Journal of Petroleum Science and Engineering 168 (2018) 419–425

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Journal of Petroleum Science and Engineering

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

pH effect on wettability of oil/brine/carbonate system: Implications for low T

salinity water flooding
Quan Xiea,∗, Ahmad Saria, Wanfen Pub, Yongqiang Chena, Patrick V. Bradyc, Nasser Al Maskaria,
Ali Saeedia
a
Department of Petroleum Engineering, Curtin University, 26 Dick Perry Avenue, 6151, Kensington, Western Australia, Australia
b
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan, 610500, China
c
Sandia National Laboratories, Albuquerque, NM, 87185-0754, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Wettability of oil/brine/carbonate system is a critical parameter to govern subsurface multi-phase flow beha-
Carbonate reservoirs viour, thus remaining oil saturation and ultimate oil recovery in carbonate reservoirs. Despite the fact that
Low salinity water salinity level, ionic strength, oil composition and rock chemistry (e.g., limestone and dolomite) have been ex-
Wettability tensively investigated, few work has been done regarding the effect of pH on oil/brine/rock interaction, thus
Geochemical modelling
wettability.
pH
We thereby measured contact angles at two different pH (pH = 3 and 8) in the presence of either 1 mol/L
Na2SO4 or 1 mol/L CaCl2 using a crude oil with acid number of 1.7 and base number of 1.2 mg KOH/g.
Moreover, we performed a geochemical modelling study in light of the diffuse double layer to understand how
pH controls the number of surface species at interfaces of oil/brine and brine/carbonate. Our results show that
pH scales with oil/brine/carbonate wettability, demonstrating that pH is one of the controlling factors to govern
the system wettability. Further, our results suggest that pH (6.5–7.5) likely triggers an oil-wet system, which is
favourable for low salinity water flooding, but pH < 5 usually exhibits a water-wet system, which explains why
low salinity effect is not always observed in carbonate reservoirs. This also confirms that CO2 flooding, carbo-
nated water flooding, and CO2 huff-and-puff EOR very likely renders a strongly water-wet system due to H+
adsorption on the interface of oil/brine and brine/carbonate as a result of CO2 dissolution.

1. Introduction While a number of mechanisms (Sheng, 2014; Myint and

Firoozabadi, 2015; Al-Shalabi and Sepehrnoori, 2016) have been pro-
Carbonates rock host most of the world's oil reserves (> 60%) posed in attempts to decipher the controlling factor(s) of low salinity
(Klemme and Ulmishek, 1991), which are composed primarily of the water flooding in sandstone reservoirs, the low salinity effect in car-
minerals calcite and dolomite together with impurities, e.g., quartz, bonate reservoirs is less clear, which limits the application of low
anhydrite, clay minerals, organic matter, and apatite (Reeder and salinity water in carbonate reservoirs (Al-Shalabi and Sepehrnoori,
America, 1983). However, average recovery typically is lower than 2016). While previous studies (Brady and Thyne, 2016; Strand et al.,
40%. Cost-effective and environmentally friendly techniques to en- 2016; Ding and Rahman, 2017; Matthiesen et al., 2017) suggest that
hance oil recovery from carbonates are therefore of broad scientific wettability alteration is the main mechanism for the low salinity water
interest (Jackson et al. 2016). One such technique that has gained in- effect in carbonate reservoirs, understanding factors which drive this
terest is to manipulate the injected water chemistry, thus shifting re- process (wettability alteration) have yet to be clearly defined (Al-
servoir wettability from oil-wet to water-wet in a process termed low Shalabi and Sepehrnoori, 2016).
salinity water flooding, which is also called LoSal flooding by BP To understand the controlling factor(s) of the low salinity effect in
(Jerauld et al., 2008; Lager et al., 2008), Smart Water flooding by its carbonate reservoirs, electrokinetic/double layer expansion theory was
originators, Austad and co-workers, at the University of Stavanger, proposed to examine the interaction of oil/brine and brine/rock inter-
Saudi Aramco (Al-sofi and Yousef, 2013), and Designer Water flooding by faces, which governs the wettability of the oil/brine/carbonate system.
Shell (Ayirala et al., 2014; Cense et al., 2014). For example, zeta potential of oil/brine and brine/limestone were

∗
Corresponding author.
E-mail address: [email protected] (Q. Xie).

https://doi.org/10.1016/j.petrol.2018.05.015
Received 22 December 2017; Received in revised form 4 May 2018; Accepted 4 May 2018
Available online 09 May 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
Q. Xie et al. Journal of Petroleum Science and Engineering 168 (2018) 419–425

Fig. 1. AFM topographic images of the cleaved carbonate substrate used for contact angle measurements.

measure, and the results show that who showed that the charges at the oil/brine/rock interaction, thus wettability.
limestone/brine and oil/brine interfaces became more negative with In this study, we hypothesize that apart from salinity level, ionic
decreasing salinity (Mahani et al., 2015), implying a weaker electro- strength, oil composition and rock mineralogy, pH of brines controls the
static adhesion between oil/brine and brine/rock interfaces, thus re- number of surface species at interfaces of oil/brine and brine/rock,
cession of the three-phase contact line. Further, a new parameter, governing the interaction of oil/brine/rock system, hence wettability.
Zf = ( Zetaoil / brine + Zetabirne / rock ) , is proposed to relate the contact To test our hypothesis, we measured contact angles at two different pH
angle data remarkably well (Sari et al., 2017), showing that the oil (pH = 3 and 8) in the presence of either 1 mol Na2SO4 or 1 mol CaCl2.
contact angle on the carbonate substrate in the presence of various Moreover, we performed a geochemical modelling study in light of
brines decreases linearly with increasing Zf . They further argued that diffuse double layer to understand how pH controls the number of
manipulating the Zf is of vital importance to shift the reservoir wett- surface species at interfaces of oil/brine and brine/carbonate. Note that
ability, thus decreasing residual oil saturation. while we did not explicitly investigate the relative contribution of the
Apart from the electrokinetic theory, multi-component ion ex- mechanisms, e.g., electrical double layer, multi-component ion ex-
change theory were also proposed to decipher the low salinity effect in change, and surface complexation, our new findings may allow us to
carbonate reservoirs. For example, sulfate ions in brines would adsorb put boundaries on designing injected water chemistries. Furthermore,
at the carbonate surface, thus triggering the adsorption of Ca2+, which these findings may also explain why low salinity effect is not always
in return releasing carboxylic materials from carbonate surface (Zhang observed in carbonate reservoirs.
et al., 2006). Note: in this mechanism, SO42− acts as a catalyst to
promote the adsorption of Ca2+ to the surface of mineral. Literature 2. Materials and methods
data also show that the retention of SO42− increases with increasing
temperature (Strand et al., 2006). This implies that adding SO42− in the 2.1. Calcite substrates
injected brine yields more incremental oil recovery in high temperature
reservoirs. Moreover, Sari et al. showed that with an absence of SO42−, Rock mineralogy is essential to wettability alteration in carbonate
the wettability of oil/brine/carbonate system shifted from water-wet to reservoirs. In this work, we used crystal calcite (Iceland Spar from
oil-wet with decreasing salinity at various pH (Sari et al., 2017). They Ward's Science) to run contact angle tests. To ensure the integrity of
conclude that the wettability alteration can probably be explained by contact angle measurements, the rock substrates were cleaned with
electrical double layer theory. methanol to remove any trace of inorganic contaminants, and rinsed
Furthermore, surface complexation modelling were also performed with equilibrated deionised water. Then, clean and dry substrates were
to interpret the low salinity effect in carbonate reservoirs. For example, exposed to air plasma for 10 min to remove organic surface con-
an independently derived diffuse layer geochemical model (Brady and tamination (Iglauer et al., 2014).
Thyne, 2016) was developed which quantitatively interprets the pH To avoid the surface roughness on contact angle tests, we imaged
shift, plateau of incremental oil recovery, and the oxyanion role in in- the cleaved calcite substrate using atomic force microscopy (AFM)
creased oil recovery observed from core-flooding experiments. To relate (WITec, ALPHA 300 RA for combined Raman-AFM imaging). Results
the surface complexation modelling to zeta potential, Mahani et al. show that the surface roughness was in a range of 0–4.8 nm (Fig. 1),
proposed a new geochemical model which demonstrates that the in- implying that the surface roughness effect on contact angle should be
crease of zeta potential with pH is triggered by surface species at in- negligible (Arif et al., 2017; Pooryousefy et al., 2017). It is worth noting
terfaces of brine/carbonate (Mahani et al., 2016a,b). In particular, > that advancing contact angle of brine on calcite surface in the presence
CaSO4− is substituted by the neutral > CaOH moiety and > CaCO3−, of CO2 decreases from 85 to 75° with increasing surface roughness from
reducing the negative charge at the surfaces. They also concluded that 7.5 to 140 nm (Arif et al., 2017).
the number of surface species of > CO3Ca+ and > CO3Mg+ are rela-
tively insensitive to pH change. However, the effect of pH on the
2.2. Experimental brines
number of surface species of oil/brine interfaces was not included in
their surface complexation modelling.
Two different ionic solutions were used to test the effect of brine pH
In general, despite the fact that based on the theories outlined
on system wettability. We measured contact angles at two different pH
above, salinity level (Puntervold and Austad, 2008; Mahani et al.,
(pH = 3 and 8) in the presence of 1 mol Na2SO4 and 1 mol CaCl2 so-
2015), ionic strength (RezaeiDoust et al., 2011; Xie et al., 2012a,b), oil
lutions. We did not manipulate and monitor the pH change during the
composition (Hadia et al., 2012; Hopkins et al., 2017; Wu et al., 2017)
contact angle tests because of the current capability of the experimental
and rock mineralogy (e.g., limestone and dolomite (Alotaibi et al.,
system. We assumed that the pH increase due to the calcite dissolution
2014; Mahani et al., 2016a,b)) have been extensively investigated, few
should not be significant because the specific reactive surface area for
studies have been conducted to exclusively focus on the effect of pH on
the brine/cubic calcite (experimental substrate, 0.000025 m2/g) is

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Q. Xie et al. Journal of Petroleum Science and Engineering 168 (2018) 419–425

much lower than brine/calcite powers (0.11 m2/g) (Lasaga et al., 1994; Table 1
Mahani et al., 2016a,b). Surface complexation model input parameters (Van Cappellen et al., 1993;
Pokrovsky et al., 1999; Hiorth et al., 2010; Brady and Thyne, 2016).
2.3. Experimental oil Interface Reaction Log K25oC Reaction

An oil was used to test the pH effect on the system wettability with oil/brine –NH+ = –N + H+ −6.0 1
–COOH = –COO- + H+ −5.0 2
acid number of 1.7, and base number 1.2 mg KOH/g. Gas chromato-
–COOH + Ca2+ = –COOCa+ + H+ −3.8 3
graph mass spectrometer (GC-MS) was used to examine the oil prop- calcite/brine > CaOH + H+ = > CaOH2+ 11.85 4
erties, showing that the oil was comprised of asphaltenes (37.1 wt %), > CaOH + HCO3− = > CaCO3− + H2O 5.8 5
naphthenes (26.3 wt %), wax (3.8 wt %) and sulphur (3.9 wt %) with > CaOH2+ + SO42− 2.1 6
= > CaSO4− + H2O
density of 0.89 g/cm3 at 20 °C.
> CO3H = > CO3− + H+ −5.1 7
> CO3H + Ca2+ = > CO3Ca+ + H+ −2.6 8
2.4. Experimental set-up
Where “ > ” denotes a site on the carbonate surface while “-” denotes a site on
In this study, contact angles for oil/brine/rock system were per- the oil surface.
formed using Vinci IFT-700 (Fig. 1 in reference (Xie et al., 2017a,b)).
The experimental temperatures were 25, 60 and 100 °C which cover the site density of surface species, and we assumed that the number of acid
temperature range for typical oil reservoirs. Pressure was kept constant (summation of -COOH, -COO-, and –COOCa+) and base (summation of
at 100 bar for all experiments. Contact angle tests were performed using –NH+ and –N) functional group did not change with pH.
the sessile droplet method. Substrates were placed inside the HT-HP cell
and vacuumed before filling with the relevant brine. Subsequently,
3. Results
pressure and temperature were applied. Once the state of temperature
and pressure equilibrium was achieved, a droplet of crude oil
3.1. Effect of pH on contact angle
(0.04–0.06 ml) was released through a small needle (D = 0.6 mm) onto
the substrate surface. A high definition video camera continuously re-
pH appeared to strongly affect the contact angle in oil/brine/car-
corded the experiment where contact angles were measured over the
bonate system (Fig. 2), indicating that pH is very likely to be one of the
period of 48 h using the built-in software. Once the state of equilibrium
controlling factors that govern the wettability in oil/brine/rock system.
was achieved and no more change in contact angle was detected, result
To be more specific, low pH (pH = 3), in the presence of Na2SO4,
was reported as the final contact angle for the system. It worth noting
rendered a slightly water-wet oil/brine/carbonate system. Rather, high
that while factors such as the substrate roughness, contact angle hys-
pH (pH = 8) led to a strongly oil-wet system. For example, at 60 °C,
teriss, and preparation procedure all may affect the macroscopoic
contact angle was measured to be 53° at low pH (pH = 3), whereas at
contact angle (Mahani et al., 2015), the philosophy of the contact angle
high pH (pH = 8) contact angle increased to 175°. While similar trend
tests in this study was to highlight the actual trend of the contact angle
was observed in the presence of CaCl2, the contact angle difference in
with pH, rather than the exact initial value of the contact angle. Also, in
the presence of pH = 3 and 8 was less pronounced compared to Na2SO4
this study, we did not age the substrates before testing contact angles.
solution. For example, at 60 °C, low pH (pH = 3) yielded a contact
This is because aging process tends to make the rock more oil-wet by re-
angle of 44°. Yet, high pH (pH = 8) gave a contact angle of 54°. Both
establishing adsorption equilibrium between the rock surface and the
pHs exhibited a water-wet system (see Fig. 3).
crude oil (Morrow, 1990). This study aims to investigate the pH effect
on the wettability. Using carbonate rocks with a strongly oil-wet surface
in our experiments would mean that possible change in the wetting 3.2. Effect of ion type on contact angle
preference from water-wet to oil-wet due to change in pH could not be
observed. Ion type had a little effect on contact angle at low pH (pH = 3). In
other words, low pH dominated the interaction of oil/brine/rock
2.5. Surface complexation modelling system, thus wettability. For example, at pH = 3 (60° C), the contact
angle in the presence of Na2SO4 and CaCl2 were 44 and 52°, respec-
Given that directly sorbed oil probably doesn't respond to low tively, showing a water-wet system.
salinity waterflooding, and that only oil-rock with an intervening water However, at high pH, ion type strongly affected the contact angle
layer will respond (Brady and Thyne, 2016). Our analysis focusses so-
lely on the water-present situation which can be modelled using surface
complexation theory (Brady et al., 2016; Brady and Thyne, 2016).
Surface complexation model input parameters were provided in Table 1
to calculate the number of charged species that are thought to cause
local adhesion of the oil/brine interface to the brine/calcite interface,
hence wetting. The bond product sum is a measure of the amount of
electrostatic attraction between the two interfaces. Surface complexa-
tion modelling (and DLVO theory) presumes an electric double layer at
each interface and the existence of charged surface species whose
concentrations depend upon the chemical makeup of water, oil and
mineral surface (Xie et al., 2017a,b). In the surface complexation
model, the calcite surface area was assumed to be 0.11 m2/g with site
density of 5 sites/nm2 (Mahani et al., 2016a,b). Geochemical reactions
in Table 1 because water chemistry dominates the surface complexation
of the oil/brine/rock system and temperature plays a secondary role
(Xie et al., 2017a,b). The surface species concentrations were calculated
using PHREEQC version 3.3.9 and a diffuse layer surface model. It is Fig. 2. Contact angle vs. temperature in the presence of Na2SO4 at pH = 3 and
worth noting that NaOH was used to adjust the pH for calculating the 8.

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Fig. 3. Contact angle vs. temperature in the presence of CaCl2 at pH = 3 and 8. Fig. 4. Site density of surface species at oil/brine interface as a function of pH
in the presence of 1 mol Na2SO4.
(pH = 8), suggesting that ion type plays a vital role in dominating the
interaction of oil/brine/rock system, thus wettability. To be more
specific, at pH = 8, Na2SO4 gave a strongly oil-wet system with a
contact angle of 175°. Rather, CaCl2 exhibited a water-wet system with
a contact angle of 54°.
In general, our results suggest that at low pH, ion type does not
govern the wettability of oil/brine/carbonate system. This is not be-
cause ion type, salinity and ionic strength are not important, rather this
is because low pH has much greater influence on governing the number
of surface species at oil/brine and brine/carbonate surfaces, thereby
wettability. This was quantitatively demonstrated using surface com-
plexation modelling in the Discussion section.

3.3. Effect of temperature on contact angle

Temperature had a little effect on contact angle. At high pH = 8,

contact angle did not change with increasing temperature for both
Fig. 5. Site density of surface species at oil/brine interface as a function of pH
Na2SO4 and CaCl2 although contact angles increased slightly with in-
in the presence of 1 mol CaCl2. Although the pH strongly affects the number of
creasing temperature at pH = 3. For example, at pH = 8, Na2SO4 gave
surface species at oil/brine for both Na2SO4 and CaCl2, in order to directly
contact angle of 175°, and CaCl2 gave contact angle of 54 °C as tem- relate pH to contact angle, hence wettability, the number of surface species at
perature increasing from 20 to 100 °C. At pH = 3, contact angle in- brine/carbonate surface need to be calculated, details of which were presented
creased from 48 to 70°, and 30 to 44° in the presence of Na2SO4 and in the section below.
CaCl2. The variation in contact angles in the presence of different pH
was physiochemically described in the Discussion section.
increasing pH although salinity level also affects the variation trend of
the number of surface species at interfaces of oil/brine.
4. Discussion pH also strongly affected the number of surface species at interfaces
of oil/brine at the presence of CaCl2 (Fig. 5). However, the number of
To gain a deeper understanding of the pH effect on the interaction of –COO- did not increase monotonically, but increased up to pH 5.2, then
oil/brine/rock system and its impact on wettability, we conducted a decreased with increasing pH. This is because the presence of Ca2+
surface complexation modelling, quantitatively describing how pH, enabled Reaction 3 shifting towards left-hand side, thus decreasing
affects the bond product sum which is an indicator of wettability (Brady –COO- in line with Brady et al. who showed that –COO- increases
and Thyne, 2016). Note: bond product sum means a measure of the slightly as pH increasing from 4 to 5.8, then decreases slowly at the
amount of oil-mineral electrostatic attraction, which is given by the presence of 0.02 M NaCl+10 mM CaCl2 (Brady et al., 2015). Fig. 5 also
summed products of the oppositely charged surface species on the in- shows that –COOCa+ increased until pH increased to 4 due to the Re-
terface of oil/brine and brine/mineral (Brady et al., 2012). action 3 shifting towards right-hand side. Moreover, –NH+ decreased
with increasing pH due to the Reaction 1 shifting towards right-hand
4.1. pH effect on number of surface species at oil/brine surfaces side. The variation of the –COOCa+ and –NH+ are in line with previous
studies (Brady and Thyne, 2016; Xie et al., 2017a,b), confirming that
pH strongly affected the number of surface species at interfaces of pH controls the number of surface species at interfaces of oil/brine and
oil/brine at the presence of Na2SO4, implying a wettability alteration in brine/rock, thus wettability.
line with contact angle results. For example, the number of -COO- in-
creased from 16 to 22 μmol/m2 with increasing pH from 2 to 9 due to
the Reaction 2 shifting towards right-hand side (Fig. 4). However, the 4.2. pH effect on number of surface species at brine/calcite surfaces
number of –NH+ decreased from 19 to 16 μmol/m2 with increasing pH
due to the Reaction 1 shifting towards right-hand side (Fig. 4). Our pH strongly affected number of surface species at brine/carbonate
results are in line with Brady et al. (Brady et al., 2015) who showed that interface in the presence of Na2SO4 (Fig. 6). For example, when pH
–NH+ decreases with increasing pH. Moreover, –COO- increases with increased from 2 to 9, > CaSO4− decreased from 2.7 to 0.9 μmol/

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Q. Xie et al. Journal of Petroleum Science and Engineering 168 (2018) 419–425

m2)2, whereas at pH = 8, contact angle was 175° with bond product

sum 172 (μmol/m2)2. Note: a greater bond product sum means more
electrostatic bridges, thus more oil-wet system (Brady and Krumhansl,
2012).
In the presence of CaCl2, bond product sum increased with in-
creasing pH up to pH = 5.2, then decreased with further increasing pH.
This is largely because –NH+ decreases with increasing pH due to the
Reaction 1 shifting towards right-hand side, thus decreasing the bond of
[ > CO3−][-NH+]. Moreover, [ > CO3−][-COOCa+] decreased with
increasing pH after pH reaches at 5.2 (Fig. 5). Surface complexation
modelling results are also in line with contact angle results in the
presence of CaCl2. For example, at pH = 3, the contact angle was 30°
with bond product sum of 91 (μmol/m2)2; whereas at pH = 8, the
contact angle was 54° with bond product sum of 139 (μmol/m2)2. To-
gether, surface complexation modelling show that low pH triggers
Fig. 6. Site density of surface species at brine/carbonate interface as a function water-wet system, and high pH triggers oil-wet or slightly water-wet
of pH in the presence of 1 mol Na2SO4. system as a result of a greater bond product sum. This result further
implies that manipulating water chemistry to disturb the in-situ oil/
m2, > CO3− increased from 0.001 to 4.5 μmol/m2, and > CaOH2+ in- brine/rock physiochemical equilibrium may lift off the oil film ad-
creased from 1.8 to 3.6 μmol/m2. sorbed at the rock surface, altering wettability towards more water-wet,
pH also strongly affected the number of surface species at brine/ thus maximizing oil recovery. However, the potential of low salinity
carbonate in the presence of CaCl2 (Fig. 7). For example, apart effect likely decreases at low pH because of the strong water-wet
from > CaOH2+, which was almost constant with increasing pH, the system. This may explain why low salinity effect was not always ob-
number of surface species, > CO3−, increased from 0.01 to 2.82 μmol/ served in carbonate reservoirs. This is also in line with Sari et al. (2017)
m2 as pH increased from 2 to 5.5. However, further pH increase had who reported that pH = 2.55 results in a strong water-wet oil/brine/
little effect on the number of surface species. Similarly, > CO3Ca+ in- carbonate system (contact angel = 35°) although in the presence of
creased from 0.01 to 1.64 μmol/m2 as pH increased from 2 to 5.5, formation brine (high salinity = 252,244 ppm). In contrast, contact
whereas further pH increase had negligible effect on the density of angle increases with increasing pH while at a lower salinity (10 times
surface species. This is because in the presence of CaCl2, Reaction 7 and diluted formation brine). Surface complexation modelling was also
8 shift towards right-hand side with increasing pH as pH is lower than applied to interpret the contact angle results, showing a lower bonds
5.5. Our results are also in line with Brady et al. who show that in the between oil-calcite in formation brine compared to 10 times diluted
presence of 0.1 M NaCl at 100 °C, > CO3− and > CO3Ca+ increase with formation brine (Chen et al., 2018). Similar results were also observed
increasing pH till pH reaches at 7 (Brady and Thyne, 2016). by Jackson et al. (2016) who found that positively charged oil-water
interface likely fails low salinity effect in carbonate. Interestingly, low
pH likely triggers positive charged oil-water interface (Mahani et al.,
4.3. pH effect on electrostatic bridges between oil and rock
2015) because –NH+ dominates the surface charges at low pH (Brady
et al., 2015; Brady and Thyne, 2016) thus a strong water-wet system.
pH strongly affected the bond product sum in the presence of either
However, it is worth noting that pH effect is likely more pronounced on
Na2SO4 or CaCl2, suggesting that pH is a critical parameter that governs
aged samples. For example, our previous results show that contact
the oil/brine/carbonate system wettability. Note that bond product sum
angle increased from 30° (in formation brine, FB, with salinity of
of oppositely charged species at oil/brine/carbonate system (Brady
252,244 ppm) to 81° (100 times diluted FB) as pH increased from 2.55
et al., 2015) is [ > CaOH2+][-COO-]+[ > CO3−][-NH+]
to 5.68 in un-aged samples (Sari et al., 2017). However, for aged
+[ > CaSO4−][-NH+] at presence of Na2SO4, and [ > CaOH2+]
samples, contact angle increased from 35° to 175° with the same pH
[-COO-]+[ > CO3−][-NH+]+[ > CO3−][-COOCa+] +[ > Ca3Ca+]
increase. Together, the experimental results show that pH effect on age
[-COO-] at presence of CaCl2. To be more specific, in the presence of
samples becomes more obvious although more quantitative work re-
Na2SO4, bond product sum increased from 84 to 172 (μmol/m2)2 as pH
mains to be made to characterize and model this physical process.
increased from 2 to 9 in line with contact angle results. For example, at
low pH = 3, contact angle was 48° with bond product sum 84 (μmol/
5. Implications

In this study, we combined contact angle with geochemical mod-

elling, particularly focusing on the effect of pH on system wettability
(see Fig. 8). Our results provide insights to demonstrate that pH sig-
nificantly controls the surface chemistries in the oil/brine and brine/
rock interfaces, consistent with previous studies (Brady and Thyne,
2016, Mahani et al., 2016a,b; Chen et al., 2018). In particular, surface
complexation modelling results show that contact angle increases with
increasing bond product sum, correlating well with contact angle
(Fig. 9). This implies that bond product sum can likely be used as a
guideline to manipulate injection water chemistry for a given reservoir.
Note that bond product sum can also be related to zeta potential
(Mahani et al., 2016a,b; Sari et al., 2017), which is another parameter
that indicates the wettability.
pH scales with contact angle, thus oil/brine/rock wettability as pH
is lower than 6 (Fig. 10). In other words, oil composition, salinity, ionic
Fig. 7. Site density of surface species at brine/carbonate interface as a function strength, ion type may play a secondary role in the interaction of oil/
of pH in the presence of 1 mol CaCl2. brine/rock system at low pH, thus wettability. This also implies that

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6. Conclusions

Low salinity water flooding has been in the centre of attention in

industry as a cost-effective and environmentally friendly technique (Xie
et al., 2016). This is particularly true in the period of low oil prices (Al-
Shalabi and Sepehrnoori, 2016). Despite the fact that salinity level
(Puntervold and Austad, 2008; Mahani et al., 2015), ionic strength
(RezaeiDoust et al., 2011; Xie, Liu et al., 2012; Xie, Wu et al. 2012), oil
composition (Hadia et al., 2012; Hopkins et al., 2017; Wu et al., 2017)
and rock mineralogy (e.g., limestone and dolomite (Mahani et al.,
2016a,b)) on low salinity effect in carbonate reservoirs have been ex-
tensively investigated, few studies have been conducted regarding the
effect of pH on oil/brine/rock interaction, thus wettability.
To test the pH effect on oil/brine/carbonate system wettability, we
measured oil contact angles in the presence of either Na2SO4 or CaCl2 at
pH of 3 and 8. To gain a deeper understanding of the physiochemical
Fig. 8. Bond product vs. pH in the presence of Na2SO4 and CaCl2, respectively. interaction of the oil/brine/carbonate system, we performed a geo-
chemical study to demonstrate that contact angle increases with in-
creasing bond product sum, implying that bond product sum can likely
be used as a guideline to manipulate injection water chemistry for a
given reservoir (Brady and Thyne, 2016). Further, we conclude that pH
scales with contact angle, thus oil/brine/rock system wettability. In
particular, low pH (pH < 5) likely triggers a strongly water-wet system
due to H+ adsorption on the interface of oil/brine and brine/carbonate
(Xie et al., 2017a,b), and the salinity, ionic strength, and ion type paly a
minor role in wettability alternation at low pH. This also confirms that
CO2 flooding, carbonated water flooding, and CO2 huff-and-puff EOR
very likely renders a strongly water-wet system as a result of CO2 dis-
solution.

Acknowledgement

We would like to extend our appreciation to Mr Bob Webb for his

help and support towards conducting the laboratory measurement. We
are also thankful for the conversations with Prof Xinwei Liao and A/
Fig. 9. Contact angle vs. bond product sum in this work and previous work.
Prof Xiaoliang Zhao from China University of Petroleum (Beijing).
Sandia National Laboratories is a multimission laboratory managed and
operated by National Technology and Engineering Solutions of Sandia,
LLC., a wholly owned subsidiary of Honeywell International, Inc., for
the U.S. Department of Energy's National Nuclear Security
Administration under contract DE-NA-0003525.

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