You are on page 1of 12

minerals

Article
CO2 Mineralization Using Brine Discharged from
a Seawater Desalination Plant
Jun-Hwan Bang, Yeongsuk Yoo, Seung-Woo Lee, Kyungsun Song and Soochun Chae *
Change Mitigation and Sustainability Division, Korea Institute of Geoscience and Mineral Resources (KIGAM),
124 Gwahang-no, Yuseong-gu, Daejeon 34132, Korea; jhbang@kigam.re.kr (J.-H.B.);
ysyoo6804@kigam.re.kr (Y.Y.); swlee21th@kigam.re.kr (S.-W.L.); kssong@kigam.re.kr (K.S.)
* Correspondence: chae@kigam.re.kr

Received: 12 September 2017; Accepted: 27 October 2017; Published: 30 October 2017

Abstract: CO2 mineralization is a method of sequestering CO2 in the form of carbonated minerals.
Brine discharged from seawater desalination is a potential source of Mg and Ca, which can precipitate
CO2 as forms of their carbonate minerals. The concentration of Mg and Ca in brine are twice those in
the seawater influent to desalination process. This study used a cycle for CO2 mineralization that
involves an increase in the pH of the brine, followed by CO2 bubbling, and, finally, filtration. To the
best of our knowledge, this is the first time that non-synthesized brine from a seawater desalination
plant has been used for CO2 mineralization. The resulting precipitates were CaCO3 (calcite),
Mg5 (CO3 )4 (OH)2 ·4H2 O (hydromagnesite), and NaCl (halite) with these materials being identified
by X-ray Diffraction (XRD), Fourier transform infrared (FTIR) and thermo gravimetric-differentail
thermal Analysis (TGA)-DTA. Despite the presence of Ca with Mg in brine being unfavorable for
the precipitation of Mg carbonate, Mg reacted with CO2 to form hydromagnesite at a yield of 86%.
Most of the Ca formed calcite, at 99% yield. This study empirically demonstrates that brine from
seawater desalination plants can be used for CO2 mineralization.

Keywords: CO2 mineralization; desalination; carbonates; brine; seawater

1. Introduction
Climate change and abnormal weather phenomena have been worsening, owing to increased
CO2 emissions around the world. Typically, the Korean peninsula is not a region that is known to
suffer from water shortages [1]. However, since in the last few years there have been severe annual
droughts, especially in west-coast areas, with increased CO2 emissions being blamed. Several methods
of preserving water resources have been examined, and seawater desalination has been found to
be a successful candidate [2,3]. Seawater desalination processes remove the salts from seawater
by distillation, membrane separation, and/or reverse osmosis (RO) to produce useful water that is
suitable for drinking and industrial purposes [3–5]. One result of these processes is that concentrated
seawater (i.e., brine) is also produced, in which the rejected salts in seawater have been concentrated.
Desalination consumes large amounts of energy, meaning that large-scale desalination plants are often
placed near power stations [2], and also leads to the emission of massive amounts of CO2 , which will
eventually exacerbate the problems that desalination is attempting to solve. Methods of limiting CO2
emissions or removing CO2 from desalination plants are, therefore, of great interest.
CO2 mineralization is one such method of sequestering CO2 . In this method, CO2 reacts with
calcium and/or magnesium to form calcium carbonate and/or magnesium carbonate [6]. The rate of
CO2 mineralization can be accelerated when the reaction takes place in the aqueous phase, as happens
in typical chemical reactions. Ionization of CO2 to CO3 2− takes place under alkaline conditions. This is
essential for CO2 mineralization, as it allows ionic reactions between CO3 2− and Ca2+ and/or Mg2+ .

Minerals 2017, 7, 207; doi:10.3390/min7110207 www.mdpi.com/journal/minerals


Minerals 2017, 7, 207 2 of 12

For this reason, alkaline chemicals such as NaOH or NH4 OH are applied to increase the pH of the
aqueous phase in CO2 mineralization [7,8].
Meanwhile, using Ca and Mg from industrial waste such as waste concrete, slags from steel
production, and liquid wastes is preferable when attempting to design feasible CO2 mineralization
processes [9–13]. Detailed principles and applications of CO2 mineralization using alkaline waste
have been summarized by Pan et al. [14]. Some pretreatment steps, such as crushing, sieving,
activation, and/or digestion are required to extract Ca and Mg from solid waste [13,15,16]. When using
liquid waste, such pretreatment procedures are not required because the Ca and/or Mg are already
present as ions. For this reason, the use of brine for CO2 mineralization is a promising route for
investigation [6,8,17]. In the implementation of this technology, both engineering and economic factors
are important, as is environmentally balanced performance [18].
It is reported that the concentrations of the rejected salts in brine from desalination plants using
reverse osmosis (RO) systems are 2–2.5 times higher than those in influent seawater [19], suggesting
that brine could be a promising material for CO2 mineralization. If Mg alone is present in a solution,
it readily reacts with CO2 to precipitate Mg carbonates; the reaction between MgCl2 ·6H2 O solution
and CO2 produced nesquehonite (MgCO3 ·3H2 O), dypingite (Mg5 (CO3 )4 (OH)2 ·5H2 O), dypingite-like
(Mg5 (CO3 )4 (OH)2 ·8H2 O), and hydromagnesite (Mg5 (CO3 )4 (OH)2 ·4H2 O) crystal phases, depending
on the reaction conditions [20]. When considering brine for CO2 mineralization, it is worth noting
that in previously reported studies, materials in a replica brine solution with coexisting Mg and Ca
were not readily carbonated. Liu and Maroto-Valer [21] synthesized oil-field brine and conducted CO2
mineralization experiments under mimicked underground conditions to precipitate calcite. An artificial
brine containing metal ions such as Na+ , Mg2+ , Ca2+ , K+ , and Sr2+ , and anions including Cl− , SO4 2− ,
Br− , BO3 3− , F− , and HCO3 − was unfavorable for the precipitation of Mg carbonates, but was
favorable for CaCO3 precipitation [22]. In the same manner, simulated brine composed of NaCl,
MgCl2 , CaCl2 , Na2 SO4 , and KCl precipitated CaCO3 by the primary separation of Mg(OH)2 from the
Ca2+ solution [23]. Owing to the significantly higher concentration of Mg than Ca in seawater and brine,
Mg would allow much more CO2 mineralization than Ca does. However, this does not necessarily mean
that more precipitating Mg carbonates than Ca carbonates will be produced, because Ca carbonates
are more sparingly soluble than Mg carbonates (for example, Ksp (hydromagnesite) = 1.26 × 10−5 [24],
and Ksp (calcite) = 3.36 × 10−9 at 25 ◦ C each [25]).
This paper introduces the first use of non-synthesized brine discharged from a functional seawater
desalination plant for CO2 mineralization; we have particularly focused on the precipitation of
Mg carbonates. Repeated cycles involved the pH adjustment of brine, and the injection of CO2
microbubbles showed that Mg carbonation could be achieved alongside Ca. Various analytical
techniques were used for the identification of the precipitates, including X-ray diffraction (XRD)
analysis. We have empirically proved that CO2 mineralization using brine for CO2 sequestration.

2. Experimental
The brine used in this study was collected from an ongoing seawater RO process for industrial
water supplementation in Korea. The major cations and anions in this brine and their concentrations
as measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES; Optima 8300,
PerkinElmer, Shelton, CT, USA) are listed in Table 1. The concentrations of Sr, Si, Li, Cu, and rare earth
elements such as W, Mo, and Rb were also measured, but the values obtained were not significant.
Anion concentrations were measured by ion chromatography (IC; Dionex ICS-5000+, Thermo Fisher
Scientific, Sunnyvale, CA, USA), and the SO4 2− concentration was measured using IC equipped with
an Ag cartridge (Dionex OnGuard II Ag, Thermo Fisher Scientific).
Minerals 2017, 7, 207 3 of 12

Table 1. Concentrations of the major cations and anions in the brine.

Ions Mg Ca Na K Cl SO4
Minerals 2017, 7, 207 3 of 12
Concentration (mg/L) 2226 714 17,987 858 32,220 4766
Table 1. Concentrations of the major cations and anions in the brine.
NaOH solution (1 M) was prepared for use as an alkaline chemical by dilution of NaOH
Ions Mg Ca Na K Cl SO4
(96%, Junsei Chemicals, Tokyo,(mg/L)
Concentration Japan) with deionized
2226 water17,987
714 (Milli-Q858 Gradient-A10,
32,220 Millipore,
4766 Billerica,
MA, USA). The pH of 0.25 L of brine was increased from an initial value of 8.2 to 10–13.5 (measured by
Orion Star A215,
NaOH Thermo
solution (1 M) Scientific,
was prepared Singapore)
for use as byanadding
alkalinethe 1 M by
chemical NaOH solution
dilution of NaOH to (96%,
the brine
in a beaker with a lid
Junsei Chemicals, at aJapan)
Tokyo, rate of with4 deionized
mL/min water using(Milli-Q
a peristaltic pumpMillipore,
Gradient-A10, (EMP-2000W,
Billerica,EMS-tech,
MA,
USA). The
GyeongGi, pH ofat0.25
Korea) L of brine
ambient was increased
temperature andfrom an initial
pressure. The value
brine of 8.2
was to stirred
10–13.5 (measured
while the by NaOH
solution was added, and as the pH of the brine increased, a suspension of white precipitatesa was
Orion Star A215, Thermo Scientific, Singapore) by adding the 1 M NaOH solution to the brine in
beaker
formed. withthe
Once a lid at a rate
target pHofwas 4 mL/min
reached,usingthea peristaltic
suspension pumpwas(EMP-2000W,
filtered with EMS-tech,
a 0.45 µmGyeongGi,
pore nylon
Korea) at ambient temperature and pressure. The brine was stirred while the NaOH solution was
membrane (Whatman, Brentford, UK) to allow the concentrations of the metal ions listed in Table 1 to
added, and as the pH of the brine increased, a suspension of white precipitates was formed. Once
be measured by ICP-OES. However, only the concentrations of Mg, Ca, and Na changed with pH and,
the target pH was reached, the suspension was filtered with a 0.45 μm pore nylon membrane
as such, only
(Whatman, theBrentford,
concentrations UK) toofallow
thesethethree elements are
concentrations of reported
the metalinions the listed
resultsinsection.
Table 1 to be
In the cyclic
measured CO2 mineralization
by ICP-OES. However, only experiments, as 1 LofofMg,
the concentrations brine
Ca, reached pH 10.5,
and Na changed wepH
with reacted
and, the
suspension
as such,with
only CO 2 (99%, Gasco)
the concentrations ofinstantly,
these threeand monitored
elements for further
are reported in the pH changes
results section.at atmospheric
pressure. InA the cyclic
jacket CO2 mineralization
reactor was used forexperiments, as 1 L of brine
CO2 mineralization, withreached
a coolant pHat 1 ◦C
10.5, webeing
reacted the
circulated
suspension with CO (99%, Gasco) instantly, and monitored for further
between the walls by a chiller, and a lid being placed on the upper part of the reactor. As CO2
2 pH changes at atmospheric
pressure. A
microbubbles jacket
were reactor into
injected was used for CO2 mineralization,
the suspension with a coolant
using a microbubble at 1 °C being
generator, circulated
the pH decreased
between the walls by a chiller, and a lid being placed on the upper part of the reactor. As CO2
rapidly, as has already been shown in the literature [7,26,27]. CO2 injection was stopped once the
microbubbles were injected into the suspension using a microbubble generator, the pH decreased
pH of the brine had decreased to 8. This was because we found that we were unable to collect the
rapidly, as has already been shown in the literature [7,26,27]. CO2 injection was stopped once the pH
CO2 -reacted precipitates when CO injection was stopped at pH 7, which was the value we had used
of the brine had decreased to 8.2 This was because we found that we were unable to collect the
in previous studies
CO2-reacted [7,26]. The
precipitates whenfinalCOproducts, which consisted of precipitates and transparent solutions,
2 injection was stopped at pH 7, which was the value we had used
were in
obtained by filtering the brine through
previous studies [7,26]. The final products, a 0.45which
µm nylon filter.ofThe
consisted experimental
precipitates cycle was then
and transparent
begunsolutions,
again, with the pH of the solution being increased to 10.5, CO bubbling
were obtained by filtering the brine through a 0.45 μm nylon2 filter. The experimental taking place, and the
cycle
was then
precipitate begunbeing
formed again,filtered
with the off.pH of the
This solution
cycle being increased
was repeated until notoprecipitates
10.5, CO2 bubbling taking on
were obtained
place,
addition ofand
NaOH,the precipitate
which occurredformed during
being filtered
the 5thoff. This This
cycle. cycleindicated
was repeated thatuntil
therenowere
precipitates
no divalent
were obtained
ions such as Mg oronCa addition
that were of NaOH,
able towhich
form occurred during thus,
hydroxides; the 5thCO cycle. This indicated that there
2 bubbling did not lead to the
were no divalent ions such as Mg or Ca that were able to form hydroxides; thus, CO2 bubbling did
formation of particles. Therefore, in our experiment, four cycles were sufficient to remove all divalent
not lead to the formation of particles. Therefore, in our experiment, four cycles were sufficient to
ions from the brine through the formation of particles. The experimental cycle is shown in Figure 1.
remove all divalent ions from the brine through the formation of particles. The experimental cycle is
We decided not to consider the effect of dissolved CO from atmosphere during the experiments,
shown in Figure 1. We decided not to consider the effect2 of dissolved CO2 from atmosphere during
because we believed that Mgwe 2+ , which was 3 times more abundant than Ca2+ in the brine, would not
the experiments, because believed that Mg2+, which was 3 times more abundant than Ca2+ in the
be carbonated by atmospheric
brine, would not be carbonated by CO 2 under the experimental
atmospheric CO2 under the conditions.
experimental conditions.

Figure
Figure 1. Experimental
1. Experimental cycles cycles
showingshowing
increaseincrease in 2pH,
in pH, CO CO2 injection,
injection, and after
and filtration filtration after CO2
CO2 mineralization.
mineralization.
Minerals 2017, 7, 207 4 of 12

After
Mineralsthe reaction
2017, 7, 207 with CO2 , the suspension was filtered, the concentrations of Mg, Ca, and 4 of 12Na in
the filtered liquid samples were analyzed, and the filter cake was dried in an oven at 80 ◦ C for 24 h,
After the reaction
then characterized with CO
using XRD 2, the suspension was filtered, the concentrations of Mg, Ca, and Na
(X’pert MPD, Philips, EA Almelo, The Netherlands), a field emission
in the filtered liquid samples were analyzed, and the filter cake was dried in an oven at 80 °C for 24 h,
scanning electron microscope (FESEM; JSM-7800 FPRIME, JEOL, Tokyo, Japan) equipped with an
then characterized using XRD (X’pert MPD, Philips, EA Almelo, The Netherlands), a field emission
energy dispersive spectrometer (EDS; X-MaxN, Oxford), thermogravimetric analysis (TGA; DTG-60H,
scanning electron microscope (FESEM; JSM-7800 FPRIME, JEOL, Tokyo, Japan) equipped with an
Shimadzu, Kyoto, Japan)
energy dispersive at argon
spectrometer (EDS;environment (10 ◦ C/min
X-MaxN, Oxford), heating rate),
thermogravimetric and(TGA;
analysis Fourier transform
DTG-60H,
infrared spectroscopy (FTIR; NICOLET 380, Thermo Fisher Scientific Inc., Costa Mesa,
Shimadzu, Kyoto, Japan) at argon environment (10 °C/min heating rate), and Fourier transform CA, USA).
infrared spectroscopy (FTIR; NICOLET 380, Thermo Fisher Scientific Inc., Costa Mesa, CA, USA).
3. Results and discussion
3. Results and discussion
3.1. Concentrations of Mg, Ca, and Na in Brine with Different pH Values
3.1. Concentrations of Mg, Ca, and Na in Brine with Different pH Values
Initial experiments aimed to obtain information on the changes in the concentrations of Mg
and Ca as Initial
the experiments
pH was varied aimedfrom
to obtain information
10–13.5 by adding on the changes
NaOH in the concentrations
solution to brine. This of Mg and
resulted in
Ca as the pH
the formation of awas
whitevaried from 10–13.5
suspension. Theby adding NaOH
suspension solutionastothe
thickened brine. This resulted
amount of NaOH in solution
the
addedformation
increased.of aICP-OES
white suspension.
was usedTheto suspension
measure the thickened as the amount
concentrations of theofions;
NaOH thesolution
results added
are shown
increased. ICP-OES was used to measure the concentrations of the ions; the results are shown in
in Figure 2. The label “raw” on the horizontal axis represents the untreated brine (i.e., no NaOH
Figure 2. The label “raw” on the horizontal axis represents the untreated brine (i.e., no NaOH
solution had been added). The left vertical axis shows the concentrations of Mg and Ca, while the
solution had been added). The left vertical axis shows the concentrations of Mg and Ca, while the
rightright
vertical axisaxis
vertical shows
showsthetheconcentration ofNa.
concentration of Na.It It
can can be seen
be seen that that the concentrations
the concentrations of Mg andof Mg
Ca and
Ca were reproducible; however, the concentration of Na showed large standard
were reproducible; however, the concentration of Na showed large standard deviations because thedeviations because
the solutions
solutions were
were prepared
prepared forforICP-OES
ICP-OESmeasurement
measurement by by diluting
diluting themthem
by aby a factor
factor of 1000.
of 1000. It wasIt was
expected thatthat
expected the the
concentration
concentration ofofNa
Nawould
would increase
increase as asthe
thepHpHincreased,
increased, owing
owing to addition
to the the addition
of of
NaOH NaOH solution
solution to the
to the brine.
brine.

20,000
2,400
2,200 Ca 19,500
2,000 Mg
1,800 Na
19,000
1,600
Mg, Ca (mg/L)

1,400
Na (mg/L)

18,500
1,200
1,000
18,000
800
600
17,500
400
200
17,000
0

raw 10 10.5 11 11.5 12 12.5 13 13.5


pH of brine

Figure 2. Concentrations of Mg, Ca, and Na as the pH of brine was increased by the addition of
Figure 2. Concentrations of Mg, Ca, and Na as the pH of brine was increased by the addition of NaOH
NaOH solution. Error bars represent one standard deviation.
solution. Error bars represent one standard deviation.
It is likely that as the measured concentrations of Mg and Ca decreased as NaOH was added to
It
theisbrine,
likelythe
that
Mgasand
theCameasured concentrations
ions had formed of Mg and
their hydroxides. If a Ca
brinedecreased
suspensionaswith
NaOH was added
a specific pH to
resulted
the brine, theinMg
a substantial
and Ca ions reduction in the concentration
had formed of one ion,
their hydroxides. it would
If a brine strongly suggest
suspension with athat this pH
specific
was in
resulted thea optimal pH for
substantial isolating in
reduction Mgtheandconcentration
Ca from each other.
of one ion, it would strongly suggest that this
CO 2 mineralization is an ionic reaction between CO32− and (divalent) metal ions. CO2 will
was the optimal pH for isolating Mg and Ca from each other.
change its form depending on the pH environment it is exposed to, as shown in the middle column
CO2 mineralization is an ionic reaction between CO3 2− and (divalent) metal ions. CO2 will
of Table 2. Therefore, increasing the pH is essential when attempting to enhance the transformation
change its form depending on the pH environment it is exposed to, as shown in the middle column of
of injected gaseous CO2 into its ionic form, CO32−. The pH can be increased by the addition of alkaline
Table 2. Therefore, increasing the pH is essential when attempting to enhance the transformation of
injected gaseous CO2 into its ionic form, CO3 2− . The pH can be increased by the addition of alkaline
Minerals 2017, 7, 207 5 of 12

agents, which will dissolve and yield OH− in aqueous solutions. If a reactant contains metal ions,
metal hydroxide particles will precipitate after reaction with existing OH− . Consequently, there is an
increase in pH results in the formation of metal hydroxides and ionization of CO2 . This is the reason
that addition of NaOH is required.

Table 2. Forms of CO2 varied at pH changes and their reactions with divalent ions.

pH Forms of CO2 Ion Reactions


Less than neutral (~<6.35) CO2 + H2 O → H2 CO3 H2 CO3 + H2 O + M2+ → H2 CO3 + H2 O + M2+
Neutral to weak alkali H2 CO3 + OH− → HCO3 − + H2 O (pKa1 = 6.4) 2HCO3 − + 2H2 O + 2M2+ → M(HCO3 )2 ↓ + 2H2 O + M2+
Strong alkali (~10.33<) HCO3 − + OH− → CO3 2− + H2 O (pKa2 = 10.2) 2CO3 2− + 2H2 O + 2M2+ → 2MCO3 ↓ + 2H2 O
M2+ represents divalent ions such as Mg2+ or Ca2+ .

When the pH was increased from 10 to 10.5, the concentration of Mg decreased by approximately
2000 mg/L, and when the pH was increased to 11, the concentration decreased by a further 180 mg/L.
After this, the Mg concentration remained relatively constant up to pH 13.5. The concentration of
Ca did not change significantly as the pH was varied. Consequently, we chose pH 10.5, to allow
Mg from brine to form Mg(OH)2 without significantly altering the concentration of Ca. Relatively
pure Mg(OH)2 can facilitate the production of pure Mg-carbonated particles by CO2 injection. This is
the reason for the separation or isolation of Mg and Ca from each other by pH adjustment before
CO2 injection.
We used the equations below by calculating the ion selectivity of Mg and Ca in hydroxide salts at
pH 10.5 and 11.

measured ion concentration at a given pH


Precipitated ratio of an ion = 1 − (1)
measured ion concentration in untreated brine
According to Equation (1), at pH 10.5, 90% of Mg and 23% of Ca in brine precipitated as their
hydroxides. As the pH was increased to 11, 99% of Mg and 29% of Ca had formed their hydroxides.
Equation (1) seems to indicate that pH 11 would be more favorable for the recovery of Mg and Ca
from brine. However, the precipitated ratio does not give enough information to allow a useful pH for
the separation of Mg and Ca to be selected: in this study, CO2 mineralization requires relatively pure
Mg- and Ca-hydroxides to ensure that pure carbonated particles are obtained.

measured ion concentration at a give pH


Ion selectivity = (2)
precipitated Mg and Ca concentrations at a given pH

Equation (2) shows that at pH 10.5, the precipitated particles were composed of 92.3% Mg(OH)2
and 7.70% Ca(OH)2 . Meanwhile, at pH 11, the precipitated particles were composed of 91.5% Mg(OH)2
and 8.50% Ca(OH)2 . Therefore, the Mg(OH)2 obtained was purer at pH 10.5. In addition, adjusting the
pH to 10.5 required 36.1 ± 0.5 mL of 1 M NaOH solution for 0.25 L brine, while adjusting to pH 11
required 42.0 ± 0.6 mL of 1 M NaOH solution. Therefore, increasing the pH from 10.5 to 11 required
an additional 5.90 mL of NaOH solution: this would increase the operational cost for the process.

3.2. Bubbling CO2 through a Suspension at pH 10.5


CO2 mineralization was performed by bubbling CO2 microbubbles through a brine suspension
at pH 10.5. In our previous studies on the precipitation of CaCO3 by CO2 mineralization, we found
that as the pH of the suspension of Ca(OH)2 into which CO2 was injected approached neutral, all the
particles had formed CaCO3 , leading us to regard this as the end of the reaction. We therefore
discontinued CO2 injection at this point [7,26]. On the basis of this experience, we initially intended to
stop CO2 injection when the pH of the brine approached neutral. However, in contrast to our previous
experiments, we found that no particles were suspended at this neutral pH. We therefore decided to
Minerals
Minerals 2017, 2017,
7, 2077, 207 6 of 126 of 12

previous experiments, we found that no particles were suspended at this neutral pH. We therefore
stop decided to stop at
CO2 injection CO injection
a2higher pHat of
a higher
8. CO2pHat of
6008. mL/min
CO2 at 600 mL/min
was wasfor
injected injected
4.5, 5,for
7, 94.5, 5, 7,for
mins 9 four
mins for four
experimental cycles. experimental cycles.
The concentrations of Mg, Ca, and Na in the suspension were measured at the end of each step
The concentrations of Mg, Ca, and Na in the suspension were measured at the end of each step in
in the cycle shown in Figure 1. The measured results are shown in Figure 3, and the concentrations of
the cycle shown in Figure 1. The measured results are shown in Figure 3, and the concentrations of the
the ions in the raw, untreated brine are given for comparison. It can be seen that the concentrations
ions in
of the
Mg raw,
and Cauntreated
decreasedbrine are given
during for comparison.
the cycles, It can be seen
while the concentration of Nathat the concentrations
increased owing to theof Mg
and Ca decreased
addition during
of NaOH the cycles,
solution. while
Filtration wasthe concentration
used to collect the of Na increased
particles after the owing to the step
CO2 bubbling addition
in of
NaOH solution.
each cycle. Filtration was used to collect the particles after the CO 2 bubbling step in each cycle.

2,400 30,000

2,200
Ca
2,000 Mg
1,800
Na

1,600 25,000
Ca, Mg (mg/L)

1,400

Na (mg/L)
1,200

1,000

800
20,000
600

400

200

0
15,000
RAW pH CO2 pH CO2 pH CO2 pH CO2 pH CO2

1st 2nd 3rd 4th 5th


Cycle
Figure 3. Changes in the concentrations of Mg, Ca, and Na during the cycles shown in Figure 1.
Figure 3. Changes in the concentrations of Mg, Ca, and Na during the cycles shown in Figure 1.
The concentration of Ca decreased to tens of mg/L after the first cycle, and then remained
The concentration
constant. of Ca
This indicates thatdecreased
all the Catointens of mg/L
the brine after the firstInterestingly,
had precipitated. cycle, and then remained constant.
the concentrations
This indicates that all the Ca in the brine had precipitated. Interestingly, the concentrations of when
of Mg fluctuated during the cycles. The concentration of Mg in the suspension decreased the
Mg fluctuated
pH was increased to 10.5, and then increased as CO 2 was bubbled through the brine. The Mg
during the cycles. The concentration of Mg in the suspension decreased when the pH was increased to 10.5,
concentration
and then increasedatas pHCO10.5was
remained
bubbledconstant
throughat around ~300The
the brine. mg/L,Mgwhile the concentration
concentration afterremained
at pH 10.5 CO2
2
bubbling decreased as the number of cycles increased. It seems that precipitation of carbonated Mg
constant at around ~300 mg/L, while the concentration after CO2 bubbling decreased as the number of
particles was less favorable than precipitation of carbonated Ca particles. However, it can be seen
cycles increased. It seems that precipitation of carbonated Mg particles was less favorable than precipitation
from the Mg and Ca concentrations measured after CO2 bubbling that Mg carbonate precipitated
of carbonated
during theCa particles.
cycles. However,
No particles wereit formed
can be seen from the Mg
after increasing the and Ca concentrations
pH and measured
bubbling CO2 through the after
CO2 bubbling that Mg carbonate
solution during the fifth cycle. precipitated during the cycles. No particles were formed after increasing
the pH and bubbling
Based on theCO 2 through
brine that wethe solution
used, during
10 million tonsthe
of fifth
brinecycle.
contains 22,260 tons of Mg and 7140
Based
tons of on
Ca.the brine that
If assume thatwe Mgused,
and Ca 10precipitate
million tons of brine
as MgCO contains
3 and CaCO322,260 tons
, each ion of Mgreacts
ideally and with
7140 tons
of Ca.40,306 and 7854
If assume tons
that Mg of and
CO2. CaAccording to theasmeasured
precipitate MgCO3 concentration
and CaCO3 ,ofeach remained Mg andreacts
ion ideally Ca in with
40,306brine
andafter
7854the fourth
tons cycle,
of CO 19,260 and 7080 tons of Mg and Ca react with 34,874 and 7788 tons of
2 . According to the measured concentration of remained Mg and Ca in
CO 2, respectively. The estimated amount of MgCO3 and CaCO3 are 66,816 and 17,700 tons by CO2
brine after the fourth cycle, 19,260 and 7080 tons of Mg and Ca react with 34,874 and 7788 tons
mineralization.
of CO2 , respectively. The estimated amount of MgCO3 and CaCO3 are 66,816 and 17,700 tons by
CO2 3.3.
mineralization.
Characterization of Suspended Particles from CO2 Mineralization
After each pH
3.3. Characterization increasing/CO
of Suspended 2-bubbling
Particles fromcycle, the particles in the suspensions were collected via
CO2 Mineralization
filtration and characterized. It should be noted that too few particles were formed during the first
After each
cycle for fullpH increasing/CO
characterization 2 -bubbling
to be cycle, the particles in the suspensions were collected via
carried out.
filtration and characterized. It should be noted that too few particles were formed during the first
cycle for full characterization to be carried out.
Figure 4 shows the XRD results. As depicted in the figure, the particles collected from the
first cycle consisted of calcite and halite. In addition, some aragonite had crystallized owing to the
coexistence of Mg and Ca ions [28]. The CaCO3 successfully precipitated from the non-synthesized
Minerals 2017, 7, 207 7 of 12

Figure 4 shows the XRD results. As depicted in the figure, the particles collected from the first
cycle consisted of calcite and halite. In addition, some aragonite had crystallized owing to the
coexistence of Mg and Ca ions [28]. The CaCO3 successfully precipitated from the non-synthesized
Minerals 2017, 7, 207 7 of 12
brine during CO2 mineralization. However, particles collected from other cycles could not be
identified positively by standard Joint Committee on Powder Diffraction Standards (JCPDS). Only
brine during
halite phase CO was2 mineralization.
identified. As However,
the numberparticles collected
of cycles from other
increased, the cycles
halite could
signalnot be identified
became more
positively
intense. by standard Joint Committee on Powder Diffraction Standards (JCPDS). Only halite phase
was identified.
Mg carbonates As the number
have been of cycles increased,
reported the halite
to form many signal
crystal became
phases, more intense.
depending on the conditions
such Mg carbonatestemperature,
as pressure, have been reported to form many
water content, crystal phases,
and agitation of thedepending on thephase
reactant liquid conditions suchWe
[29–32]. as
pressure, temperature, water content, and agitation of the reactant liquid phase [29–32].
utilized other analytical methods that would provide information regarding the presence of Mg We utilized other
analytical methods
carbonates that would provide information regarding the presence of Mg carbonates in the particles.
in the particles.

C: calcite (05-0586) C
A: aragonite (24-0025) 1st cycle
H
A

*
H: halite (05-0628)
*: unknown H 2nd cycle
A.U.

* * H
*
3rd cycle

* * H
*
4th cycle

10 20 30 40 50 60

2θ (degree)

Figure
Figure 4.
4. XRD
XRD results
results of
of the
the particles
particles collected
collected from
from the
the first
first to
to fourth cycles.
fourth cycles.

Elemental mapping by SEM-EDS revealed that the particles from the second, third, and fourth
Elemental mapping by SEM-EDS revealed that the particles from the second, third, and fourth
cycles consisted of Ca and Mg carbonates (Figure 5). This shows that the Mg formed carbonates,
cycles consisted of Ca and Mg carbonates (Figure 5). This shows that the Mg formed carbonates,
despite the fact that the precipitation of Mg carbonates is less favorable than the precipitation of Ca
despite the fact that the precipitation of Mg carbonates is less favorable than the precipitation of Ca
carbonates because Mg carbonates are more soluble than Ca carbonates and hydrated Mg ions
carbonates because Mg carbonates are more soluble than Ca carbonates and hydrated Mg ions possess
possess more energy [33]. Figure 5 shows that the elemental distributions of Ca, Mg, C, and O were
more energy [33]. Figure 5 shows that the elemental distributions of Ca, Mg, C, and O were broadly
broadly similar. The second cycle produced Ca carbonate, while the third and fourth cycles
similar. The second cycle produced Ca carbonate, while the third and fourth cycles produced Mg
produced Mg carbonate. The samples were prepared on silicon wafers to prevent the appearance of
carbonate. The samples were prepared on silicon wafers to prevent the appearance of the carbon signal
the carbon signal from the commonly used carbon adhesive tape.
from the commonly used carbon adhesive tape.
The particles were also subjected to FTIR analysis; the results are shown in Figure 6. The
The particles were also subjected to FTIR analysis; the results are shown in Figure 6. The particles
particles that precipitated during the second cycle showed FTIR absorption bands at 727, 873, and
that precipitated during the second cycle showed FTIR absorption bands at 727, 873, and 1406 cm−1 .
1406 cm−1. Several research papers that identified Mg carbonates using FTIR analysis suggest that the
Several research papers that identified Mg carbonates using FTIR analysis suggest that the peak at
peak at−727
1
cm−1 was likely caused by the presence CaCO3 in the structure. Long et al. [34] reported
727 cm was likely caused by the −1presence CaCO3 in the structure. Long et al. [34] reported that
that peaks at 724, 726, and 730 cm were obtained from calcite particles including 30 mol% Mg.
peaks at 724, 726, and 730 cm−1 were obtained from calcite particles including 30 mol% Mg. Similarly,
Similarly, Gunasekaran et al. [34,35] and Xu and Poduska [36] reported dolomite peaks at 729 and
Gunasekaran et al. [34,35] and Xu and Poduska [36]2−reported dolomite peaks at 729 and 730 cm−1 ,
730 cm−1, respectively. These peaks arose from CO3 . Consequently, it is possible to assign the IR
respectively. These peaks arose from CO3 2− . Consequently, it is possible to−1assign the IR peak at
peak at−727 cm−1 to Mg carbonates. In addition, the peaks at 873 and 1406 cm were from the CO32−
727 cm 1 to Mg carbonates. In addition, the peaks at 873 and 1406 cm−1 were from the CO3 2− ions in
ions in CaCO3 [35,37], which was already known to be present due to XRD analysis.
CaCO3 [35,37], which was already known to be present due to XRD analysis.
The particles obtained after the third and fourth cycles both showed peaks at 852 and 877 cm−−11.
The particles obtained after the third and fourth cycles both showed peaks at 852 and 877 cm .
In these cycles, both Ca and Mg carbonates formed. The peak at 852 cm−−11 was due to calcite that
In these cycles, both Ca and Mg carbonates formed. The peak at 852 cm was due to calcite that
included Mg. Long et al. [34] reported that calcite including Mg at 20 and 39 mol% absorbed IR at
included Mg. Long et al. [34] reported that calcite including Mg at 20 and 39 mol% absorbed IR at
852 cm−1−.1CO32− ions in dolomite also absorbed IR near this position, at 853 cm−1. Meanwhile, the peak
852 cm −1 . CO3 2− ions in dolomite also absorbed IR near this position, at 853 cm−1 . Meanwhile,
at 877 cm indicates the presence of CaCO3 [35,36,38–40]. Although we expected that the third and
the peak at 877 cm−1 indicates the presence of CaCO3 [35,36,38–40]. Although we expected that the
fourth cycles would produce Mg carbonates that excluded Ca, some of the Ca remaining in the
third and fourth cycles would produce Mg carbonates that excluded Ca, some of the Ca remaining
suspension after the second cycle managed to participate in the carbonation of Mg. The peaks at 1418
in the suspension after the second cycle managed to participate in the carbonation of Mg. The peaks
at 1418 and 1479 cm−1 are typical absorption peaks of hydromagnesite. In addition, the peak at
Minerals 2017,
Minerals 2017, 7,
7, 207
207 88 of
of 12
12

and 1479 cm−1 are typical absorption peaks of hydromagnesite. In addition, the peak at 3647 cm−1
3647 cm−1further
provides providesevidence
further evidence
of the of the presence
presence of hydromagnesite.
of hydromagnesite. MgMg frombrine
from brine successfully
precipitated hydromagnesite,
as hydromagnesite,
Minerals 2017, 7, 207 indicatingthat
indicating thatbrine
brinecould
couldbe
beaauseful
usefulresource
resourcefor
forCO
CO2 2mineralization.
mineralization.
8 of 12

and 1479 cm−1 are typical absorption peaks of hydromagnesite. In addition, the peak at 3647 cm−1
provides further evidence of the presence of hydromagnesite. Mg from brine successfully
precipitated as hydromagnesite, indicating that brine could be a useful resource for CO2 mineralization.

Figure 5. Elemental distributions ofofMg,


Elemental Ca, C, and O in particles producedduring
during the experimental cycles.
Figure 5. 5.
Figure Elementaldistributions
distributions ofMg,
Mg,Ca,
Ca,C,
C,and
andOO in
in particles
particles produced
produced during the
the experimental
experimental cycles.
cycles.

877
1418 877
1418 852
852 798 708708
798
36473647 1479
1479 590590

2nd2nd cycle
cycle
3rd3rd cycle
cycle
4th cycle
4th cycle
Transmittance
Transmittance

727
1406 873
727
4000 3500 3000 2500 2000 873
1500 14061000 500

-1
4000 3500 3000 Wavenumber
2500 (cm ) 1500
2000 1000 500

-1
Figure
Figure 6. FTIR
6. FTIR spectra
spectra of particles
of particles Wavenumber
fromthe
from thesecond,
second, )
(cmthird,
third,and
andfourth
fourthcarbonation cycles.
carbonation cycles.

Figure 6. FTIR spectra of particles from the second, third, and fourth carbonation cycles.
Minerals 2017, 7, 207 9 of 12

In addition, characterization by TGA was used to confirm the presence of hydromagnesite.


Minerals 2017, 7, 207 9 of 12
The weight losses of the particles we obtained, shown in Figure 7a, were compared with those of
commercial In addition,
Mg(OH)characterization
2 , CaCO3 , MgCO by3TGA
, andwas usedwhich
NaCl, to confirm the presence
are shown of hydromagnesite.
in Figure 7b. Weight loss Thedue to
Mg(OH)weight losses
occurred of the
between particles
328 we
and 422 ◦ C. Losses
obtained, shownat in Figure
589–778 ◦ C7a,
and were
180–524 ◦ C were
compared with those
due to of
CaCO
2 3
commercial Mg(OH)
and hydromagnesite, 2, CaCO3, MgCO3, and NaCl, which are shown in Figure 7b. Weight loss due to
respectively. By comparing Figure 7a,b, it can be seen that the particles from
Mg(OH)2 occurred between 328 and 422 °C. Losses at 589–778 °C and 180–524 °C were due to CaCO3
the second cycle were composed of Mg(OH)2 and CaCO3 . A small amount of NaCl was included
and hydromagnesite, respectively. By comparing Figure 7a,b, it can be seen that the particles from
in all the particles, as shown by the weight losses that began at 810 ◦ C. The TGA curves of the
the second cycle were composed of Mg(OH)2 and CaCO3. A small amount of NaCl was included in
particles from the third and fourth cycles were quite different from that obtained for the particles
all the particles, as shown by the weight losses that began at 810 °C. The TGA curves of the particles
from from
the second
the thirdcycle. The weight
and fourth losses
cycles were quite ~450 ◦ Cfrom
at different in the curves
that of the
obtained particles
for the particlesfrom
fromthethethird
and fourth cycles did not quite match with what would be expected for the loss
second cycle. The weight losses at ~450 °C in the curves of the particles from the third and fourth of hydromagnesite.
Montes-Hermandez
cycles did not quite et al. [41]
matchsynthesized
with what hydromagnesite
would be expected andforcharacterized
the loss of particles of it using
hydromagnesite.
TGA.Montes-Hermandez et al. [41] synthesized
They found that hydromagnesite hydromagnesite
exhibited weight loss atand ◦ C with some
450characterized particles of it using
fluctuation at around
375 ◦ C,
TGA.whichThey found that
precisely hydromagnesite
matched the resultsexhibited
shown for weight loss at 450
the particles °C the
from with some
third andfluctuation at in
fourth cycles
around 375 °C, which precisely matched the results shown for the particles from
Figure 7a. There were also some differences between the TGA curves obtained for the particles from the third and fourth
cycles in Figure 7a. There were also some differences between the TGA curves obtained for the
the third and fourth cycles. The curve for cycle three indicated an additional weight loss of 4.5% in the
particles from◦ the third and fourth cycles. The curve for cycle three indicated an additional weight
range of 635–665 C, which indicates the coexistence of calcite and hydromagnesite. As the number of
loss of 4.5% in the range of 635–665 °C, which indicates the coexistence of calcite and hydromagnesite.
cyclesAsincreased, the purity of the hydromagnesite that precipitated increased.
the number of cycles increased, the purity of the hydromagnesite that precipitated increased.

110
(a)
100

90

80
Weight (%)

70

60
2nd cycle
50 3rd cycle
4th cycle
40

30

200 400 600 800 1000


o
Temperature ( C)
110
(b)
100

90

80
weight (%)

70

60

50

40
Mg(OH)2 CaCO3
30 MgCO3 NaCl

200 400 600 800 1000


ο
Temperature ( C)

Figure 7. Thermogravimetric analysis (TGA) curves of (a) the precipitates obtained from the second,
Figure 7. Thermogravimetric analysis (TGA) curves of (a) the precipitates obtained from the second,
third, and fourth cycles; and (b) the commercial reagents of Mg(OH)2, MgCO3, CaCO3, and NaCl.
third, and fourth cycles; and (b) the commercial reagents of Mg(OH)2 , MgCO3 , CaCO3 , and NaCl.
Minerals 2017, 7, 207 10 of 12

4. Conclusions
Non-synthesized brine from a functional RO seawater desalination plant was used for CO2
mineralization to fix CO2 under ambient temperature and pressure. To the best of our knowledge,
this is the first time that non-synthesized brine has been used for CO2 mineralization. Cycles consisting
of an increase in pH followed by CO2 injection and finally filtration precipitated 99% of Ca and 86% of
Mg from the brine, using them to fix CO2 in the form of carbonated minerals. CO2 was successfully
mineralized with Ca to yield CaCO3 and with Mg to produce hydromagnesite. This was shown by the
characterization of the precipitates obtained from the cycles by XRD, SEM-EDS, FTIR, and TGA-DTA.
It was thought that co-presence of Ca with Mg was not favorable for the precipitation of Mg
carbonates. In this study, we precipitated hydromagnesite followed by precipitation of calcite from
brine. This means that the concentrations of Mg and Ca in brine are twice those in influent seawater,
making it a good source of divalent ions for CO2 mineralization. According to our experiments,
42,662 tons of CO2 could be sequestered from 10 million tons of the brine used for a year. Moreover,
17,700 tons of CaCO3 and 66,816 tons of MgCO3 would be obtained.

Acknowledgments: This research was supported by the Basic Research Project (17-3422) of the Korea Institute
of Geoscience and Mineral Resources (KIGAM), funded by the Ministry of Science and Information and
Communications Technologies (ICT).
Author Contributions: Jun-Hwan Bang and Soochun Chae conceived and designed the experiments; Yeongsuk Yoo,
Seung-Woo Lee and Kyungsun Song performed experiments and analyzed the data; Jun-Hwan Bang wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Ko, D.-H. Drought Causes Water Shortage Crisis in Southern Korea; The Korea Times: Seoul, Korea, 2017.
2. Papapetrou, M.; Cipollina, A.; la Commare, U.; Micale, G.; Zaragoza, G.; Kosmadakis, G. Assessment of
methodologies and data used to calculate desalination costs. Desalination 2017, 419, 8–19. [CrossRef]
3. Charcosset, C. A review of membrane processes and renewable energies for desalination. Desalination 2009,
245, 214–231. [CrossRef]
4. Alkhudhiri, A.; Darwish, N.; Hilal, N. Membrane distillation: A comprehensive review. Desalination 2012,
287, 2–18. [CrossRef]
5. Piyadasa, C.; Ridgway, H.F.; Yeager, T.R.; Stewart, M.B.; Pelekani, C.; Gray, S.R.; Orbell, J.D. The application
of electromagnetic fields to the control of the scaling and biofouling of reverse osmosis membranes—A
review. Desalination 2017, 418, 19–34. [CrossRef]
6. Sanna, A.; Uibu, M.; Caramanna, G.; Kuusik, R.; Maroto-Valer, M.M. A review of mineral carbonation
technologies to sequester CO2 . Chem. Soc. Rev. 2014, 43, 8049–8080. [CrossRef] [PubMed]
7. Bang, J.-H.; Kim, W.; Song, K.S.; Jeon, C.W.; Chae, S.C.; Cho, H.-J.; Jang, Y.N.; Park, S.-J. Effect of experimental
parameters on the carbonate mineralization with CaSO4 ·2H2 O using CO2 microbubbles. Chem. Eng. J. 2014,
244, 282–287. [CrossRef]
8. Druckenmiller, M.L.; Maroto-Valer, M.M. Carbon sequestration using brine of adjusted pH to form mineral
carbonates. Fuel Process. Technol. 2005, 86, 1599–1614. [CrossRef]
9. Dri, M.; Sanna, A.; Maroto-Valer, M.M. Mineral carbonation from metal wastes: Effect of solid to liquid ratio
on the efficiency and characterization of carbonated products. Appl. Energy 2014, 113, 515–523. [CrossRef]
10. Zevenhoven, R.; Wiklund, A.; Fagerlund, J.; Eloneva, S.; Veen, B.I.; Geerlings, H.; van Mossel, G.; Boerrigter, H.
Carbonation of calcium-containing mineral and industrial by-products. Front. Chem. Eng. China 2010, 4,
110–119. [CrossRef]
11. Baciocchi, R.; Costa, G.; di Bartolomeo, E.; Polettini, A.; Pomi, R. The effects of accelerated carbonation on
CO2 uptake and metal release from incineration APC residues. Waste Manag. 2009, 29, 2994–3003. [CrossRef]
[PubMed]
12. Baciocchi, R.; Costa, G.; Lategano, E.; Marini, C.; Polettini, A.; Pomi, R.; Postorino, P.; Rocca, S. Accelerated
carbonation of different size fractions of bottom ash from RDF incineration. Waste Manag. 2010, 30, 1310–1317.
[CrossRef] [PubMed]
Minerals 2017, 7, 207 11 of 12

13. Bang, J.-H.; Lee, S.-W.; Jeon, C.; Park, S.; Song, K.; Jo, W.; Chae, S. Leaching of Metal Ions from Blast Furnace
Slag by Using Aqua Regia for CO2 Mineralization. Energies 2016, 9, 996. [CrossRef]
14. Pan, S.-Y.; Chang, E.; Chiang, P.-C. CO2 capture by accelerated carbonation of alkaline wastes: A review on
its principles and applications. Aerosol Air Qual. Res. 2012, 12, 770–791. [CrossRef]
15. Bałdyga, J.; Henczka, M.; Sokolnicka, K. Utilization of carbon dioxide by chemically accelerated mineral
carbonation. Mater. Lett. 2010, 64, 702–704. [CrossRef]
16. Lee, S.; Kim, J.-W.; Chae, S.; Bang, J.-H.; Lee, S.-W. CO2 sequestration technology through mineral carbonation:
An extraction and carbonation of blast slag. J. CO2 Util. 2016, 16, 336–345. [CrossRef]
17. Soong, Y.; Fauth, D.L.; Howard, B.H.; Jones, J.R.; Harrison, D.K.; Goodman, A.L.; Gray, M.L.; Frommell, E.A.
CO2 sequestration with brine solution and fly ashes. Energy Convers. Manag. 2006, 47, 1676–1685. [CrossRef]
18. Li, P.; Pan, S.-Y.; Pei, S.; Lin, Y.J.; Chiang, P.-C. Challenges and perspectives on carbon fixation and utilization
technologies: An overview. Aerosol Air Qual. Res. 2016, 16, 1327–1344. [CrossRef]
19. Shenvi, S.S.; Isloor, A.M.; Ismail, A.F. A review on RO membrane technology: Developments and challenges.
Desalination 2015, 368, 10–26. [CrossRef]
20. Morrison, J.; Jauffret, G.; Galvez-Martos, J.L.; Glasser, F.P. Magnesium-based cements for CO2 capture and
utilisation. Cem. Concr. Res. 2016, 85, 183–191. [CrossRef]
21. Liu, Q.; Maroto-Valer, M.M. Studies of pH buffer systems to promote carbonate formation for CO2
sequestration in brines. Fuel Process. Technol. 2012, 9, 6–13. [CrossRef]
22. Wang, W.; Liu, X.; Wang, P.; Zheng, Y.; Wang, M. Enhancement of CO2 Mineralization in Ca2+ -/Mg2+ -Rich
Aqueous Solutions Using Insoluble Amine. Ind. Eng. Chem. Res. 2013, 52, 8028–8033. [CrossRef]
23. Xie, H.; Liu, T.; Hou, Z.; Wang, Y.; Wang, J.; Tang, L.; Jiang, W.; He, Y. Using electrochemical process to
mineralize CO2 and separate Ca2+ /Mg2+ ions from hard water to produce high value-added carbonates.
Environ. Earth Sci. 2015, 73, 6881–6890. [CrossRef]
24. Langmuir, D. Stability of Carbonates in the System MgO-CO2 -H2 O. J. Geol. 1965, 73, 730–754. [CrossRef]
25. Lide, D.R. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL, USA, 1997.
26. Bang, J.-H.; Jang, Y.N.; Kim, W.; Song, K.S.; Jeon, C.W.; Chae, S.C.; Lee, S.-W.; Park, S.-J.; Lee, M.G.
Precipitation of calcium carbonate by carbon dioxide microbubbles. Chem. Eng. J. 2011, 174, 413–420.
[CrossRef]
27. Bang, J.-H.; Song, K.; Park, S.; Jeon, C.; Lee, S.-W.; Kim, W. Effects of CO2 Bubble Size, CO2 Flow Rate and
Calcium Source on the Size and Specific Surface Area of CaCO3 Particles. Energies 2015, 8, 12304. [CrossRef]
28. Santos, R.M.; Bodor, M.; Dragomir, P.N.; Vraciu, A.G.; Vlad, M.; van Gerven, T. Magnesium chloride as a
leaching and aragonite-promoting self-regenerative additive for the mineral carbonation of calcium-rich
materials. Miner. Eng. 2014, 59, 71–81. [CrossRef]
29. Cheng, W.; Li, Z. Nucleation kinetics of nesquehonite (MgCO3 ·3H2 O) in the MgCl2 -Na2 CO3 system.
J. Cryst. Growth 2010, 312, 1563–1571. [CrossRef]
30. Hales, M.C.; Frost, R.L.; Martens, W.N. Thermo-Raman spectroscopy of synthetic nesquehonite —Implication
for the geosequestration of greenhouse gases. J. Raman Spectrosc. 2008, 39, 1141–1149. [CrossRef]
31. Coleyshaw, E.E.; Crump, G.; Griffith, W.P. Vibrational spectra of the hydrated carbonate minerals ikaite,
monohydrocalcite, lansfordite and nesquehonite. Spectrochim. Acta Part A Mol. Biomolecul. Spectroscop. 2003,
59, 2231–2239. [CrossRef]
32. Hopkinson, L.; Kristova, P.; Rutt, K.; Cressey, G. Phase transitions in the system MgO–CO2 –H2 O during
CO2 degassing of Mg-bearing solutions. Geochim. Cosmochim. Acta 2012, 76, 1–13. [CrossRef]
33. Xu, J.; Yan, C.; Zhang, F.; Konishi, H.; Xu, H.; Teng, H.H. Testing the cation-hydration effect on the
crystallization of Ca–Mg–CO3 systems. Proc. Natl. Acad. Sci. USA 2013, 110, 17750–17755. [CrossRef]
[PubMed]
34. Long, X.; Nasse, M.J.; Ma, Y.; Qi, L. From synthetic to biogenic Mg-containing calcites: A comparative study
using FTIR microspectroscopy. Phys. Chem. Chem. Phys. 2012, 14, 2255–2263. [CrossRef] [PubMed]
35. Gunasekaran, S.; Anbalagan, G.; Pandi, S. Raman and infrared spectra of carbonates of calcite structure.
J. Raman Spectrosc. 2006, 37, 892–899. [CrossRef]
36. Xu, B.; Poduska, K.M. Linking crystal structure with temperature-sensitive vibrational modes in calcium
carbonate minerals. Phys. Chem. Chem. Phys. 2014, 16, 17634–17639. [CrossRef] [PubMed]
37. Pandey, S.; Sengupta, J. Fourier transform infrared spectroscopy: A tool for detection of lime content in hot
mix asphalt. In Proceedings of the 26th ARRB Conference, Sydney, Australia, 19–22 October 2014; p. 11.
Minerals 2017, 7, 207 12 of 12

38. Bourrata, X.; Qiao, L.; Feng, Q.; Angellier, M.; Dissaux, A.; Beny, J.-M.; Barbin, V.; Stempflé, P.; Rousseau, M.;
Lopez, E. Origin of growth defects in pearl. Mater. Charact. 2012, 72, 94–103. [CrossRef]
39. Junfeng, J.; Yun, G.; Balsam, W.; Damuth, J.E.; Jun, C. Rapid identification of dolomite using a Fourier
transform infrared spectrophotometer (FTIR): A fast method for identifying Heinrich events in IODP Site
U1308. Mar. Geol. 2009, 258, 60.
40. Bang, J.-H.; Song, K.S.; Lee, M.G.; Jeon, C.W.; Jang, Y.N. Effect of Critical Micelle Concentration of Sodium
Dodecyl Sulfate Dissolved in Calcium and Carbonate Source Solutions on Characteristics of Calcium
Carbonate Crystals. Mater. Trans. 2010, 51, 1486–1489. [CrossRef]
41. Montes-Hernandez, G.; Renard, F.; Chiriac, R.; Findling, N.; Toche, F. Rapid Precipitation of
Magnesite Microcrystals from Mg(OH)2 -H2 O-CO2 Slurry Enhanced by NaOH and a Heat-Aging Step
(from ~20 to 90 ◦ C). Cryst. Growth Des. 2012, 12, 5233–5240. [CrossRef]

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).