2018).
Reaction Log-Stability Constant

Surfactant Adsorption on Calcite
– –
>CO3H + A(aq) = >CO3HA 4.9
– –
>CaOH + A (aq) = >CaOHA 0.7
+ –
>CaOH + A 2 (aq) = >CaOH2A 2.4
+ –
>CO3Ca + A (aq) = >CO3CaA 4.2
Surfactant Adsorption on HFO
– –
>Fe(w)OH + A(aq) = >Fe(w)OHA 3.9
+ –
>Fe(w)OFe + A (aq) = >Fe(w)OFeA 0.2
+ –
>Fe(s)OFe + A (aq) = >Fe(s)OFeA 0.2
Table 6—Surfactant-adsorption reactions and equilibrium constants

used in diffuse-layer-model calculations.
Static Surfactant Adsorption vs. pH. The surfactant-adsorption model was used to assess adsorption vs. pH. Fig. 6 displays the pla-
teau of surfactant adsorption on Indiana limestone (mineralogy given in Table 4) as a function of pH at the constant ionic strength and
temperature. The experimental data are shown by symbols and the surface-complexation-modeling results by solid lines. The pH is
adjusted by adding Na2CO3 and NaOH to the solution. Total adsorption in the model is the sum of adsorption on calcite and ferrihydrite
surfaces. At pH values lower than 9, both the data and the model reach the same adsorption plateau of 3 mg/g. At pH values greater
than 9, the amount of adsorption decreases approximately linearly with pH. The reduction of adsorption with pH is partly because of
the reduction in the positive surface charges as pH increases and partly because of the decrease of weak or hydrogen-bonding adsorp-
tion at pH values greater than 10 (Tagavifar et al. 2018). Notable features of Fig. 6 include the following. First, at pH values of 7.6 to 9
(buffered by the rock) and low surfactant concentrations, adsorption is similar on calcite and HFO. At higher surfactant concentration,
adsorption increases considerably on calcite, whereas it increases slightly on HFO. This suggests a higher affinity of HFO for anionic
surfactant. Second, adsorption on calcite decreases monotonically by pH when pH is greater than 9. This is unlike adsorption on HFO,
which either shows a maximum at pH of approximately 9 or remains constant below pH of approximately 10, whereupon it starts
decreasing. Third, total adsorption remains nearly constant at pH values lower than approximately 9.
3.5 3.5
Data Data
3 Total 3 Total
Calcite Calcite
2.5 2.5 Clay
Clay
Γ (mg/g)
Γ (mg/g)
2 2
1.5 1.5
CS = 0.2 wt% CS = 1.5 wt%
1 1
0.5 0.5
0 0
7 8 9 10 11 12 7 8 9 10 11 12
pH pH
(a) (b)
Fig. 6—Model calculations for static surfactant adsorption on Indiana limestone vs. pH when the initial surfactant concentration,
Cs, is (a) 0.2 wt.% and (b) 1.5 wt.%. Total adsorption is the sum of adsorption on calcite and on HFO. Experimental data are adopted
form Tagavifar et al. (2018). The surfactant mixture contains C24-PO45-EO30-COONa (0.43 wt%), C15–18IOS (0.23 wt%), and C19–23IOS
(0.34 wt%) (concentrations are normalized to 1 wt%). The solid/water ratio is unity, and the temperature is 78 C. The brine contains
43 000 mg/L NaCl and 20 000 mg/L Na2SO4.
Dynamic Surfactant Adsorption With or Without Alkali. To determine whether the surfactant-adsorption model is mechanistic and
can be used to deduce the mechanics of surfactant adsorption/desorption, comparisons were made with a single-phase dynamic adsorp-
tion flood (i.e., no oil in the core). Table 7 provides the surfactant formulation, and Table 8 provides a summary of the flooding data
and simulation parameters. The 0.4-PV surfactant slug (1.5 wt%) was injected in an Indiana limestone core (u ¼ 0.185, q ¼ 2.2 g/cm3)
at 78 C and followed by a polymer drive. Both the slug and drive contained 0.30 wt% NaOH and 2.0 wt% Na2SO4, and were injected
at a frontal velocity of 1 ft/D. A salinity gradient was used, which is typical in chemical enhanced-oil-recovery (EOR) processes (Lake
2018 SPE Journal 7

et al. 2014). The salinities of the waterflood brine, ASP slug, and polymer drive were 65,000, 63,150, and 32,550 ppm TDS, respec-
tively. Effluent surfactant concentration was measured by high-performance liquid chromatography, and a dynamic surfactant adsorp-
tion of 0.14 mg/g rock was calculated from the mass balance. The core was extremely heterogeneous, as indicated by the salinity-tracer
test (not shown). Full experimental details can be found in Wang et al. (In press).
ASP Slug Polymer Drive

0.65 wt% C24-PO45-EO30-COONa 0.35 wt% Flopaam-3330S HPAM
0.35 wt% C15–18IOS 1.0 wt% phenol-EO4
0.50 wt% C19–23IOS 0.30 wt% of NaOH
0.25 wt% phenol-EO4 2.0 wt% Na2SO4
0.35 wt% Flopaam-3330S HPAM –
0.30 wt% of NaOH –
2.0 wt% Na2SO4 –
Table 7—Chemical composition of the formulation used in the dynamic single-phase-

adsorption coreflood.
Parameter Value Comment

Cells 20 –
Length (m) 0.015 1-ft core
Shifts 8 and 40 8/20 = 0.4-PV slug
40/20 = 2-PV drive
Timestep (seconds) 4,320 1ft sec
1ft/D /
20 × 86,400
D
= 4,320 seconds
Flow direction Forward –

Boundary conditions Flux-flux –
Dispersivity (m) 0.02 The core was heterogeneous.
Brine composition (mg/L) Na: 25 569.22 6.5 wt% NaCl
Cl: 39 430.78 –
Slug composition (mg/L) Na: 23 992.25 A = surfactant
Cl: 24 356.09 4.015 wt% NaCl
S(6): 13 525.99 0.3 wt% NaOH
A: 15 000 2.0 wt% Na2SO4
Drive composition (mg/L) Na: 11 837.04 0.955 wt% NaCl
Cl: 56 11.30 0.3 wt% NaOH
S(6): 13 525.99 2.0 wt% Na2SO4
Rock mineralogy Refer to Table 4 Dissolution kinetics shown in Fig. 3 and Appendices A and B
–3
Surface sites (mol) 6.55×10 (Calcite 1) Parameters for adsorption given in Table 6.
–3
6.55×10 (Calcite 2)
–3
4.03×10 (HFO-w)
–4
1.01×10 (HFO-s)
Table 8—Simulation input parameters and data for the dynamic single-phase-adsorption coreflood. Frontal velocity is 1 ft/D; temperature is
78º C; and core length and diameter are 1 and 0.17 ft, respectively.
Fig. 7 compares the effluent surfactant concentration, pH, and ionic composition obtained from the model with the experimental
data. The simulations were performed with and without the surfactant-adsorption model under high- and low-pH conditions. The agree-
ment with experimental data is extremely good. Moreover, the model shows reasonable dependence on pH and suggests that a surfac-
tant slug with a concentration of 0.5 wt% cannot be propagated in single-phase coreflood in a limestone rock without using an alkali.
Typical to carbonate rocks, surfactant breakthrough is early because of heterogeneity at approximately 0.8 PV with adsorption and at
approximately 0.5 PV without modeling adsorption. An example PHREEQC input file for modeling dynamic surfactant adsorption cor-
efloods is given in Appendix B. The model parameters for surfactant adsorption, dissolution kinetics, and surface charges and complex-
ations are identical in simulating the static and dynamic (coreflood) experiments. However, the following assumptions were made in
fitting the ionic composition in the static and dynamic experiments. First, it was assumed that the polished dolomite and Fe-dolomite
(i.e., static experiments with crushed rock) have higher dissolution rates compared with the unpolished/untreated minerals in the core-
flood experiments. This assumption is consistent with experimental data (Saldi et al. 2017). Second, it was assumed that the uncrushed
rock (i.e., core) contained less mica compared with the crushed rock. In other words, it was assumed that mica is not evenly distributed
within the rock, and thus not all mica (0.5 wt%) was in contact with the pore fluid during the coreflood. Needless to say, crushing the
rock would expose all the mica, as is the case in static adsorption and X-ray experiments.
8 2018 SPE Journal

10 000 Data 14
Data
No asdorption
Effluent Surfactant (mg/L)

Adsorption modeled and high-pH flood Adsorption modeled and high-pH flood
8000 Adsorption modeled and no alkali
12
6000
pH
10
4000
8
2000
0 6
0 0.5 1 1.5 2 2.5 0 0.5 1 1.5 2 2.5
PV PV
100
10
Concentration (ppm)
0.1
0.01
Ca Mg
Al Fe
0.001
0 0.5 1 1.5 2 2.5
PV
Fig. 7—Effluent surfactant concentration (top left) and pH (top right) in the single-phase dynamic adsorption coreflood. Lines are
obtained from the surfactant-adsorption model. The calculated effluent ionic composition (bottom) is compared with experimental
data for Corefloods 1 through 3. The surfactant mixture contains C24-PO45-EO30-COONa (0.65 wt%), C15–18IOS (0.35 wt%), and
C19–23IOS (0.50 wt%). The core length is 1 ft, and the temperature is 78 C.
Conclusions
Indiana limestone was characterized by an inverse-modeling approach that uses influent and effluent ionic compositions, XRD whole-
rock mineralogy, and dissolution kinetics. The SO2 4 , Al, and Fe ions were measured in the effluent of ASP corefloods with NaOH,
although they were absent in the influent. PHREEQC calculations indicate that anhydrite is the likely source of SO2 4 , whereas mica-
illite clays are the source of Al and Fe. The increase of effluent Al and, in some cases, Fe concentrations with pH were found to corre-
late with the greater dissolution of mica-illite clays at high pH. This assertion was supported by the pH-dependent dissolution kinetics
of K-mica and biotite. These experimental and modeling results suggest that the design of ASP flooding in carbonates could be
improved by adding Na2SO4 to the influent to suppress the dissolution of anhydrite when present; using both Na2CO3 and NaOH in
anhydrite-free cores to improve pH propagation in Fe-bearing carbonates; and considering the effects of pH-dependent concentrations
of Al and Fe on the transport of surfactants and polymer. With regard to the surfactant adsorption, a multisite surface-complexation
model was used to elucidate the equilibrium adsorption and coupled adsorption/transport of anionic surfactants in carbonate rocks. The
model suggests a comparable adsorption on the abundant low-surface-area calcite and the trace high-surface-area minerals such as clay
and metal oxides, especially with diluted surfactant solutions. Both the corefloods and the model suggest that raising the pH to 11 is
necessary to sufficiently reduce surfactant adsorption on both major and trace minerals. The model is mechanistic and can be used in
assessing effects of variable chemical conditions, such as pH and salinity.
AQ4 Nomenclature
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Appendix A—Example PHREEQC Input File Calculating the Static Surfactant Adsorption
and Rock/Fluid Interactions With Indiana Limestone
SOLUTION 1
units ppm;density 1.0;temp 78.0;pe 0.0;ph 7.5 charge;
#Na 9834.32; Cl 15165.68;S(6) 0; ## 2.5%NaCl ¼ ¼¼¼¼¼¼¼¼¼¼
Na 23602.36;Cl 36397.64;S(6) 0;
#Na 393.37; Cl 606.63;S(6) 0; ## 0.1%NaCl ¼ ¼¼¼¼¼¼¼¼¼¼
Ca 0;C(4) 0;Al 0;K 0;Fe 0;A 15000; ## A denotes surfactant.
SOLUTION_MASTER_SPECIES
A A- 0 452 452
SOLUTION_SPECIES
A- ¼ A-;log_k 0.0;
PHASES
Biotite; KMgFe2AlSi3O10(OH)2 þ 4H2O þ 6Hþ ¼ Kþ þ Mgþ2 þ 2Feþ2 þ Al(OH)4- þ 3H4SiO4;
Fe-dolomite; CaFe0.1Mg0.9(CO3)2 ¼ Caþ2 þ 0.1Feþ2 þ 0.9Mgþ2 þ 2CO3-2;
K-mica; KAl3Si3O10(OH)2 þ 10 Hþ ¼ Kþ þ 3 Alþ3 þ 3 H4SiO4; -log_k 12.703;
Dolomite; CaMg(CO3)2 ¼ Caþ2 þ Mgþ2 þ 2 CO3-2; -log_k -17.09;
Ca(OH)2; Ca(OH)2 ¼ Caþ2 þ 2OH-;log_k -5.25; ##Assumed to be fast
Mg(OH)2; Mg(OH)2 ¼ Mgþ2 þ 2OH-;log_k -8.85; ##Assumed to be fast
Fix_ph # Define pH fixing mineral
Hþ ¼ Hþ; log_k 0 # pH ¼ 10^(-SI)
Fix_pe # Define pe
e- ¼ e-; log_k 0 # pe ¼ 10^(-SI)
EQUILIBRIUM_PHASES 1
#CO2(g) -3.5 10
Fix_ph -6. Na(OH)
Fix_pe -1.5 O2(g)
KINETICS 1
Calcite ##default PHREEQC rate
-m0 9.83
-parms 110.1, .67
Dolomite
-m0 .0271 #crushing the rock exposed more Dolomite
-parms 184.4, .67
Biotite
-m0 .0021
-parms 576
k-mica #KAl3Si3O10(OH)2
-m0 0.013
parms 13941
Anhydrite
-formula CaSO4
-m0 .001
-parms 4.5, 95.3, .9
Fe-dolomite
2018 SPE Journal 11

-m0 .0267 #crushing the rock exposed more Fe-dolomite

-parms 146.3, 0.67
-steps 86400 #total time that water and rock interact
-step_divide 10 #number of time intervals in kinetics integration
-tol 1e-11
-runge_kutta 6
-bad_step_max 500
-cvode_order 5
-cvode_steps 100
RATES
Calcite
-start
1 rem M ¼ current number of moles of calcite
2 rem M0 ¼ number of moles of calcite initially present
3 rem PARM(1) ¼ A/V, cm^2/L
4 rem PARM(2) ¼ exponent for M/M0
10 si_cc ¼ SI(“Calcite”)
20 if (M <¼ 0 and si_cc <0) then goto 200
30 k1 ¼ 10^(0.198 - 444.0 / TK )
40 k2 ¼ 10^(2.84 - 2177.0 / TK)
50 if TC <¼ 25 then k3 ¼ 10^(-5.86 - 317.0 / TK)
60 if TC > 25 then k3 ¼ 10^(-1.1 - 1737.0 / TK)
70 t ¼ 1
80 if M0 > 0 then t ¼ M/M0
90 if t ¼ 0 then t ¼ 1
100 area ¼ PARM(1) * (t)^PARM(2)
110 rf ¼ k1*ACT(“Hþ”)þk2*ACT(“CO2”)þk3*ACT(“H2O”)
120 rem 1e-3 converts mmol to mol
130 rate ¼ area *0.1*1e-3* rf * (1 - 10^(2/3*si_cc))
140 moles ¼ rate * TIME
200 SAVE moles
-end
Dolomite
-start
1 REM PARM(1) ¼ specific surface area of dolomite, cm^2/L
2 REM PARM(2) ¼ exponent for M/M0
10 si_cc ¼ SI(“Dolomite”)
20 IF (M <¼ 0 and si_cc <0) THEN GOTO 200
30 k1 ¼ 10^(0.198 - 444.0 / TK)
40 k2 ¼ 10^(2.84 - 2177.0 /TK)
50 IF TC <¼ 25 THEN k3 ¼ 10^(-5.86 - 317.0 / TK)
60 IF TC > 25 THEN k3 ¼ 10^(-1.1 - 1737.0 / TK)
70 t ¼ 1
80 IF M0 > 0 THEN t ¼ (M/M0)^PARM(2)
90 IF t ¼ 0 THEN t ¼ 1
100 area ¼ PARM(1) * M0 * t
110 rate ¼ area*1*0.1*0.001*(k1 * ACT(“Hþ”) þ k2 * ACT(“CO2”) þ k3 * ACT(“H2O”))
120 moles ¼ rate * (1 - SR(“Dolomite”)) * time
200 SAVE moles
-end
Biotite
-start
10 dif_temp ¼ 1/TK - 1/298
20 pk_H ¼ 11.5 þ 3359 * dif_temp
30 pk_w ¼ 14.8 þ 2648 * dif_temp
40 pk_OH ¼ 13.37 þ 3359 * dif_temp
#41 rem ^12.9 in Sverdrup, but larger than for oligoclase…
50 pk_CO2 ¼ 14.0 þ 1677 * dif_temp
#60 pk_org ¼ 12.5 þ 1254 * dif_temp # …rate increase for DOC
70 rate ¼ 10^-pk_H * ACT(“Hþ”)^0.5 þ 10^-pk_w þ 10^-pk_OH * ACT(“OH-”)^0.3
71 rate ¼ rate þ 10^-pk_CO2 * (10^SI(“CO2(g)”))^0.6
#72 rate ¼ rate þ 10^-pk_org * TOT(“Doc”)^0.4
77 t¼1
78 if M0 > 0 then t¼(M/M0)^0.67
80 moles ¼ rate * parm(1) * M0 * t * (1 - SR(“Biotite”)) * time
81 rem decrease rate on precipitation
90 if SR(“Biotite”) > 1 then moles ¼ moles * 0.1
100 save moles
-end
K-mica
-start
12 2018 SPE Journal

10 dif_temp ¼ 1/TK - 1/298

20 pk_H ¼ 12.3 þ 3359 * dif_temp
30 pk_w ¼ 14.5 þ 2648 * dif_temp
40 pk_OH ¼ 12.7 þ 3359 * dif_temp
50 pk_CO2 ¼ 14.0 þ 1677 * dif_temp
77 t¼1
78 if M0 > 0 then t¼(M/M0)^0.67
80 moles ¼ rate * parm(1) * M0 * t * (1 - SR(“K-mica”)) * time
90 if SR(“K-mica”) > 1 then moles ¼ moles * 0.1
100 save moles
-end
Anhydrite
-start
10 pk_H ¼ PARM(1) # log_k
20 SpArea ¼ PARM(2) # m2/mole
30 n_pH ¼ PARM(3)
40 dif_temp ¼ 1/TK
50 rate ¼ 10^-pk_H * exp(-2020.19/TK) * ACT(“Hþ”)^n_pH
60 t¼1
70 if M0 > 0 then t¼(M/M0)^0.67
80 area ¼ SpArea * M0 * t
90 rate ¼ area * rate * (1-SR(“Anhydrite”))
100 moles ¼ rate * time
110 SAVE moles
-end
Fe-dolomite
-start
1 REM PARM(1) ¼ specific surface area of calcite, m^2/mol calcite
10 si_cc ¼ SI(“Fe-dolomite”)
30 k1 ¼ 10^(0.198 - 444.0 / TK)
40 k2 ¼ 10^(2.84 - 2177.0 /TK)
50 IF TC <¼ 25 THEN k3 ¼ 10^(-5.86 - 317.0 / TK)
60 IF TC > 25 THEN k3 ¼ 10^(-1.1 - 1737.0 / TK)
70 t ¼ 1
80 IF M0 > 0 THEN t ¼ (M/M0)^PARM(2)
90 IF t ¼ 0 THEN t ¼ 1
100 area ¼ PARM(1) * M0 * t
110 rate ¼ (k1 * ACT(“Hþ”) þ k2 * ACT(“CO2”) þ k3 * ACT(“H2O”))
111 rate ¼ rate
120 rate ¼ rate *0.1*0.1*0.001 * area *(1 - SR(“Fe-dolomite”))
200 SAVE moles
-end
#SAVE SOLUTION 1 #note: uncomment for equilibrium, e.g., zeta potential.
END
SURFACE_MASTER_SPECIES
Surf_w Surf_wH
Surf_s Surf_sOH2þ
SURFACE_SPECIES
Surf_wH ¼ Surf_wH; log_k 0;
Surf_sOH ¼ Surf_sOH; log_k 0;
##### Calcite surface ¼ ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Surf_wH ¼ Surf_w- þ Hþ; log_k -6.2;
Surf_wH þ Caþ2 ¼ Surf_wCaþ þ Hþ; log_k -6.1;
Surf_sOH2þ ¼ Surf_sOH þ Hþ; log_k -11;
Surf_sOH ¼ Surf_sO- þ Hþ; log_k -14;
Surf_sOH þ Hþ ¼ Surf_sOH2þ; log_k 7.;
Surf_sOH þ CO3-2 þ Hþ ¼ Surf_sCO3- þ H2O; log_k -2.6;
Surf_sOH þ CO3-2 þ 2Hþ ¼ Surf_sHCO3 þ H2O; log_k 6.5;
##### Hfo surface representing clay edge ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Hfo_wOH þ Hþ ¼ Hfo_wOH2þ; log_k 8.49;
Hfo_wOH ¼ Hfo_wO- þ Hþ; log_k -9.1;
Hfo_sOH þ Hþ ¼ Hfo_sOH2þ; log_k 8.49;
Hfo_sOH ¼ Hfo_sO- þ Hþ; log_k -8.93;
Hfo_wOH þ Feþ2 ¼ Hfo_wOFeþ þ Hþ; -log_k -2.98
Hfo_wOH þ Feþ2 þ H2O ¼ Hfo_wOFeOH þ 2Hþ; -log_k -15.98
2018 SPE Journal 13

Hfo_sOH þ Feþ2 ¼ Hfo_sOFeþ þ Hþ; -log_k -.98

Hfo_wOH þ Caþ2 ¼ Hfo_wOCaþ þ Hþ; -log_k -6.05
Hfo_wOH þ Mgþ2 ¼ Hfo_wOMgþ þ Hþ; -log_k -6.8
#Hfo_sOH þ Mgþ2 ¼ Hfo_sOHMgþ2; -log_k -15.98
#Hfo_sOH þ Caþ2 ¼ Hfo_sOHCaþ2; -log_k -15.98
##### Surfactant ads on calcite ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Surf_wH þ A- ¼ Surf_wHA-; log_k 4.9
Surf_sOH þ A- ¼ Surf_sOHA-; log_k .7
Surf_sOH2þ þ A- ¼ Surf_sOH2A; log_k 2.4
Surf_wCaþ þ A- ¼ Surf_wCaA; log_k 4.2;
##### Surfactant ads on Hfo ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Hfo_wOFeþ þ A- ¼ Hfo_wOFeA; log_k .2;
Hfo_wOH þ A- ¼ Hfo_wOHA-; log_k 3.9
Hfo_sOFeþ þ A- ¼ Hfo_sOFeA; log_k .21;
SURFACE 1
Hfo_w 2.24e-3 600 1 ###solid-brine ratio¼1, total solid¼1000 gr
Hfo_s 5.61e-5
Surf_w 3.65e-3 1.1 999
Surf_s 3.65e-3
-Donnan #neutralize the charge
#-diffuse_layer
#-equil 1
END
SELECTED_OUTPUT
-file Surfactant-Adsorp-1.sel
-reset false
-pH true
USER_PUNCH 1
-headings Ca(ppm) Mg(ppm) Al(ppm) Fe(ppm) SO4(ppm)
-start
30 CaSolu ¼ TOT(“Ca”)*40.08*1000
31 MgSolu ¼ TOT(“Mg”)*24.305*1000
32 AlSolu ¼ TOT(“Al”)*26.981539*1000
33 FeSolu ¼ TOT(“Fe”)*55.845*1000
34 SO4Solu ¼ TOT(“S(6)”)*96.06*1000
35 PUNCH CaSolu MgSolu AlSolu FeSolu SO4Solu
-end
END
SELECTED_OUTPUT 2
-file Surfactant-Adsorp-2.sel
-reset false
-pH true
USER_PUNCH 2
-headings Ads_Calcite Ads_Hfo Ads(mgg) Calc_psi(mV) Hfo_psi(mV)
-start
10 Mwsurf¼452
11 grrock ¼ 1000
12 Ads_Calcite ¼ SURF(“A”,“Surf”)*Mwsurf*1e3
13 Ads_Hfo ¼ SURF(“A”,“Hfo”)*Mwsurf*1e3
14 Ads_Calcite ¼ Ads_Calcite /grrock
15 Ads_Hfo ¼ Ads_Hfo /grrock
16 Ads_mgg¼Ads_Calcite þ Ads_Hfo
31 Calc_psi ¼ EDL(“psi”, “Surf”)*1000
33 Hfo_psi ¼ EDL(“psi”, “Hfo”)*1000
50 PUNCH Ads_Calcite Ads_Hfo Ads_mgg Calc_psi Hfo_psi
-end
END
USER_GRAPH 1
-chart_title “Indiana limestone”
-headings B Ca Mg Al Fe K Si SO4
-axis_titles “pH” “Concentration (ppm)”
-axis_scale x_axis 7 13
-axis_scale y_axis 0.0001 1000 1 1 log
-start
10 x ¼ -la(“Hþ”)
20 graph_x x #-la(“Hþ”) # pH on x-axis
22 graph_y TOT(“Ca”)*40.08*1000
23 graph_y TOT(“Mg”)*24.305*1000
24 graph_y TOT(“Al”)*26.981539*1000
25 graph_y TOT(“Fe”)*55.845*1000
26 graph_y TOT(“K”)*39.0983*1000
14 2018 SPE Journal

27 graph_y TOT(“Si”)*60.08*1000
28 graph_y TOT(“S(6)”)*96.06*1000
-end
END
USER_GRAPH 3
-headings Total Ads_calcite Ads_hfo
-chart_title “Adsorption vs pH”
-axis_titles “pH” \
“Adsorption (mgr/gram)”
-axis_scale x_axis 7 13
-axis_scale y_axis¼1 auto
-axis_scale sy_axis 0 100
-start
9 x ¼ -LA(“Hþ”)
10 Mwsurf¼452
11 grrock ¼ 1000
12 Ads_1 ¼ (SURF(“A”,“Hfo”)þSURF(“A”,“Surf”))*Mwsurf*1e3
13 PLOT_XY x, Ads_1/grrock, color ¼ Orange, symbol ¼ square,symbol_size ¼ 7, line_width ¼ 2
14 Ads_calcite ¼ SURF(“A”,“Surf”)*Mwsurf*1e3
15 PLOT_XY x, Ads_calcite/grrock, color ¼ Yellow, symbol ¼ None,symbol_size ¼ 7, line_width ¼ 2
33 Ads_hfo ¼ (SURF(“A”,“Hfo”))*Mwsurf*1e3
34 PLOT_XY x, Ads_hfo/grrock, color ¼ Red, symbol ¼ None,symbol_size ¼ 7, line_width ¼ 2
-end
END
USE SOLUTION 1; USE SURFACE 1; -equil 1;

USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -7 Na(OH)
END;
USE SOLUTION 1; USE SURFACE 1; #-equil 1;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -7.5 Na(OH)
END;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -8 Na(OH)
END;
USE Kinetics 1;
#Calcite 0 10
2018 SPE Journal 15

#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -8.5 Na(OH)
END;
USE SOLUTION 1; USE SURFACE 1 ; #-equil 1;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -9 Na(OH)
END;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -9.5 Na(OH)
END;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -10 Na(OH)
END;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -10.5 Na(OH)
END;
USE Kinetics 1;
#Calcite 0 10
#Dolomite 0 0
16 2018 SPE Journal

Mg(OH)2 0 0
Ca(OH)2 0 0
#Fe-dolomite 0 0
#Biotite 0 0
#K-mica 0 0
Anhydrite 0 0.0002
Fix_pe -.5 O2(g)
Fix_ph -11.3 Na(OH);
END;
Appendix B—Example PHREEQC Input File Calculating the Surfactant Adsorption and
Rock/Fluid Interactions in Dynamic Single-Phase-Adsorption Corefloods
SOLUTION 100 Initial solution in column 6.5%NaCl
units ppm;density 1.0;temp 78.0;pe 0.0;ph 7.5 charge;
Na 25569.22;Cl 39430.78;S(6) 0;C(-4) 40;A 0;
SOLUTION_MASTER_SPECIES
A A- 0 452 452
SOLUTION_SPECIES
A- ¼ A-;log_k 0.0;
PHASES
Biotite; KMgFe2AlSi3O10(OH)2 þ 4H2O þ 6Hþ ¼ Kþ þ Mgþ2 þ 2Feþ2 þ Al(OH)4- þ 3H4SiO4;
Fe-dolomite; CaFe0.1Mg0.9(CO3)2 ¼ Caþ2 þ 0.1Feþ2 þ 0.9Mgþ2 þ 2CO3-2;
K-mica; KAl3Si3O10(OH)2 þ 10 Hþ ¼ Kþ þ 3 Alþ3 þ 3 H4SiO4; -log_k 12.703;
Dolomite; CaMg(CO3)2 ¼ Caþ2 þ Mgþ2 þ 2 CO3-2; -log_k -17.09;
Ca(OH)2; Ca(OH)2 ¼ Caþ2 þ 2OH-;log_k -5.25; ##Assumed to be fast
Mg(OH)2; Mg(OH)2 ¼ Mgþ2 þ 2OH-;log_k -8.75; ##Assumed to be fast
Fix_ph # Define pH fixing mineral
Hþ ¼ Hþ; log_k 0 # pH ¼ 10^(-SI)
Fix_pe # Define pe
e- ¼ e-; log_k 0 # pe ¼ 10^(-SI)
EQUILIBRIUM_PHASES 1-100 ## The fluid was allowed to remain in the core overnight.
#CO2(g) -3.5
#Fix_ph -7.8 Na(OH)
Fix_pe -2.5 O2(g)
Calcite 0 0.0001
Dolomite 0 0.00001
Mg(OH)2 0 0
Ca(OH)2 0 0
K-mica 0 0.00001
#Biotite 0 0
Fe-dolomite 0 1e-7
Anhydrite 0 0.0001
KINETICS 1-100
Calcite ##default PHREEQC rate
-m0 95.97
-parms 110.1, .67
Dolomite
-m0 0.053
-parms 184.4, .67
Biotite
-m0 0.020
-parms 576
k-mica #KAl3Si3O10(OH)2
-m0 0.061 #0.122/2 #Unlike the crushed sample, not all clay is reacting with water
parms 13941
Anhydrite
-formula CaSO4
-m0 0.0011
-parms 4.5, 95.3, .9
Fe-dolomite
-m0 0.052
-parms 146.3, 0.67
#-steps 86400
#-step_divide 10
-tol 1e-11
-runge_kutta 6
-bad_step_max 500
-cvode_order 5
-cvode_steps 100
RATES
Calcite
2018 SPE Journal 17

-start
1 rem M ¼ current number of moles of calcite
2 rem M0 ¼ number of moles of calcite initially present
3 rem PARM(1)
4 rem PARM(2) ¼ exponent for M/M0
10 si_cc ¼ SI(“Calcite”)
20 if (M <¼ 0 and si_cc <0) then goto 200
30 k1 ¼ 10^(0.198 - 444.0 / TK)
40 k2 ¼ 10^(2.84 - 2177.0 / TK)
50 if TC <¼ 25 then k3 ¼ 10^(-5.86 - 317.0 / TK)
60 if TC > 25 then k3 ¼ 10^(-1.1 - 1737.0 / TK)
70 t ¼ 1
80 if M0 > 0 then t ¼ M/M0
90 if t ¼ 0 then t ¼ 1
100 area ¼ PARM(1) * (t)^PARM(2)
110 rf ¼ k1*ACT(“Hþ”)þk2*ACT(“CO2”)þk3*ACT(“H2O”)
120 rem 1e-3 converts mmol to mol
130 rate ¼ area *0.1*1e-3* rf * (1 - 10^(2/3*si_cc))
200 SAVE moles
-end
Dolomite
-start
1 REM PARM(1)
10 si_cc ¼ SI(“Dolomite”)
30 k1 ¼ 10^(0.198 - 444.0 / TK)
40 k2 ¼ 10^(2.84 - 2177.0 / TK)
50 IF TC <¼ 25 THEN k3 ¼ 10^(-5.86 - 317.0 / TK)
60 IF TC > 25 THEN k3 ¼ 10^(-1.1 - 1737.0 / TK)
70 t ¼ 1
80 IF M0 > 0 THEN t ¼ (M/M0)^PARM(2)
90 IF t ¼ 0 THEN t ¼ 1
100 area ¼ PARM(1) * M0 * t
110 rate ¼ area*0.1*0.1*0.001*(k1 * ACT(“Hþ”) þ k2 * ACT(“CO2”) þ k3 * ACT(“H2O”))
120 moles ¼ rate * (1 - SR(“Dolomite”)) * time
200 SAVE moles
-end
Biotite
-start
10 dif_temp ¼ 1/TK - 1/298
20 pk_H ¼ 11.5 þ 3359 * dif_temp
30 pk_w ¼ 14.8 þ 2648 * dif_temp
40 pk_OH ¼ 13.37 þ 3359 * dif_temp
#41 rem ^12.9 in Sverdrup, but larger than for oligoclase…
50 pk_CO2 ¼ 14.0 þ 1677 * dif_temp
#60 pk_org ¼ 12.5 þ 1254 * dif_temp # …rate increase for DOC
#72 rate ¼ rate þ 10^-pk_org * TOT(“Doc”)^0.4
77 t¼1
78 if M0 > 0 then t¼(M/M0)^0.67
80 moles ¼ rate * parm(1) * M0 * t * (1 - SR(“Biotite”)) * time
90 if SR(“Biotite”) > 1 then moles ¼ moles * 0.1
100 save moles
-end
K-mica
-start
10 dif_temp ¼ 1/TK - 1/298
20 pk_H ¼ 12.3 þ 3359 * dif_temp
30 pk_w ¼ 14.5 þ 2648 * dif_temp
40 pk_OH ¼ 12.7 þ 3359 * dif_temp
50 pk_CO2 ¼ 14.0 þ 1677 * dif_temp
77 t¼1
78 if M0 > 0 then t¼(M/M0)^0.67
80 moles ¼ rate * parm(1) * M0 * t * (1 - SR(“K-mica”)) * time
18 2018 SPE Journal

90 if SR(“K-mica”) > 1 then moles ¼ moles * 0.1

100 save moles
-end
Anhydrite
-start
10 pk_H ¼ PARM(1) # log_k
20 SpArea ¼ PARM(2) # m2/mole
30 n_pH ¼ PARM(3)
40 dif_temp ¼ 1/TK
50 rate ¼ 10^-pk_H * exp(-2020.19/TK) * ACT(“Hþ”)^n_pH
60 t¼1
70 if M0 > 0 then t¼(M/M0)^0.67
80 area ¼ SpArea * M0 * t
90 rate ¼ area * rate * (1-SR(“Anhydrite”))
100 moles ¼ rate * time
110 SAVE moles
-end
Fe-dolomite
-start
1 REM PARM(1) ¼ specific surface area of calcite, m^2/mol
10 si_cc ¼ SI(“Fe-dolomite”)
30 k1 ¼ 10^(0.198 - 444.0 / TK)
40 k2 ¼ 10^(2.84 - 2177.0 /TK)
50 IF TC <¼ 25 THEN k3 ¼ 10^(-5.86 - 317.0 / TK)
60 IF TC > 25 THEN k3 ¼ 10^(-1.1 - 1737.0 / TK)
70 t ¼ 1
80 IF M0 > 0 THEN t ¼ (M/M0)^PARM(2)
90 IF t ¼ 0 THEN t ¼ 1
100 area ¼ PARM(1) * M0 * t
110 rate ¼ (k1 * ACT(“Hþ”) þ k2 * ACT(“CO2”) þ k3 * ACT(“H2O”))
111 rate ¼ rate
120 rate ¼ rate *0.01*0.1*0.001 * area *(1 - SR(“Fe-dolomite”))
200 SAVE moles
-end
SAVE SOLUTION 100
END
SURFACE_MASTER_SPECIES
Surf_w Surf_wH
Surf_s Surf_sOH2þ
SURFACE_SPECIES
Surf_wH ¼ Surf_wH; log_k 0;
Surf_sOH ¼ Surf_sOH; log_k 0;
##### Calcite surface ¼ ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Surf_wH ¼ Surf_w- þ Hþ; log_k -6.2;
Surf_wH þ Caþ2 ¼ Surf_wCaþ þ Hþ; log_k -6.1;
Surf_sOH2þ ¼ Surf_sOH þ Hþ; log_k -11.;
Surf_sOH ¼ Surf_sO- þ Hþ; log_k -14;
Surf_sOH þ Hþ ¼ Surf_sOH2þ; log_k 7.;
Surf_sOH þ CO3-2 þ Hþ ¼ Surf_sCO3- þ H2O; log_k -2.6;
Surf_sOH þ CO3-2 þ 2Hþ ¼ Surf_sHCO3 þ H2O; log_k 6.5;
##### Hfo surface representing clay edge ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Hfo_wOH þ Hþ ¼ Hfo_wOH2þ; log_k 8.49;
Hfo_wOH ¼ Hfo_wO- þ Hþ; log_k -9.1;
Hfo_sOH þ Hþ ¼ Hfo_sOH2þ; log_k 8.49;
Hfo_sOH ¼ Hfo_sO- þ Hþ; log_k -8.93;
Hfo_wOH þ Feþ2 ¼ Hfo_wOFeþ þ Hþ; -log_k -2.98
Hfo_wOH þ Feþ2 þ H2O ¼ Hfo_wOFeOH þ 2Hþ; -log_k -15.98
Hfo_sOH þ Feþ2 ¼ Hfo_sOFeþ þ Hþ; -log_k -.98
Hfo_wOH þ Caþ2 ¼ Hfo_wOCaþ þ Hþ; -log_k -8.05
Hfo_wOH þ Mgþ2 ¼ Hfo_wOMgþ þ Hþ; -log_k -8.8
#Hfo_sOH þ Mgþ2 ¼ Hfo_sOHMgþ2; -log_k -15.98
#Hfo_sOH þ Caþ2 ¼ Hfo_sOHCaþ2; -log_k -15.98
##### Surfactant ads on calcite ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
Surf_wH þ A- ¼ Surf_wHA-; log_k 4.9
Surf_sOH þ A- ¼ Surf_sOHA-; log_k .7
Surf_sOH2þ þ A- ¼ Surf_sOH2A; log_k 2.4
Surf_wCaþ þ A- ¼ Surf_wCaA ; log_k 4.2;
##### Surfactant ads on Hfo ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
2018 SPE Journal 19

Hfo_wOFeþ þ A- ¼ Hfo_wOFeA; log_k .2;

Hfo_wOH þ A- ¼ Hfo_wOHA-; log_k 3.9
Hfo_sOFeþ þ A- ¼ Hfo_sOFeA; log_k .21;
SURFACE 1-100
Hfo_w 4.03e-3 600 1.8
Hfo_s 1.04e-4
Surf_w 6.55e-3 1.1 1791.2 # ml W/ml PV¼9.69;gr surface for adsorption ¼ 9682.21*0.185 ¼ 1791.2 g;mole sites ¼ 1791.2g*7.03e-
6 mol/g¼6.55e-3 mol
Surf_s 6.55e-3
-Donnan
#-diffuse_layer
#-equil 81
KNOBS; -iter 500
#save solution 100
END
#¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼ ¼ Surfactant Slug ¼ ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼

COPY CELL 100 1-20 END;
SOLUTION 0 Displacing solution Slug
units ppm;density 1.0;temp 78.0;pe 0.0;ph 7 charge;
#4.015NaClþ0.3NaOHþ2Na2SO4
Na 23992.25;Cl 24356.09;S(6) 13525.99;C(þ4) 0;A 10000;C(-4) 200; #CO2 activity
#6.315NaCl
#Na 24841.48;Cl 38308.52;S(6) 0;A 15000;C(-4) 0;C(þ4) 0;
END
SELECTED_OUTPUT 1
-file SurfAds-Coreflood-1.sel
-reset false
-high_precision false
USER_PUNCH 1
-headings XD PV A_ppm Ads_Calcite Ads_Hfo Ads_mgg
-start
1 Ngrid ¼ 20
2 t_s ¼ 8
3 Mw_surf¼452
4 grrock ¼ 9608.2
11 PUT(Ngrid,1)
12 PUT(t_s,2)
13 PUT(Mw_surf,3)
14 PUT(grrock,4)
20 x ¼ dist /.3
21 PV ¼ step_no / Ngrid
24 A_ppm¼TOT(“A”)*Mw_surf*1000
40 Ads_Calcite ¼ SURF(“A”,“Surf”)*Mw_surf*1e3
41 Ads_Hfo ¼ SURF(“A”,“Hfo”)*Mw_surf*1e3
50 PUNCH x, PV, A_ppm, Ads_Calcite, Ads_Hfo, Ads_mgg
200 a¼1
-end
END
SELECTED_OUTPUT 2
-file SurfAds-Coreflood-2.sel
-reset false
-high_precision false
USER_PUNCH 2
-headings PV Ca_ppm Fe_ppm A_ppm pH Mg_ppm Al_ppm SO4_ppm
-start
8 Ngrid ¼ GET(1)
9 Mw_surf¼GET(3)
10 grrock ¼ GET(4)
11 PV¼(STEP_NO ) / Ngrid
12 if PV¼0 then goto 200
21 ph¼-LA(“Hþ”)
22 Ca_ppm¼TOT(“Ca”)*40.08*1000
23 Fe_ppm¼TOT(“Fe”)*55.845*1000
25 Mg_ppm ¼ TOT(“Mg”)*24.305*1000
26 Al_ppm ¼ TOT(“Al”)*26.981539*1000
27 SO4_ppm ¼ TOT(“S(6)”)*96.06*1000
20 2018 SPE Journal

50 PUNCH PV Ca_ppm Fe_ppm A_ppm pH Mg_ppm Al_ppm SO4_ppm
200 a¼1
-end
END
TRANSPORT
-cells 20
-lengths 0.015 # column length¼20*0.015 ¼ 0.3 m or 1ft
-shifts 8 # 8/20 ¼ 0.4 PV
-time_step 4320.0 #velocity ¼ 1 ft/day ¼ >time_step ¼ 1 ft / 1. ft/day /number of cells*86400
-flow_direction forward
-boundary_conditions flux flux # at coulmn ends
-diffusion_coefficient 0.0e-9 # m2/s
-dispersivities 0.02
-correct_disp true
-punch_cells 20 # only punch/print cell 10
-punch_frequency 1
-print_cells 20
-print_frequency 20
USER_GRAPH 1
-chart_title “Indiana limestone Effluent”
-headings Ca Mg Al Fe K Si SO4
-axis_titles “Pore volumes” “Concentration (ppm)”
-axis_scale x_axis 0 2.5
-axis_scale y_axis 0.0001 1000 1 1 log
-plot_concentration_vs time
9 Mw_surf¼GET(3)
10 x ¼ (STEP_NO ) / cell_no #Add 0.5 to transfer cell centeblue conc to column end
22 PLOT_XY x, TOT(“Ca”)*40.08*1000,symbol ¼ Square,color ¼ red
23 PLOT_XY x, TOT(“Mg”)*24.305*1000,symbol ¼ Diamond,color ¼ green
24 PLOT_XY x, TOT(“Al”)*26.981539*1000,symbol ¼ Triangle,color ¼ blue
25 PLOT_XY x, TOT(“Fe”)*55.845*1000,symbol ¼ Circle,color ¼ Orange
26 PLOT_XY x, TOT(“K”)*39.0983*1000,symbol ¼ XCross,color ¼ Magenta
27 PLOT_XY x, TOT(“Si”)*60.08*1000,symbol ¼ Plus,color ¼ black
28 PLOT_XY x, TOT(“S(6)”)*96.06*1000,symbol ¼ TriangleDown,color ¼ Cyan
-END
USER_GRAPH 2
-chart_title “Indiana limestone Effluent”
-headings Surfactant pH
-axis_titles “Pore volumes” “Surfactant (ppm)” “pH”
-axis_scale x_axis 0 2.5
-axis_scale y_axis 0 auto
-axis_scale sy_axis 0 14
9 Mw_surf¼GET(3)
10 x ¼ (STEP_NO ) / cell_no # transfer cell centered conc to column end
70 PLOT_XY x, TOT(“A”)*Mw_surf*1000, y-axis ¼ 1,symbol ¼ Plus,color ¼ red
71 PLOT_XY x, -LA(“Hþ”), y-axis ¼ 2,symbol ¼ Plus,color ¼ blue
END
#¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼ ¼ Polymer drive ¼ ¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼
SOLUTION 0 # Polymer drive
units ppm;density 1.0;temp 78.0;pe 0.0;ph 7 charge;
#0.925NaClþ0.3NaOHþ2Na2SO4
Na 11837.04;Cl 5611.30;S(6) 13525.99;C(þ4) 0;A 0;C(-4) 150;
END
TRANSPORT
-shifts 40 # 40/20 ¼ 2 PV
USER_PUNCH 1
-headings XD PV A_ppm Ads_Cal Ads_Hfo Ads_tot
-start
7 t_s ¼ GET(2)
8 Ngrid ¼ GET(1)
9 Mw_surf¼GET(3)
10 grrock ¼ GET(4)
12 if STEP_NO ¼ 0 then goto 200
20 x ¼ dist /.3
21 PV ¼ (step_noþt_s) / Ngrid
2018 SPE Journal 21

50 PUNCH x, PV, A_ppm, Ads_Calcite, Ads_Hfo, Ads_mgg
200 a¼1
-end
-END
USER_PUNCH 2
-headings PV Ca_ppm Fe_ppm A_ppm pH Mg_ppm Al_ppm SO4_ppm
-start
7 Ngrid ¼ GET(1)
8 t_s ¼ GET(2)
9 Mw_surf¼GET(3)
10 grrock ¼ GET(4)
11 PV¼(STEP_NO ) / Ngrid þ (t_s)/Ngrid
12 if STEP_NO¼0 then goto 202
21 ph¼-LA(“Hþ”)
22 Ca_ppm¼TOT(“Ca”)*40.08*1000
23 Fe_ppm¼TOT(“Fe”)*55.845*1000
25 Mg_ppm ¼ TOT(“Mg”)*24.305*1000
26 Al_ppm ¼ TOT(“Al”)*26.981539*1000
27 SO4_ppm ¼ TOT(“S(6)”)*96.06*1000
50 PUNCH PV Ca_ppm Fe_ppm A_ppm pH Mg_ppm Al_ppm SO4_ppm
202 a¼1
-end
-END
USER_GRAPH 1
8 t_s ¼ GET(2)
10 x ¼ (STEP_NO ) / cell_no þ (t_s)/cell_no #Add 0.5 to transfer cell centeblue conc to column end
22 PLOT_XY x, TOT(“Ca”)*40.08*1000,symbol ¼ Square,color ¼ red
23 PLOT_XY x, TOT(“Mg”)*24.305*1000,symbol ¼ Diamond,color ¼ green
24 PLOT_XY x, TOT(“Al”)*26.981539*1000,symbol ¼ Triangle,color ¼ blue
25 PLOT_XY x, TOT(“Fe”)*55.845*1000,symbol ¼ Circle,color ¼ Orange
26 PLOT_XY x, TOT(“K”)*39.0983*1000,symbol ¼ XCross,color ¼ Magenta
27 PLOT_XY x, TOT(“Si”)*60.08*1000,symbol ¼ Plus,color ¼ black
28 PLOT_XY x, TOT(“S(6)”)*96.06*1000,symbol ¼ TriangleDown,color ¼ Cyan
-END
USER_GRAPH 2
8 t_s ¼ GET(2)
9 Mw_surf¼GET(3)
10 x ¼ (STEP_NO ) / cell_no þ (t_s)/cell_no # transfer cell centered conc to column end
70 PLOT_XY x, TOT(“A”)*Mw_surf*1000, y-axis ¼ 1,symbol ¼ Plus,color ¼ red
71 PLOT_XY x, -LA(“Hþ”), y-axis ¼ 2,symbol ¼ Plus,color ¼ blue
END
Mohsen Tagavifar is a post-doctoral-degree fellow at the Center for Petroleum and Geosystems Engineering at the University
of Texas at Austin. His research interests include EOR, reservoir simulation, soft-matter physics, and rheology of complex fluids.
Tagavifar holds a PhD degree in petroleum engineering from the University of Texas at Austin.
Himanshu Sharma is a post-doctoral-degree researcher at the University of Texas at Austin. His research interests include interfa-
cial phenomena and reactive transport in porous media, particularly during ASP flooding and wettability alteration. Sharma
holds bachelor’s and master’s degrees in chemical engineering from Indian Institute of Technology and a PhD degree in petro-
leum engineering from the University of Texas at Austin.
Denning Wang is a graduate student at the Department of Petroleum and Geosystems Engineering at the University of Texas at
Austin. His research interests include EOR and transport phenomena in porous media. Wang holds bachelor’s and master’s
degrees in petroleum engineering from the University of Texas at Austin.
Sunghyun Jang is a post-doctoral-degree fellow at the Center for Petroleum and Geosystems Engineering at the University of
Texas at Austin. His research interests include EOR, reservoir simulation, interfacial phenomena, and fluid-phase equilibria. Jang
holds a PhD degree in chemical engineering.
Gary A. Pope is a professor in the Hildebrand Department of Petroleum and Geosystems Engineering at the University of Texas at
Austin, where he holds the Texaco Centennial Chair in Petroleum Engineering. His teaching and research are in the areas of
EOR, reservoir engineering, natural-gas engineering, and reservoir simulation. Pope holds a bachelor’s degree from Oklahoma
State University and a PhD degree from Rice University, both in chemical engineering. He was elected to the National Academy
of Engineering in 1999. Pope’s awards include the AIME Environmental Conservation Distinguished Service Award, the Billy and
Claude R. Hocott Distinguished Centennial Engineering Research Award, the SPE IOR Pioneer Award, the SPE/AIME Anthony F.
AQ5 Lucas Gold Medal, the SPE John Franklin Carll Award, the SPE Distinguished Achievement Award, and the Reservoir Evaluation
and Engineering Award. He is an SPE Honorary Member and an SPE Distinguished Member.
22 2018 SPE Journal
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Alkaline/Surfactant/Polymer Flooding With Sodium Hydroxide in Indiana

Article in SPE Journal · October 2018

Mohsen Tagavifar Himanshu Sharma

SEE PROFILE SEE PROFILE

Chemical Flooding in Low Permeability Carbonates View project

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Alkaline/Surfactant/Polymer Flooding With

Mineral Description Salt pH

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Effluent Ion Measurements and Geochemical Calculations

Coreflood 1 0.1 Coreflood 1

Coreflood 1 0.01 Coreflood 1

Mineral Composition (wt%)

Table 2—Mineralogy of Indiana limestone core by XRD.

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Coreflood 1 Coreflood 2 Coreflood 3

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1018 SBET mads Ns

Specific Rate, rk (mol/m /s)

Table 4—Simulated composition and dissolution kinetics of Indiana limestone.

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Surface Area Site Density

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Surfactant Adsorption by Surface-Complexation Modeling

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Reaction Log-Stability Constant

Table 6—Surfactant-adsorption reactions and equilibrium constants

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ASP Slug Polymer Drive

Table 7—Chemical composition of the formulation used in the dynamic single-phase-

Parameter Value Comment

Flow direction Forward –

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Effluent Surfactant (mg/L)

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-m0 .0267 #crushing the rock exposed more Fe-dolomite

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10 dif_temp ¼ 1/TK - 1/298

2018 SPE Journal 13

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Hfo_sOH þ Feþ2 ¼ Hfo_sOFeþ þ Hþ; -log_k -.98

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USE SOLUTION 1; USE SURFACE 1; -equil 1;

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2018 SPE Journal 17