Desalination 353 (2014) 84–90

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Desalination
journal homepage: www.elsevier.com/locate/desal

Seawater desalination by gas hydrate process and removal characteristics

of dissolved ions (Na+, K+, Mg2 +, Ca2 +, B3 +, Cl−, SO42 −)
Kyung Chan Kang a, Praveen Linga b, Kyeong-nam Park a, Sang-June Choi c, Ju Dong Lee a,⁎
a
Offshore Plant Resources R&D Center, Korea Institute of Industrial Technology, 1274 Jisa-dong, Gangseo-gu, Busan 618-230, Republic of Korea
b
Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117586 Singapore
c
Department of Environmental Engineering, Kyungpook National University, Sangyeok 3-dong, Buk-gu, Daegu 702-701, Republic of Korea

H I G H L I G H T S

• We evaluated an application possibility of hydrate-based desalination process.

• Increasing hydraulic pressure increased the removal efficiency of ions.
• CO2 as a guest gas is more suitable than CH4 for the HBD process.
• The property of ionic behavior depending on its concentration should be examined further in the future.

a r t i c l e i n f o a b s t r a c t

Article history: In order to evaluate hydrate-based desalination (HBD), experiments with seawater samples were carried out at
Received 27 May 2014 various conditions (i.e. hydraulic pressure, washing step, and hydrate-forming gas). Before and after the hydrate
Received in revised form 3 September 2014 process, cations (Na+, K+, Mg2+, Ca2+, and B3+) and anions (Cl− and SO42−) were analyzed by inductively
Accepted 6 September 2014
coupled plasma atomic emission spectroscopy (ICP-AES) and ion chromatography (IC). In a single stage of CO2
Available online 29 September 2014
hydrate process without any pretreatment, 71%–94% of each cation was removed in the following order:
Keywords:
K+ N Na+ ≈ Mg2+ ≈ Ca2+ N B3+ and 73%–83% of each anion was removed. When the brines on the surface
Desalination of hydrate pellets were removed, the ion removal efficiency increased above 4%. It was also found that the
Clathrate process desalting efficiency depended on the hydrate-forming gas (CO2 N CH4) and the hydraulic pressure (6–10 MPa)
Gas hydrates to produce hydrate pellets. In this study, the removal efficiency of cations and anions in a real seawater sample
Seawater using HBD processes were reported for the first time.
Ion rejection © 2014 Elsevier B.V. All rights reserved.

1. Introduction
In the foreseeable future, worldwide problems associated with
the lack of fresh water are predicted and the major causes are well
known: climate change, population explosion, and unsustainable devel-
opment. Presently, many researchers focus on the development of desa-
lination technologies in order to secure water resources. The traditional
desalination technologies include distillation and membrane methods,
and there are a variety of desalination methods: multi-stage flash
distillation (MSF), membrane distillation (MD), reverse osmosis (RO),
forward osmosis (FO), and electrodialysis (ED) [1–3]. Currently, a
majority of the desalination plants worldwide are based on reverse
osmosis, while some old MSF plants are also operational [4]. In general,
for desalination processes, a large amount of energy is required to
separate salts from seawater [5]. The most important technological
challenge is to minimize the cost of seawater desalination processes.
⁎ Corresponding author. Tel.: +82 51 974 9311; fax: +82 51 974 9378.
E-mail address: julee@kitech.re.kr (J.D. Lee).
Kavvadias and Khamis recognized that the energy consumed and subse-
quently the costs involved in any desalination plant may play an impor-
tant role in economic feasibility and optimization of desalination
systems [6]. For instance, the energy required in the seawater reverse
osmosis (SWRO) process has decreased following the design of higher-
performance membranes, pumps, and energy recovery devices [4]. It is
noted that the SWRO process is a mature technology, and hence process
enhancements are very limited and it is often confined to the membrane
development section. Overall, there is still a need to develop innovative
novel technologies that can process seawater at a large scale with a
focus on minimizing energy costs, maximizing water recovery, and
becoming more environment friendly. In this view, many researchers
have also focused on a novel method called hydrate-based desalination
(HBD) process.
Gas hydrates are nonstoichiometric crystalline compounds that are
formed by water and a number of gas molecules at specific temperature
and pressure conditions, which depend on hydrate-forming gases. Gas
hydrates exist in three distinct structures depending on guest molecules;
structure I sI (small, 512; large, 51262), structure II (small, 512; large,

http://dx.doi.org/10.1016/j.desal.2014.09.007
0011-9164/© 2014 Elsevier B.V. All rights reserved.
 K.C. Kang et al. / Desalination 353 (2014) 84–90 85

51264), and structure H (small, 512; medium, 435663; large, 51268), having
cavities of different types and sizes [7]. Pure CO2 and CH4 form sI, which
has 2 small (512) and 6 large (51262) cavities. In the past decade or so,
technologies based on gas hydrates have been researched for CO2 cap-
ture [8–13], gas separations [14], gas storage and transport [15], cold
storage, CO2 sequestration [16], and seawater desalination [17–22]. The
hydrate-based desalination (HBD) process is based on a liquid to solid
phase change of water such as a freezing method. In other words, a phys-
ical reaction coupled with an exclusion of ions by the hydrogen bonding
of water molecules during hydrate formation is the core of the HBD pro-
cess. It is also important to separate the solids (hydrates) from the
remaining liquid phase (brines) in the process after hydrate formation.
In the 1980s and 1990s, there were efforts for the development of
desalination processes by gas hydrate method. Makogon reported that
hydrate-based desalination process can be cheaper than other methods
such as thermal and membrane processes [17]. But the outputs were
different from the expected results because there were problems in sep-
arating hydrate crystals and brines [18–20]. The problems led to the fol-
lowing research to determine the filterability of hydrate crystals, design
a wash column, and investigate guest molecules that form hydrates at
higher temperature conditions [21]. Recently, some researchers have
proposed the use of cyclopentane as a hydrate former for the HBD pro-
cess to desalinate water [23,24]. Cyclopentane is immiscible in water
and hence when hydrate formation happens, water from seawater
will combine with cyclopentane to form sII hydrates. The morphology
of cyclopentane hydrates is different from traditional sII hydrates [25],
whereby cyclopentane forms tiny spherical-shaped crystals, which can
be a challenge to separate from the brine solution for dissociation. In
addition, the dissociation of cyclopentane hydrate to recover water
may result in an emulsion formation or tiny drops of cyclopentane
trapped in recovered water if the dissociation is not well controlled.
The major chemical ions contributing to seawater salinity are
chloride (55.03%), sodium (30.65%), sulfate (7.71%), and magnesium
(3.65%), while boron (2.4%), calcium (1.17%), and potassium (1.13%)
are minor ions [26]. The ionized salt in seawater interacts with the
water molecules by Coulombic force, and hydrate formation is thermo-
dynamically inhibited by salt ions [7]. Lu et al. mentioned that anion in
electrolyte solution will be a stronger inhibitor than cation in gas Fig. 1. Micro bubbles generated by tube type static mixer to form gas hydrate.
hydrate formation because of its strong interaction, which is kept with
the ambient water molecule cluster even after being hydrated [27].
Our previous study was the first to report ion removal efficiency in
hydrate-based seawater desalination [22], in which only cations were 10 μm, which was measured using optical microscopic analysis through
analyzed. In this study, the effect of anions and their removal efficiencies the windows.
for the HBD process was investigated. In addition, desalination experi- Minor modifications were made to the apparatus presented by Park
ments were carried out in a single-stage hydrate method and the effect et al. [22]. A scraper was installed to improve the heat transfer rate asso-
of various factors (i.e. hydraulic pressure, removal of brines on the ciated with the reactor and the cooling system (i.e. jacket type) and to
surface of hydrate pellets, and type of guest gas) were determined. upgrade the mixing effect in the reactor, because it was observed that
Removal efficiency for each dissolved ion was also investigated from hy- hydrate crystals disturb heat transfer by adhering to the inner walls of
drate pellets of real seawater samples using inductively coupled plasma the reactor. A drive shaft from a gear motor equipped at the top of the
atomic emission spectroscopy (ICP-AES) and ion chromatography (IC). reactor has two wings with a plastic brush that can scrape the inner
This study illustrates the possibility of using the hydrate method in wall of the reactor. The micro bubbles were introduced into the reactor
desalination, and the results may provide fundamental information for by a high-pressure circulation pump, a swirling flow was formed, and
process design. the scraper turned in the same direction of the swirling flow. When
hydrate slurries were compressed and squeezed in the connection
pipe by the strokes of the dual cylinder operation, a metallic mesh was
2. Experimental section used to minimize the amount of hydrate slurries flowing out through
the numerous small passing holes. The metallic mesh having holes of
2.1. Apparatus a uniform size (0.6 mm) consisting of a wire of 0.2 mm thickness
wrapped over the connection pipe.
A detailed description of the hydrate-based desalination (HBD)
apparatus is available in Park et al. [22]. The apparatus can produce
hydrate pellets in a continuous manner by a squeezing operation of a 2.2. Seawater samples and guest gases
dual cylinder unit. In this apparatus, a high-pressure circulation pump
(Samec, multiple-stage electric pumps, Italy) and tube type bubble The seawater sample was obtained from southeast coast of Korea
generator are used for the mixing of the reactor contents. Preliminary (Gadeok Island, 35°0′44.19″ north, 128°49′38.06″ east). Detailed analysis
experiments in Fig. 1 showed that the average bubble size was around data from the salt concentrations of the seawater is presented in Table 1.
86 K.C. Kang et al. / Desalination 353 (2014) 84–90
Table 1
Average value of concentration of contents and pH in seawater samples used in this study.
Total (mg/L) Cation (mg/L)
Na+ Mg2+ Ca2+
35,913.09 10,247.78 1,199.69 390.89
CO2 (99.9%, PS Chem Co. Ltd., Korea) and CH4 (99.9%, PS Chem Co. Ltd.,
Korea) were the gases employed in this work.
2.3. Experimental procedure
When the system was cooled to the desired temperature, the gas
tank and hydrate reactor were flushed at least three times with the
hydrate-forming gas to remove any residual air. Subsequently, a volume
of 10 L of seawater was injected into the reactor from the water feed
tank by the high-pressure pump and hydrate-forming gas was filled
until the desired pressure was obtained. The experiments were carried
out at 280 K and a pressure of 2.9 MPa and 4.6 MPa was reached for
CO2 and CH4, respectively. When gas was consumed in the reactor dur-
ing hydrate formation, additional gas was automatically supplied from
the gas tank with the operation of a PID controller and control valve,
and the reactor was maintained at constant pressure. After hydrate
formation time of 120 min, a pellet was produced and squeezed out of
the reactor for further analysis. For each experiment, 10 pellets were
produced (1.2 cm diameter and 5 cm thickness).
As shown in Table 2, we varied the relative hydraulic pressures for
the production of pellets from the guest gas hydrates employed in this
work. Additionally, for the CO2 at 8 MPa hydraulic pressure, we per-
formed another type of dissociation experiment by removing the salt
adsorbed on the pellet surface by wiping it using dry wipes (KimWipes)
before dissociation.
The initial and final pH values of the seawater were measured by pH
meter (ORION 720A+, Thermo Electron Co., USA). Salinity changes of
raw seawater, extracted pellet samples, and brines were analyzed by
inductively coupled plasma atomic emission spectroscopy (ICP-AES)
and ion chromatography (IC). The removal (or desalination) efficiency
was calculated by Eq. (1).
C A0 −C A
Removal ðdesalinationÞ efficiencyðηÞ ¼  100
C A0
where CA0 is the salinity in feed seawater and CA is the salinity in
dissociated hydrate pellet. Removal efficiencies for each dissolved ions
were calculated from the ion contents of the initial seawater and disso-
ciated hydrate sample.
2.4. Inductively coupled plasma spectrometer
In order to evaluate desalination efficiency, each cation (Na+, Mg2+,
Ca , K+, and B3 +) was measured by inductively coupled plasma
2+
atomic emission spectroscopy (ICP-AES; ACTIVA, JY HORIBA). The
sample was filtered with cellulose nitrate membrane filter (Whatman,
0.22 μm) and it was boiled with 1 mL nitric acid at 150 °C for 30 minutes
Table 2
Experimental conditions.
Gas hydrate Pressure (MPa) Temperature (K)
CO2 2.9 280
CH4 4.6
a
Dissociation without washing the surface of hydrate pellet.
b
Dissociation with washing the surface of hydrate pellet.
Anion (mg/L) pH
K+ B3+ Cl− SO4 2−
716.32 2.66 20,934.98 2,419.57 7.94
to eliminate organics. After pretreatment, the concentration of dissolved
ions was measured by ICP-AES. The test result was assured by Korea
Basic Science Institute (KBSI).
2.5. Ion chromatography
Each anion (Cl− and SO42−) was quantified by ion chromatography
(IC; ICS-3000, DIONEX). The sample was filtered using a syringe filter
(Whatman, 0.2 μm). The sample to analyze a chloride ion was only
diluted, and the sample to quantify a sulfate ion was diluted after elim-
inating chloride ion with a silver cartridge. After pretreatment, the
concentration of dissolved ions was measured by IC with IonPac AS18
analytical column and 32 mm MKOH as an eluent. The test result was
also assured by Korea Basic Science Institute (KBSI).
3. Results and discussions
Hydrate formation experiments in this work were performed for
120 minutes to produce pellets similar to the work of Park et al. [22].
The experimental results along the salt concentrations of the seawater
and the hydrate pellets are presented in Table 3. As shown in Table 3,
about 77% of salinity was removed by using CO2 as a guest gas in the
HBD process, and the removal efficiency of cation (76.18%) was similar
to that of anion (76.94%). It is noted that Park et al. reported a cation re-
moval efficiency for seawater in the range of 72% to 80%. In this work, in
the presence of anions, the cation removal efficiency was also consistent
with the data reported by Park et al. [22], which was conducted in the
absence of anions. Moreover, the salinity in the reactor was slightly
increased as the water was separated in the form of hydrate pellets.
Fig. 2 shows the ion removal efficiency of each dissolved mineral
using the HBD process with CO2 gas as a guest. The results comparing
the removal efficiency obtained by dissociation of pellets made through
80 kgf/cm2 (7.85 MPa) and 100 kgf/cm2 (9.81 MPa) hydraulic pressures
ð1Þ
suggest that the removal efficiency is higher at 100 kgf/cm2 (9.81 MPa)
hydraulic pressure for pellet production. At higher hydraulic pressure,
more brines (or ions) may diffuse through pellets into the bulk solution
during the pelletizing step. It is also noted that the removal efficiency
for each ion is slightly higher if the pellets' surfaces are wiped with
KimWipes. The overall increase by cleaning the surface is by about
2.1% to 4.4%
The removal efficiency of each dissolved mineral using the HBD
process with CH4 gas as the guest is shown in Fig. 3, in which a similar
pattern between the 80 (7.85 MPa) and 100 kgf/cm2 (9.81 MPa) was
observed with pellets formed with CO2 as a guest gas (see Fig. 2). In
the CO2 hydrate process (Fig. 2), 71%–94% of each cation was removed
in the following order: K+ N Na+ ≈ Mg2 + ≈ Ca2 + N B3 + and
73%–83% of each anion was removed, in which sulfate ion (SO42 −)
Hydraulic pressures (MPa) for pellet formation
60 80 100
a b
80 80
√ √ √ √
− √ − √
 K.C. Kang et al. / Desalination 353 (2014) 84–90
Table 3
Experimental results with salt concentrations and removal efficiencies (CO2 hydrate
formation at 2.9 MPa and 280 K).
Sample Salt concentration Removal efficiency (%) Remainder in
(mg/L) reactor (mg/L)
Total Cations Anions
Seawater 35,739.99 – – – 45,727.09
CO2 hydrate a 8,338.84 76.67 76.18 76.94
a
The hydraulic pressure was 80 kgf/cm2. About 20 pellets of CO2 hydrate were used.
was approximately equal to chloride ion (Cl−). In the CH4 hydrate pro-
cess, the trend of the results was similar to the CO2 hydrate process. It is
interesting to note from Figs. 2 and 3 that there is a reduction in the re-
moval efficiency of each ion when methane is used as a guest gas. There
are two factors that should be given consideration. The first one is that
the hydraulic pressure for both CO2 hydrate pellets and CH4 hydrate pel-
lets were the same but the relative hydraulic pressure will be different
since the CO2 hydrate formation experiments were conducted at
2.9 MPa and the methane hydrate formation experiments were con-
ducted at 4.5 MPa. Another factor is the type of guest gas used for hy-
drate formation. If we compared with the hydraulic pressure at 80
(7.85 MPa) and 100 kgf/cm2 (9.81 MPa), for all of the ions, efficiency
is higher if CO2 is used as a guest gas. Similarly, if we compare based
on relative hydraulic pressure accounting for the different experimental
pressures employed, the removal efficiency of ions with CO2 hydrate at
80 kgf/cm2 (relative hydraulic pressure = 4.95 MPa) is still higher than
the removal efficiency of ions with CH4 hydrate at 100 kgf/cm2 (relative
hydraulic pressure = 5.31 MPa). Clearly, the higher efficiency in the re-
moval of ions is dependent on the type of guest gas employed the HBD
process. It would be difficult to explain why this phenomenon is occur-
ring based on our work. There is a need to investigate this behavior at
the molecular or morphological level to understand this phenomenon.
The total removal efficiency for the formation guest gases (i.e. CO2 and
CH4) were compared at the same relative hydraulic pressures (3.2 and
5.2 MPa) in Fig. 4 and presented in the following order: CO2 N CH4
(Table 4).
During the experiments, CO2 hydrate pellets were successfully
produced and extracted from the reactor, but CH4 hydrate pellets com-
pressed at the low hydraulic pressure (i.e. below 8 MPa) were exposed
to atmospheric pressure and occasionally broke at the same time. It
seems that the relative pressure for CH4 hydrate pellets was lower
Fig. 2. Removal efficiency of each dissolved mineral (CO2 hydrate formation at 2.9 MPa and
280 K). The hydrate samples were pelletized at 80 kgf/cm2 (dissociation with and without
surface washing) and 100 kgf/cm2.
87
Fig. 3. Removal efficiency of each dissolved mineral with its effective ionic radius (CH4
hydrate formation at 4.5 MPa and 280 K). The hydrate samples were pelletized at
80 kgf/cm2 (low hydraulic pressure) and high hydraulic pressure was 100 kgf/cm2.
than that for CO2 hydrate pellets because the formation pressure
(4.6 MPa) of CH4 hydrate is higher than that (2.9 MPa) of CO2 hydrate
in this study. For the same reason, when CH4 hydrate slurries in the con-
nection pipe were compressed and squeezed by the strokes of the dual
cylinder operation, the hydraulic pressure was not enough to make
pellets in contrast with CO2 hydrate pellets. Likewise, it seems that ion
removal efficiencies not only depend on the hydrate-forming gas but
also the physical property (i.e. crystal system, compressibility, and
critical pressure for pelletizing) of gas hydrate. In Durham et al.'s mea-
surements, methane hydrate was more than 20 times stronger (creep
resistant) than ice at temperatures just below the freezing point [28].
Shimizu et al. indicated that methane hydrate is slightly more com-
pressible than ice, based on the evaluation of the compressional compo-
nents of elastic moduli [29]. Both carbon dioxide and methane form
hydrate structures I with cubic crystals. But the pelletizing properties
of CO2 and CH4 hydrates were different in the same apparatus. It
seems that an agglomerative property of the hydrates is different from
each other, which can be analyzed by a morphological study.
The effect of temperature (T), pressure (P), and salinity (S) on pK1*
and pK2* is illustrated in Fig. 5. The reference case is Tc = 25 °C,
S = 35‰, and P = 1 atm (solid line). At typical seawater conditions,
bicarbonate is a dominant species, followed by carbonate ion, whereas
dissolved carbon dioxide is only present in small concentrations [30]. In
the formation of CO2 hydrate, the concentration of dissolved carbon
dioxide dramatically increases because CO2 gas is fed to maintain a
Fig. 4. Removal efficiency of total dissolved minerals in gas hydrate formation by guest
gases depending on hydraulic pressures.
88 K.C. Kang et al. / Desalination 353 (2014) 84–90
Table 4
Removal efficiency of ions dependent on the relative hydraulic pressure and hydrate for-
mation gas.
Gas hydrate Relative hydraulic pressures pH
(MPa)
32 52 82 nitial
Removal efficiency (%)
CO2 75.07 75.49 83.23 7.844
CH4 60.49 68.86 – 8.044
constant high pressure in the reactor. The value of pH measured during
hydrate formation process was 4.75, in which carbonate ion (CO32−)
does not exist in the bulk liquid phase. A vertical dotted line in Fig. 5
shows the pH value measured during CO2 hydrate formation in this
study. Dissolved carbon dioxide was a dominant species in our experi-
mental condition (2.9 MPa at 280 K), and the precipitation of calcium
carbonate did not occur.
It is also noted from Figs. 2 and 3 that the removal efficiency of all
ions had a similar value except boron and potassium. The removal effi-
ciency of boron was 5% to 8% less than in other ions. In natural seawater,
the pK value of boron is 8.6 due to ionic composition, and with a pH
value lower than the pK value, boric acid B(OH)3 dominates [31]. In
this study, pH value (i.e. CO2 = 4.75 and CH4 = 7) was lower than
8.6, which means that boron exists in acid form in all hydrate processes.
The size of boric acid is smaller than borate, and it is not electrically
charged.
Most ions were hydrated by water molecules and interacted with
gas hydrate. Sloan and Koh indicate that ionized salts in seawater inter-
act with water molecules by Coulombic force and hydrate formation is
inhibited by salt ions [7]. Generally, it is proposed that concepts to illus-
trate ion hydration are kosmotrope and chaotrope. Kosmotrope and
chaotrope mean solutes, which have an effect on stability and structure
of water–water interactions. The kosmotropic ions (e.g. Mg2 +, Ca2 +,
Na+, and SO42−) contribute to stability and structure of water–water
interactions and cause water molecules to favorably interact with a
strongly held hydration shell [32]. On the other hand, the chaotropic
ions (e.g. Cl− and K+) have weakly held hydration shells with low
charge density and have weaker interactions with water molecules
than kosmotropic ions.
It has been recognized that the polarisability of hydrated ion
is increased by adding that of a water molecule, multiplied by the
hydration number of the ion [33]. In particular, Ninham and coworkers
Fig. 5. Illustration of the effect of temperature, pressure, and salinity on pK⁎1 and pK⁎2 . The
reference case is Tc = 25 °C, S = 35‰, and P = 1 atm (Zeebe and Gladrow, 2001). A
vertical dotted line means that pH value was measured during CO2 hydrate formation in
this study.
have extensively explored ionic specificities such as ionic size,
polarisability, hydration, and shape [34–37]. They estimated ion size
from quantum chemical calculations of ion volumes and calculated dy-
namic polarisabilities. Parsons and Ninham determined that increased
ionic size of kosmotropic ions by hydration lead to weakening of the
Final ion's dispersion forces, while the increased polarisability strengthens
them [32]. In contrast, they suggested that chaotropic ions have a
weakly held hydration layer without effectively changing ionic size or
4.754
7.035
polarisability in their ionic hydration model. Fig. 6 shows illustrations
of hydration model of ions and the hydrate surface, modified from
that of Parsons and Ninham. The kosmotropic ion is strongly hydrated,
and may penetrate into the hydrate surface, while the chaotropic ion is
weakly hydrated or has no hydration shell. Nevertheless, kosmotropic
ions can be weakly hydrated due to the decreased polarisability caused
by excessively increased ionic size.
From this viewpoint, the results (Figs. 2 and 3) show that the removal
efficiencies of ions (i.e. Mg2+, Ca2+, Na+, and SO42−) are similar to each
other due to the property of kosmotropic ions, in which ions with
a strongly held hydration shell are adsorbed on the hydrate surface.
Potassium ion, a representative chaotropic ion, was eliminated more
than the ions (i.e. Mg2+, Ca2+, Na+, and SO42−) because it remained in
the bulk water of the reactor without adsorption on the hydrate surface.
However, it was not enough to account for the properties of ionic
behavior in this study.
Recently, Tansel [38] classified ionic hydrations according to
hydrated radius and hydration free energy: (a) small hydrated ions
with strong hydration shells (SS), (b) small hydrated ions with weak
hydration shells (SW), (c) large hydrated ions with strong hydration
shells (LS), and (d) large hydrated ions with weak hydration shells
(LW). Tansel indicated that the more the charge density of the ions
Fig. 6. Illustrations of ionic hydration and hydration model of kosmotropic (e.g. Mg2+,
Ca2+, Na+, and SO4 2−) and chaotropic (e.g. Cl− and K+) ions, and the hydrate surface.
The figure of hydration model was modified from that of Parsons and Ninham (2011).
 K.C. Kang et al. / Desalination 353 (2014) 84–90
Fig. 7. Ionic behavior in terms of hydration free energy and hydrated radius. There are four
groups; small hydrated ions with strong hydration shells (SS), small hydrated ions with
weak hydration shells (SW), large hydrated ions with strong hydration shells (LS), and
large hydrated ions with weak hydration shells (LW).
increased, the more the hydration free energy increased, and the
smaller one for ions with the same charge would be hydrated stronger
than the other [38].
As shown in Fig. 7 and Table 5 [39–47], we classified ions (i.e. Na+,
K+, Mg2+, Ca2+, Cl−, and SO42−) by hydration free energy and hydrated
their radius, and it was found that the distribution of ions was similar to
our results from ion removal efficiencies. They were divided into two
groups: LW (Na+, Mg2 +, Ca2 +, Cl−, SO42 −) and SW (K+). Although
specific hydration information on the boron species is not currently
available, we believe that boron (i.e. boric acid) is classified as the SS.
As mentioned earlier, boron in bulk water exists as boric acid, which is
strongly combined with three water molecules. In addition, the
polarisability of boric acid was increased by adding the polarisability
of a water molecule. Due to these links with the water molecules, the
removal efficiency of boron ion was lower than other ions because
boric acid was easily adsorbed on the hydrate surface.
4. Conclusions
The purpose of this study was to evaluate an application possibility
of hydrate-based desalination process. It is essential to clarify more
detailed ion rejection mechanisms in the HBD process. Experiments
without the pretreatment were carried out by our novel apparatus
in the single stage of hydrate process, depending on various factors
(i.e. the hydraulic pressure, the removal of brines on the surface of
hydrate pellets, and the formation of guest gas). The type of guest gas
will have an impact on removal efficiency. It was observed that CO2 as
a guest gas is more suitable than CH4 for the HBD process. In CO2
hydrate process, 71%–94% of each cation was removed and 73%–83%
of each anion was removed. It was also observed that an increase in
the hydraulic pressure to produce pellets resulted in an increase in the
removal efficiency of ions for both the guest gasses tested in this
Table 5
Hydrated radius and hydration free energy of ions.
Ion Hydrated radius (pm) hydration free energy (KJ/mol)
Na+ 299 [39] −365 [45]
Mg2+ 470 [40] −1828 [45]
K+ 201 [41] −271 [46]
Ca2+ 420 [40] −1650 [47]
B3+ N.A. [42] N.A. [42]
Cl− 332 [43] −340 [45]
SO4 2− 379 [44] −1145 [44]
N.A. not available
89
study. It seems reasonable to conclude that ionic hydration due to
ionic charge and size can be considered as key factors to understand
the mechanism of ion removal in the HBD process. However, due to
these links with the water molecules, the mechanism behind the ionic
exclusion process is very complicated. Therefore, the correlation
between ionic hydration and clathrate hydrate remains a matter to be
discussed further, and the property of ionic behavior depending on its
concentration should be examined further in the future.
Acknowledgements
This research was a part of the project titled “Development of Key
Technology in Seawater Desalination Using Gas Hydrate Process,”
funded by the Ministry of Oceans and Fisheries, Korea. Praveen Linga
would like to thank the Ministry of Education's Academic Research
Fund (AcRF) Tier 1 (R-279-000-386-112) in Singapore for financial
support.
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