International Journal of Greenhouse Gas Control 83 (2019) 256–264

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International Journal of Greenhouse Gas Control

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

Injection of in-situ generated CO2 microbubbles into deep saline aquifers for T
enhanced carbon sequestration
Seokju Seoa, Mohammad Mastiania, Mazen Hafeza, Genevieve Kunkela, Christian Ghattas Asfoura,
Kevin Ivan Garcia-Ocampoa, Natalia Linaresa, Cesar Saldanaa, Kwangsoo Yangb,
Myeongsub Kima,
⁎

a
Department of Ocean and Mechanical Engineering, Florida Atlantic University, 777 Glades Road, Boca Raton, FL33431, USA
b
Department of Computer & Electrical Engineering and Computer Science, Florida Atlantic University, 777 Glades Road, Boca Raton, FL33431, USA

ARTICLE INFO ABSTRACT

Keywords: Carbon sequestration into deep saline aquifers has been considered a promising technology for mitigating heavy
Carbon sequestration atmospheric carbon dioxide (CO2) concentration. When gaseous CO2 is continuously injected into these aquifers,
CO2 dissolution resident brine near a wellbore area is rapidly evaporated while precipitating significant amounts of salt at pores,
CO2 injectivity thereby damaging the aquifer media unfavorable for subsequent CO2 injection. In addition, the continuous
Deep saline aquifers
injection of CO2 at a large volume significantly hinders dissolution of CO2 into brine. In this study, we propose a
Microfluidics
new method of sequential water injection with gaseous CO2 for in-situ generation of micro-sized CO2 bubbles
that minimizes the brine drying-out and simultaneously accelerates CO2 dissolution. We observed that, with this
method, a partial volume of CO2 dissolves effectively into the co-injected water during pumping, thereby de-
creasing the rate of brine drying-out at pores. Another benefit of sequential injection is the significantly in-
creased rate of CO2 hydration induced by the large surface-to-volume ratio of tiny bubbles at micro to nanoscale.
To further accelerate CO2 hydration, we investigated reactive dynamics of bubble-driven CO2 hydration at
different frequencies of sequential injection and pH levels of the solution. Operation at a higher frequency with
higher basicity proved to be the most effective in decreasing the bubble size and therefore accelerating CO2
hydration into brine, which is a more feasible CO2 storage plan.

1. Introduction
Carbon capture and sequestration (CCS) technology has been pro-
posed as a promising method of global carbon dioxide (CO2) mitigation
(Gunter et al., 1998; Herzog, 2001). This technology aims to capture
CO2 from industrial and power plant combustion processes, and then
store the captured CO2 away in safe areas (e.g., depleted oil and gas
reservoirs, unmineable coal seams, and deep saline aquifers) to prevent
it from reaching the atmosphere. Among various possibilities, CO2 in-
jection into geological formations has proven to be the most attractive
method at a reasonable cost. Specifically, deep saline aquifers, defined
as porous and permeable reservoir rocks containing brine, located at
800 to 2000 m from the surface level are widely available for CO2
storage with the injection rate at more than 1 metric megaton per year
(Chow et al., 2003).
Although the storage capacity of these aquifers is known to be tre-
mendous, the potential of this option is currently limited by drying-out
of saline formations in the near-wellbore (Fuller et al., 2006; Kim et al.,
2013) and the slow rate of CO2 hydration (Bhaduri and Šiller, 2013; Seo
et al., 2017, 2018b). The large volume of continuous CO2 injection
creates a dried zone near the injection well (Miri and Hellevang, 2016;
Peysson et al., 2014). In the dried zone, the majority of the pores
contain trapped brine that will be eventually evaporated while salinity
of brine increases due to continuous CO2 injection (Miri and Hellevang,
2016). The brine drying-out results in salt precipitation and the pre-
cipitated salt blocks pores leading to a significant reduction in CO2
injectivity. Salt precipitation near the wellbore in the field-scale pro-
jects has been reported at the Snøhvit field (Grude et al., 2014; Hansen
et al., 2013) and the Ketzin pilot reservoir (Baumann et al., 2014), re-
spectively. Especially, a rapid pressure increase by salt precipitation
was observed after 5000 h of CO2 injection, resulting in a significant
decrease in injectivity at the Snøhvit field (Grude et al., 2014). Some
laboratory studies have investigated the rate of brine drying-out under
different injection/fluid conditions and found important controlling

⁎
Corresponding author.
E-mail address: kimm@fau.edu (M. Kim).

https://doi.org/10.1016/j.ijggc.2019.02.017
Received 17 October 2018; Received in revised form 26 February 2019; Accepted 27 February 2019
1750-5836/ © 2019 Elsevier Ltd. All rights reserved.
S. Seo, et al.
parameters for this phenomenon (Peysson et al., 2014; Pruess and
Müller, 2009; Rathnaweera et al., 2016; Zhao and Cheng, 2017). CO2
flow rates at 0.0083–0.83 mL/s (Miri et al., 2015) and 0.667 mL/s
(Wang et al., 2017) have been used to study the mechanisms of salt
crystallization and the changes in formation properties, respectively. In
addition, a range of salinity at 0.25–25% has been used (Tang et al.,
2015); note that the salt concentration of real brine has been found at
0.71–35% (Michael et al., 2010).
Another technical challenge to the feasibility of CO2 sequestration
in saline aquifers is the slow reaction rate of carbonic acid (H2CO3)
formation from CO2 hydration (Bhaduri and Šiller, 2013; Seo et al.,
2017, 2018b). This slow reaction rate can be negatively impacted fur-
ther by brine containing high salinity contents in natural formations.
When CO2 dissolves into brine, the CO2-saturated brine sinks toward
the bottom of the aquifers and thereby reduces the risk of CO2 leakage
since the density of CO2-saturated brine is greater than that of the
original brine (Pau et al., 2010; Zhang and Song, 2014). The dissolved
CO2 will combine with metal cations leading to precipitation of mi-
nerals. Resultantly, properties of brine in porous media are changed to
be the favorable condition for increasing permanent storage of CO2.
Therefore, to accelerate CO2 dissolution into deep saline aquifers, a new
methodology needs to be developed.
The brine drying-out, salt precipitation, and slow CO2 hydration are
attributed mainly to a continuous injection of CO2 to the formation
fluid. Over the years, many methods other than the continuous injec-
tion of CO2 have been proposed to resolve these challenges. For mini-
mizing the brine drying-out, one study suggested a preflush of the saline
formation with fresh water and it showed that this method delayed the
onset of salt precipitation and reduced its severity significantly. For
enhancing CO2 hydration, an ex-situ dissolution of CO2 via an external
reactor (Leonenko and Keith, 2008; Zendehboudi et al., 2011; Zirrahi
et al., 2013a, 2013b), a reverse gas-lift technology (Shafaei et al.,
2012), a static mixer at the bottom of well (Zirrahi et al., 2013a,
2013b), the injection of nanosized CO2 bubbles (Uemura et al., 2016),
and catalyst addition to the injection fluid (Seo et al., 2018b, 2017)
have been proposed. Among these strategies, the injection of CO2
bubbles, instead of the CO2 stream, has shown promising results to
accelerate CO2 hydration remarkably (Leonenko and Keith, 2008;
Uemura et al., 2016; Zendehboudi et al., 2011). One limitation of this
method is that the pumping process to generate CO2 bubbles in external
reactors requires huge energy consumption. Although numerous studies
have shown the important mechanisms associated with the brine
drying-out and CO2 hydration, they still lack a practical strategy to
resolve these concerns.
In this study, we present a practical methodology that could address
these challenges: significant reduction of drying-out and acceleration of
CO2 hydration by sequential injection of water with CO2 into the for-
mation. It is broadly known that the sequential injection of CO2-water
into a pipeline will generate various CO2 bubbles in their size due to the
gas-liquid two-phase flow (Abdulmouti, 2014; Das et al., 2009). In the
literature, it is well known that the fragmentation of large air cavities
by the turbulent flow can produce submillimeter bubbles (Rodríguez-
Rodríguez et al., 2015). Especially, after the liquid flow has established
in a large reactor or tubing, microbubbles can be generated by injecting
a short burst of gas into the liquid flow using a solenoid valve (Millard
et al., 2015; Ohl, 2001). We hypothesize that the sequential injection of
water with CO2 into the aquifers increases the CO2 dissolution rate by
producing microsized bubbles in the reservoirs and also effectively
decreases brine evaporation by supplying fresh water to salt-saturated
pores. This study aims to test this hypothesis and provide a new venue
for geologic CO2 injection while minimizing the brine drying-out and
maximizing CO2 storage capacity. The time-dependent brine evapora-
tion, resultant salt precipitation, and formation of CO2 bubbles were
visualized at high-speed through a microfluidic technique. Micro-
fluidics allowed us to quantify the amounts of brine evaporation and
mobile free-phase CO2 successfully by measuring both the velocity of
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International Journal of Greenhouse Gas Control 83 (2019) 256–264
the liquid−CO2 interface and the amount of gaseous CO2 at pore-scale.
The results show that the amount of mobile free-phase CO2 injected,
which is one of the main sources for the brine drying-out, can be re-
duced by changing the frequency of sequential injection and pH levels
of the injected solution.
2. Materials and methods
2.1. Microfluidic platforms
A microfluidic approach was used to visualize and quantify phase
equilibria and fluid transport associated with brine evaporation and
CO2 dissolution at the pore scale. The potential of this technique to
examine phase change analyses and fluid transport at micro- to na-
noscale has been proven in many studies due to the fast mass transfer at
these scales and its excellent capability for visualization of multiphase
flow (Kim et al., 2013; Mastiani et al., 2018, 2017a, 2017b; Seo et al.,
2018a). In this approach, an experimental platform containing fluidic
channels, called a microfluidic chip, is essential. Microfluidic chips
were fabricated by laser ablation using a laser cutter (VersaLaser
VLS2.30, Universal Laser Systems, Inc.). Poly(methyl methacrylate)
(PMMA) was used for a chip material due to its high chemical resistance
and mechanical stability (Sher et al., 2017). As illustrated in Fig. 1, the
microfluidic chip consists of 1000 μm wide straight channels for sup-
plying gaseous CO2 and isolated pore channels for trapping brine. The
height of all channels is 1500 μm.
2.2. Experimental procedure
All tests were performed by pumping fluids under two different
conditions: continuous and sequential injection (Fig. 1a). For the con-
tinuous injection of CO2 (Fig. 1b), once the microfluidic chip was filled
with brine at different salinities, a clamping device sealed the inlet port
for the solution to prevent backflow of trapped brine induced by in-
jection of CO2. Then, the CO2 gas with 99.9% purity (Airgas®, Miami,
FL) was introduced to the microfluidic chip at different flow rates
through the connected inlet port to a regulator mounted on a CO2 tank.
For the sequential injection of water with CO2, a fast switching me-
chanism of a three-way solenoid valve operated by microcontroller-
based (Arduino Uno) electronic control circuits (Fig. 1c) was employed.
Two inlets of this solenoid valve were connected to a syringe pump
(PHD ULTRA™ 4400, Harvard Apparatus, Natick, MA) and the CO2
regulator. This valve sequentially injected water at 0.03 mL/s from the
syringe pump and CO2 gas at 118 mL/s from the tank into the micro-
fluidic platform. This ensures precisely controlled frequencies (0.1 to
0.5 Hz) of sequential injection of water with gaseous CO2. When gas-
eous CO2 was sequentially introduced with water, CO2 bubbles with a
diameter range of 40–150 μm were generated in the trapped brine. The
microbubble is defined as bubbles having a diameter less than few
hundred μm in this study similar to that in the previous literature in the
field of fluid physics (Parmar and Majumder, 2013). Once the tests for
CO2 bubble formation at different frequencies were completed, the
behavior of brine evaporation and the amount of mobile free-phase CO2
in brine were investigated at various pH levels of pumping water (pH 3,
pH 7, and pH 11). A high-speed camera (Fastec IL5S, Fastec Imaging,
CA) attached to an inverted microscope (IX73, Olympus Corporation,
Japan) was used to capture time-resolved images of the liquid-gas in-
terface and the amount of trapped CO2 in brine.
2.3. Materials and experimental conditions
For the fabrication of microfluidic devices, PMMA sheets were
purchased from Good Fellow (Berwyn, PA). Sodium chloride (NaCl,
≥99.5% purity), sodium hydroxide (NaOH, ≥98% purity), hydro-
chloric acid (HCl, 37%), and phosphate buffer powder were purchased
from Sigma − Aldrich (St. Louis, MO). One millimolar (mM) phosphate
S. Seo, et al.
Fig. 1. (a) Schematic of the experimental setup (not to scale). (b) Continuous CO2 injection to the microfluidic chip with time-dependent brine evaporation at the
trapped channel. (c) Sequential water−CO2 injection to the same channel generating CO2 microbubbles.
buffer solution used in all tests was prepared using deionized water
produced from a Millipore Milli − Q integral 5 purification system
(Millipore, Bedford, MA). Brine evaporation experiments were per-
formed at concentrations of 0%, 5%, 10%, 20%, and 30% NaCl added to
1 mM phosphate buffer solution at different injection rates of dry gas-
eous CO2 (68, 97 and 118 mL/s). Then, the highest salinity at 30% with
the highest injection rate of dry CO2 at 118 mL/s was used to in-
vestigate how effectively sequential water injection with CO2 can re-
duce brine evaporation and the amount of gaseous CO2 in brine. The pH
of the sequential water was titrated to desired levels that were created
by adding either one M of HCl or NaOH while monitoring with a pH
meter (Accumet AE150, Fisher Scientific, Pittsburgh, PA). All experi-
ments were performed at room temperature of 25 °C and atmospheric
pressure. An atmospheric pressure condition was used at the outlet.
2.4. Image processing for evaporated brine and gaseous CO2
The volumes of evaporated brine and gaseous CO2 in the isolated
pore channel were analyzed on the ImageJ software, an open-source
image processing program. To measure brine evaporation in various
conditions, the changes in the interface between CO2 gas and trapped
brine in the isolated pore channel corresponding to water evaporation
were tracked by the ImageJ. In addition, the volume fraction of the
mobile free-phase CO2 in trapped brine was determined by changes in
its volume at 0.04 s intervals. The CO2 bubble diameter (D) was
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International Journal of Greenhouse Gas Control 83 (2019) 256–264
determined through the projected area of CO2 bubble. Then, the CO2
bubble volume (V = (4/3)π(D/2)3) was determined using the average
diameter (D) of CO2 bubbles.
3. Results and discussion
3.1. Continuous injection of CO2
The experiments on the water evaporation at various salinity levels
and CO2 flow rates were performed to characterize how different fluid
and flow rate conditions in deep saline aquifers influence the brine
drying-out. Fig. 2 shows time-lapse optical microscopy images of
changes in the gas-liquid interface at an isolated pore channel. The
interface was formed when dry gaseous CO2 was continuously injected
at 68, 97 and 118 mL/s at different salinities (0, 5, 10, 20, and 30%
NaCl). In these conditions, CO2 velocities are 23.51, 33.25, and
40.72 m/s, which represent assumed conditions around injection wells
at the CO2 storage site. In general, as the volume flow rate increases, the
speed of interface retraction also increases; for example, compare time-
dependent changes in the location of the interface at 0% salinity in
Fig. 2a and c. This behavior was quantitatively analyzed by tracking
changes in volume of evaporated brine at a T-junction (Fig. 3). Ap-
proximately 2.2 μL of volume of pure water in the channel was eva-
porated within 120, 46, and 4.6 s at 68, 97 and 118 mL/s of CO2 flow
rates, respectively. This analysis shows that the amount of brine
S. Seo, et al. International Journal of Greenhouse Gas Control 83 (2019) 256–264

Fig. 2. Sequential images for changes in the CO2-water interface location at a T-junction at different salinities (0, 5, 10, 20, and 30% NaCl) with different CO2
injection rates at (a) 68, (b) 97, and (c) 118 mL/s.

evaporated exponentially increased as CO2 flow rate increased from 68

to 118 mL/s. In general, an increase in air velocity over water leads to
an increase in rate of escaping water molecules (Arnal et al., 2005). In
line with this phenomenon, we observed forced convective mass
transfer between horizontal CO2 gas flow and water increases with
increasing gaseous CO2 flow rates. Reynolds numbers (Re) at different
flow rates were determined to be 4464.37, 6313.92, and 7732.42 using
8.36 × 10−6 m2/s of kinematic viscosity of CO2 at 25 °C, 1.58 × 10-3 m
of tubing diameter, and CO2 velocities at 23.51, 33.25, and 40.72 m/s.
For the impact of salinity on brine evaporation, the kinetics of brine
evaporation at different salinity levels are plotted in Fig. 4. This figure
is determined by different slopes for the relationship between evapo-
rated brine and the elapsed time (Fig. 3). As the concentration of sali-
nity increases up to 10%, the evaporation rate decreases in all flow rate
conditions. However, by increasing the salinity from 10% to 30%, an
increase in the evaporation rate is observed in three flow rate condi-
tions. The highest rate of evaporation was determined to be 0.57 μL/s
Fig. 4. A diagram of changes in the evaporation rate of brine as a function of
under 30% salinity at the highest CO2 flow rate (118 mL/s). This de-
the salinity (0, 5, 10, 20, and 30% NaCl) with different CO2 injection rates (68,
crease-to-increase behavior can be explained by an activity coefficient
97, and 118 mL/s) and the graph (◊) of the activity coefficients of NaCl solution
of NaCl solution controlling brine evaporation dynamics. The activity at 25 °C.
coefficient is used in thermodynamics to explain the behavior of che-
mical substances. As the activity coefficient decreases, the energy re-
quired to separate constituent molecules increases. Conversely, when 0.5067 IM
log = + 0.0316 2IM log(1 + 0.036M )
the activity coefficient increases, molecules have a strong repelling 1 + 0.837 2IM
force, and thereby less energy is required to separate them (Pitzer et al.,
where IM, M, and γ are the ionic strength (mol/L), the concentration
1984). Evaporation occurs when molecules in a liquid gain enough
(mol/L), and the activity coefficient of NaCl solution at 25 °C, respec-
energy to overcome an attraction force from other molecules. The ac-
tively. We estimated each value of the activity coefficient at different
tivity coefficients of brine at different salinities can be calculated from
salinities ranging from 0% to 30% to characterize the salinity effect on
the electromotive force data by Hückel's equation (Harned and Nims,
the evaporation rate. A decrease in the activity coefficient while in-
1932).
creasing the salinity concentration up to 7% led to a decrease in brine
evaporation into the CO2 gas phase (Fig. 4). In contrast, increasing

Fig. 3. Variations of evaporated brine vs. elapsed time at different salinities and CO2 flow rates. (Error bars represent the standard error of the mean from triplicated
experiments in each condition.)

259
S. Seo, et al.
Fig. 5. Representative time-lapse optical microscopy images showing the generation and coalescence of CO2 microbubbles during sequential water−CO2 injection.
salinity concentration from 7% to 30% displays an increase in the ac-
tivity coefficient to 0.869, resulting in a proportional increase in the
evaporation rate of brine. The observations of our test results are in a
good agreement with the theory of the activity coefficient. These mi-
crofluidic tests confirm that continuous injection of gaseous CO2 into
deep saline aquifers may lead to an increase in risks of the brine drying-
out. The extreme drying-out creates salt precipitation behind and
causes formation damage. We observed that the degree of brine drying-
out increases as CO2 flow rate increases at salinity greater than 10%.
3.2. Sequential water injection with CO2
We hypothesized that sequential injection of water with CO2 ad-
dresses the challenge with the brine drying-out and provides another
benefit to accelerate the rate of CO2 hydration. To test the feasibility of
the sequential injection strategy, microfluidic experiments were per-
formed in a simple T-junction microchannel. Fig. 5 shows re-
presentative images of CO2 microbubble generation in the micro-
channel taken by an optical microscope from selected time points
(t = 1, 20, and 50 s) at a controlled frequency of 0.1 Hz. As pure water
and CO2 were sequentially injected, CO2 microbubbles were generated
due to the nature of two-phase flow (Abdulmouti, 2014; Das et al.,
2009). Locations of the gas-liquid interface were maintained constant
near the T-junction during sequential injection, which consequently
delayed the evaporation rate of water. Not only does decreasing the
brine drying-out and therefore reducing a risk of salt precipitation, but
the sequential injection of pure water−CO2 also increases CO2 hydra-
tion into brine. The physical absorption of gaseous CO2 by the liquid
phase is determined by Henry’s law.
Pco2 = kH [CO2 ]aq
where kH is Henry’s constant for CO2 in pure water (3.45 × 103 kPa L/
mol), [CO2]aq is the concentration of dissolved CO2 in the aqueous
phase, and PCO2 is the partial pressure of the CO2. The rate for this
physical absorption can be increased further by agitation in the liquid
phase (Noyes et al., 1996). The agitation can generate CO2
Fig. 6. Representative microscopy images showing the generation and coalescence of CO2 microbubbles at different pore angles (30, 90, and 120° between an inlet
channel with isolated pore channel) during sequential water−CO2 injection.
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International Journal of Greenhouse Gas Control 83 (2019) 256–264
microbubbles effectively with a large surface-to-volume ratio leading to
significant improvement of a CO2 solubility trapping process because
the mass transfer of gaseous CO2 into water will further increase with
larger interface areas between these two phases. As in Fig. 5, due to the
physical agitation, number and size of CO2 bubbles change over time.
The figure shows that the onset of CO2 bubble formation is observed at
a few locations at t = 1 s. The CO2 bubbles are accumulated im-
mediately near the T-junction and start to coalesce due to the collision
between the CO2 bubbles (see Video 2). It should be noted that mi-
crobubbles in an aqueous solution are negatively charged under a wide
range of pH (Takahashi, 2005). However, as increasing the ionic
strength in the aqueous phase, the reduction in the zeta (ζ) potential of
microbubbles was reported (Takahashi, 2005). As a result, CO2 mi-
crobubbles in 30% NaCl near the T-junction are easily coalesced to
minimize their surface areas when they are in touch. The size of CO2
bubbles apart from the T-junction is significantly decreased due to ef-
fective CO2 hydration.
As typical natural saline aquifers are characterized as random
porous structures, the directional water−CO2 injection into pore
structures is certainly of interest. The pore-throat and pore sizes of ty-
pical sandstones range from 1 to 500 μm in conventional reservoirs
(Nelson, 2009; Radlinski et al., 2004; Wardlaw and Cassan, 1979). To
examine the behaviors of CO2 bubble generation in different geome-
tries, transient CO2 bubble formation during sequential water and CO2
injection was recorded at different pore angles (30°, 90°, and 120°,
Fig. 6 and see Video 3). The results show that an insignificant variation
in the amount of CO2 bubbles was observed in the pore channel at these
angles.
3.3. Frequency effect
The high solubility coefficient of CO2 makes it immediately diffuse
into an aqueous phase when it is in contact with water. In addition, as
aforementioned the high surface-to-volume ratio will improve CO2
hydration into water. To further enhance CO2 gas dissolution and safe
storage potential, generation of a much smaller volume of CO2 bubbles
S. Seo, et al.
Fig. 7. Time-dependent images of CO2 microbubble generation and coalescence near the T-junction at different water−CO2 injection frequencies (0.1, 0.2, and
0.5 Hz).
is important. We found that the frequency of water-gas injection plays a
role in varying the gas bubble sizes. Fig. 7 shows the total volume of
CO2 bubbles generated at t = 0˜60 s in a T-junction channel at fre-
quencies of 0.1, 0.2, and 0.5 Hz. At a frequency of 0.5 Hz, number of
CO2 micro-bubbles was increased as time increases while their sizes are
less than 100 μm at t = 60 s. On the other hand, at 0.1 Hz number of
CO2 bubbles was decreased while their sizes are greater than 500 μm at
t = 60 s. This implies that an increase in frequency leads to a decrease
in the volume of CO2 bubbles occupying the brine at the channel (VCO2/
VChannel) owing to improved CO2 hydration.
Fig. 8 shows the change in ratio of the volume of CO2 bubbles to
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International Journal of Greenhouse Gas Control 83 (2019) 256–264
trapped brine (VCO2/VChannel) in the microchannel at different fre-
quencies. In agreement with the observation in Fig. 7, as the frequency
increases, the volume of trapped water is slowly replaced by that of CO2
bubbles. Particularly at the 0.5 Hz, the volume of CO2 bubbles at 60 s
was estimated to be approximately 2-fold smaller than that in the
0.1 Hz condition. These significant differences in the volume of CO2
bubbles trapped in brine at different frequencies can be characterized
by bubbly two-phase flow. The volume of CO2 bubbles in bubbly two-
phase flow is likely to be dominated by the ratio of liquid-gas flow rates.
Fraga and Stoesser (Fraga and Stoesser, 2016) revealed that smaller
bubbles are generated when a high flow rate of an aqueous phase and a
S. Seo, et al. International Journal of Greenhouse Gas Control 83 (2019) 256–264

results can be explained by the behavior of the effective Henry’s con-

stant (Seinfeld and Pandis, 2016). The total quantity of dissolved CO2 in
brine includes the amount of all species of aqueous CO2, the inter-
mediate bicarbonate (HCO3−) form, and the equilibrium carbonate
(CO32-) form in water. First, physical absorption of CO2 into brine is
governed by Henry’s law.

PCO2
CO2(g ) + H2 O CO2(aq) , kH =
[CO2 ]aq

CO2 (aq) reacts with water to form carbonic acid (H2CO3), then
dissociates into H+ and HCO3− ions at the intermediate stage.
CO2(aq) + H2 O H2 CO3

H2 CO3 H+ + HCO3 ,
H+ HCO3 7
K1 = = 4.45 × 10
Fig. 8. Variations in the ratio of the volume of CO2 microbubbles to the total CO2(aq)
volume of brine at the isolated channel at different injection frequencies. The
inset figures represent images of the channel taken at t = 60 s. Then, HCO3− dissociates further into H+ and CO32- ions.

HCO3 H+ + CO32 ,
low flow rate of a gaseous phase are mixed. In our tests, when a valve is
H+ CO32
operating at low frequency (0.1 Hz), CO2 gas is compressed, thereby K2 = = 4.69 × 10 11

creating a high flow rate of a CO2 phase. Due to the incompressibility of HCO3
the continuous aqueous phase (i.e., water), its flow rate remains con- The total amount of CO2 in the aqueous phase can be calculated by
stant, which thereby increases the ratio of liquid-gas flow rates in the solving for the equilibrium constants (K1 and K2) with Henry’s constant.
system. The generation of much smaller CO2 bubbles at 0.5 Hz fre-
quency accelerates CO2 hydration. These results imply that sequential PCO2 K1 KK
CO2(total) = CO2(aq) + HCO3 + CO32 = 1 + + 1+ 22
water injection with CO2 at high frequency would facilitate CO2 hy- kH [H+] [H ]
dration in brine leading to rapid mineral precipitation. Another im-
An effective Henry’s constant, kH*, which accounts for the total
portant observation is that a decreasing drying-out effect by sequential
dissolved CO2, can be described by the following equation:
water injection with gaseous CO2 leads to 15-fold slower brine eva-
poration rate than continuous injection of CO2 (Fig. 2a vs. Fig. 7). PCO2 kH
kH * = =
3.4. The pH effect
CO2(total)
(1 + K1
[H +]
+
K1 K2
[H +]2 )
Each value of the effective Henry’s constant at different pH levels
The pH of an aqueous solution is considered as another parameter was determined to identify the pH effect on VCO2/VChannel (Fig. 9). In
which controls the CO2 solubility trapping process (Seinfeld and Pandis, theory, CO2 dissolution into water increases as the value of effective
2016). Fig. 9 shows a time-dependent ratio of the volume of CO2 Henry’s constant decreases; for example, kH* = 1.36 × 10−2 at pH 11,
bubbles to trapped brine (VCO2/VChannel) at different pH levels. When pH 6.33 × 102 at pH 7, and 3.44 × 103 kPa L/mol at pH 3, respectively.
changes from pH 7 to pH 3, the relative volume of CO2 bubbles at the Taking this fact into consideration, Fig. 9 shows significant increases in
isolated pore channel increases. In contrast, no significant differences in the value of effective Henry’s constant from pH 7 to pH 3 led to a de-
VCO2/VChannel were found between pH 7 and pH 11. These experimental crease in the CO2 dissolution. In contrast, as noted earlier, no sub-
stantial difference was observed at pH 7 and 11.

3.5. Discussion and outlook

The impacts of sequential CO2 and water injection into geologic

Fig. 9. Bottom-X left-Y: Variations in the ratio of the volume of CO2 micro-
bubble to the total volume of brine at the isolated pore channel at 0.5 Hz fre-
quency at different pH. Top-X right-Y: A diagram of effective Henry’s constant
as a function of pH.
aquifers are significant with an important perspective of water eva-
poration and resultant brine drying-out when compared with the con-
ventional methods. Up to this point, several methods other than the
direct injection of dry CO2 through injection wells have been proposed
to improve formation damage during carbon sequestration due to the
brine drying-out. One method is an ex-situ approach, where brine is
extracted from the saline aquifers, sparged with pressurized gaseous
CO2 to produce CO2-saturated brine in reservoir conditions, and then
reinjected through the pipeline into the original aquifer (Leonenko and
Keith, 2008; Zendehboudi et al., 2011). The main benefit of this
methodology is that CO2 dissolution into an aqueous phase can be ac-
celerated by the generation of CO2 bubbles in a mixing chamber due to
the gas-liquid two-phase flow. When gaseous CO2 is introduced into
water, two-phase flow occurs along with generation of CO2 bubbles in a
continuous aqueous phase (Abdulmouti, 2014; Das et al., 2009), ulti-
mately enhancing the CO2 trapping within deep saline aquifers. Al-
though this approach has shown a potential for great reduction of a
mobile CO2 phase causing dreadful leakage, the pumping process that

262
S. Seo, et al.
circulates brine from the reservoir to the ground pipeline and the
pressurization of CO2 in aquifer conditions requires significant energy
consumption, making this approach impractical. In addition to this
method, simultaneous injection of CO2 and geologic saline water into
reservoirs has been considered as a substitute of the ex-situ approach
(Hassanzadeh et al., 2009; Leonenko and Keith, 2008; Shafaei et al.,
2012). It has been considered that this method not only increases the
possibility of permanent storage of CO2 but also reduces economic
strain notably, as the energy cost associated with this process is less
than 20% of the cost for compressing the CO2 to reservoir conditions
(Leonenko and Keith, 2008). However, many bottlenecks restricting
field applications of this technology still remain, including the re-
quirement of the additional pipeline installation for brine circulation.
On the other hand, the proposed sequential water injection with gas-
eous CO2 could be a solution by combining advantages of the afore-
mentioned ex-situ approach with simultaneous injection of CO2 with
water. The sequential injection of water via a single pipeline can
eliminate the need for an additional pipeline for economical tech-
nology.
In the context of a methodology, a microfluidic-based approach
provides new perspectives regarding the brine drying-out at the pore
scale in geologic aquifers in a simple and cost-effective manner.
However, it should be noted that there still exist opportunities to im-
prove our current results in terms of the material and surface properties
of microfluidic models and a variety of ions other than NaCl. In addi-
tion, although the ratio of the volume of CO2 bubbles to trapped brine
(VCO2/VChannel) strongly depends on the flow rate ratio of the two
phases, the operation pressure is still not relevant to the actual oper-
ating condition. Temperature is an important parameter to change the
rates of brine evaporation and CO2 solubility. The reservoir-specific
temperature conditions (e.g., 40 °C (Rathnaweera et al., 2016) and
62 °C (Holt et al., 1995)) can decrease the brine drying-out and CO2
dissolution rates. The water content of CO2 at room temperature of
25 °C and atmospheric pressure is approximately 23 times higher than
that at 10 MPa and 40 °C (Salari et al., 2011). Due to this higher CO2
water content, the brine drying-out in our experiments is possibly
greater than that in the actual reservoir-specific condition. Never-
theless, the microfluidic approach, for the first time, demonstrates the
efficacy of a new novel injection strategy for CO2 into geologic for-
mations. To test the feasibility of the proposed sequential injection
approach to the actual saline aquifers, water evaporation and the brine
drying-out experiments in the 2D and 3D porous media that mimic the
natural aquifers in terms of surface properties and geometry will be
performed at higher pressures. The complex nature of these random
networks will offer dynamic physicochemical processes close to the
actual phenomena and direct visualization of these interactions would
provide new understandings of the pertinent multiphase interplay in
geologic formations.
4. Conclusion
We performed pore-scale experiments of geofluid dynamics oc-
curred in deep saline aquifers when gaseous CO2 is sequentially in-
troduced with water using microfluidic platforms. A simple microfluidic
imaging technique enabled quantification of a volume fraction of in-
jected CO2 and resultant evaporated brine to open a new opportunity
for strategic carbon sequestration plans into deep saline aquifers.
Specifically, the principal factors contributing to the brine drying-out
by traditional dry CO2 injection can be identified through quantifica-
tion of the amount of evaporated brine at the pore-scale. The results
from this observation are well aligned with the conventional theory of
the activity coefficient and offer reliable modeling of interactions be-
tween CO2-brine occurred in actual saline aquifers. To overcome the
brine drying-out challenge, this study suggests a new strategy of se-
quential water injection with CO2. This scenario was experimentally
tested through the microfluidic technique for quantification of the
263
International Journal of Greenhouse Gas Control 83 (2019) 256–264
amounts of brine evaporation and mobile free-phase CO2 and proven to
be a potential solution to mitigate the concerns about the brine drying-
out. We found that the brine evaporation rate in the new strategy was
approximately 15-fold slower than the conventional gaseous CO2 in-
jection. In addition, the new strategy generated large surface-to-volume
ratio microbubbles and these CO2 bubbles effectively accelerated their
dissolution in brine due to the increased gas-liquid interfaces. To fur-
ther enhance CO2 dissolution, operating condition parameters, i.e., in-
jection frequency and solution pH, were controlled. The results show
that sequential of water with CO2 injection at a low frequency at higher
basicity accelerated CO2 dissolution effectively and decreased the vo-
lume fraction of CO2 bubbles occupying the pore.
Acknowledgments
The authors gratefully acknowledge the funding provided by Janke
Research Fund at Florida Environmental Studies. We also thank
Heather Crawford for her help with laboratory experiments; Babak
Mosavati and Minh Nguyen for their comments on the manuscript.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.ijggc.2019.02.017.
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