Chemical Engineering Science 218 (2020) 115563

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Chemical Engineering Science

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

Hydrate-based desalination (HyDesal) process employing a novel

prototype design
Ponnivalavan Babu a,⇑, Abhishek Nambiar a, Zheng Rong Chong a, Nagu Daraboina b,
Mohammad Albeirutty c,d, Omar A. Bamaga c, Praveen Linga a,⇑
a
Department of Chemical and Biomolecular Engineering, National University of Singapore, Engineering Drive 4, Singapore 117585, Singapore
b
Russell School of Chemical Engineering, The University of Tulsa, Tulsa, OK, USA
c
Department of Mechanical Engineering, King Abdulaziz University, PO Box 80204, Jeddah 21589, Saudi Arabia
d
Center of Excellence in Desalination Technology, King Abdulaziz University, Jeddah 21589, Saudi Arabia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A novel prototype of Hydrate-based

Desalination (HyDesal) process is
demonstrated.
 Water recovery and salt rejection rate
were investigated in the prototype.
 Water recovery of 34.85% and salt
rejection of 87.5% was achieved with
3 wt% NaCl solution.

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

Article history: Water and energy are intricately interlinked and therefore it is imperative to develop sustainable tech-
Received 25 September 2019 nologies to strengthen water-energy nexus. One such industry where the energy – water nexus can be
Received in revised form 14 January 2020 addressed is at Liquefied natural gas (LNG) regasification terminals. At the LNG regasification terminals,
Accepted 8 February 2020
LNG is converted back to natural gas by heating using seawater which gets cooled during the process.
Available online 10 February 2020
This cooled seawater is dumped back to the sea leading to wastage of cold energy. One potential technol-
ogy that can harvest and utilize this waste cold energy is the hydrate-based desalination (HyDesal) pro-
Keywords:
cess. HyDesal process is based on a liquid to solid phase change by employing a suitable hydrate former
Gas hydrates
Desalination
for the phase change. While the HyDesal process was proposed almost 70 years ago, it was never com-
Clathrate process mercialized primarily due to slow hydrate formation, inefficient hydrate crystal separation from brine
Seawater and refrigeration. To address the above challenges, we proposed an innovative HyDesal process utilizing
Water-energy nexus LNG cold energy with enhanced water recovery based on the unusual behavior of propane. In this study,
we present the design and demonstration of a prototype for the HyDesal process. With our innovative
prototype design, we carried out water recovery experiments and salt rejection studies. Water recovery
of 34.85 (±0.35)% and salt rejection of 87.5 (±1.84)% was achieved with 3 wt% NaCl solution.
Ó 2020 Elsevier Ltd. All rights reserved.

⇑ Corresponding authors.
E-mail addresses: valavan@u.nus.edu (P. Babu), praveen.linga@nus.edu.sg (P. Linga).

https://doi.org/10.1016/j.ces.2020.115563
0009-2509/Ó 2020 Elsevier Ltd. All rights reserved.
2 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563
1. Introduction
Energy and water are key resources for sustainable and smart
nation development. Water is required to produce energy and
energy is required to pump and transport water. Hence, water
and energy are intricately interlinked and energy-water nexus
examines the interaction between these two interlinked sectors.
Global energy demand is expected to increase by about 27% from
2017 to 2040 and a great amount of water is required for energy
supply (Chen and Chen, 2016; Hightower and Pierce, 2008). How-
ever, one of the biggest challenges facing mankind today is the lack
of availability of potable water. The existing technologies to pro-
duce water through desalination are energy intensive (Raluy
et al., 2005; Subramani and Jacangelo, 2015). Therefore, there is a
need to address these challenges in a holistic way and develop
state of the art innovative technologies to address water-energy
nexus (Dai et al., 2018; Liu et al., 2018).
One such industry where the energy-water nexus can be
addressed is at Liquefied natural gas regasification terminals. Nat-
ural Gas is the cleanest fossil fuel available on Earth and is widely
regarded as the fuel for the future. Liquefied Natural Gas (LNG) is
the preferred mode of transport of natural gas (Kumar et al.,
2011). To produce LNG, natural gas needs to be purified and then
liquefied through an energy intensive operation where NG is con-
verted to liquid at 162 °C. The LNG is then transported as a liquid
by maintaining the temperature at 162 °C to the receiving termi-
nals. At the receiving terminals, LNG is converted back to the gas
phase through a process called re-gasification. At the LNG terminal,
the cold energy is removed through heating the LNG to 25 °C by
employing seawater. This seawater which gets cooled during
regasification is dumped backed to the sea. To re-gasify one
tonne/h of LNG, about 40 tonnes/h of seawater is required. One
tonne of LNG requires the removal of 214 kWh of cold energy
(He et al., 2019). This huge cold energy is currently not being har-
vested and utilized. Therefore, there is a need to develop an inno-
vative technology that can harvest and utilize the waste LNG cold
energy effectively for energy conservation.
One potential technology that can utilize the waste cold energy
and produce water is clathrate hydrate based desalination (HyDe-
sal) (Babu et al., 2018; Englezos, 1993; He et al., 2019; Kang et al.,
2014; Park et al., 2011). In the HyDesal process, water molecules
form cages around a guest gas/liquid component, effectively sepa-
rating itself from the brine solution at temperatures higher than
the normal freezing temperature of the water (Sloan Jr and Koh,
2007). Hydrates have the inherent ability to reject salts and impu-
rities present in seawater (Kang et al., 2017). In other words, one
cubic meter of hydrate consists of 85–94% water and 6–15% guest
gas which signifies the high potential of producing relatively pure
water from this process. Other applications of hydrate based tech-
nology are gas separation, CO2 sequestration, natural gas storage
and transport, cold storage and refrigeration (Babu et al., 2014a;
Babu et al., 2015; Babu et al., 2016; Chong et al., 2016; Englezos,
1993; Eslamimanesh et al., 2012; Ogawa et al., 2006; Sum et al.,
2009; Veluswamy et al., 2018; Zhou et al., 2018).
Hydrate based desalination (HyDesal) process was proposed
since the 1940s as a potential technology for desalination
(Parker, 1942). Although research in both academics and industrial
scale has been made since then, this process has not been success-
fully commercialized. The major challenges that impede the
deployment of the HyDesal process are slow kinetics of hydrate
formation, crystal separation from concentrated brine and the cold
energy required for the process (Babu et al., 2018; Englezos, 1993).
Efforts have been focused to mitigate these challenges to develop a
process that can desalinate seawater/ brackish water in energy-
efficient and cost-effective manner. Operating conditions for the
HyDesal process depend primarily on guest gas/ liquid component
employed. Research has primarily been focused on identifying suit-
able hydrate formers to mitigate challenges of salt removal, slow
kinetics and guest recovery (Barduhn et al., 1962; Cai et al.,
2014; Corak et al., 2011; Fakharian et al., 2017; Mekala et al.,
2014; Simmons et al., 2009). A comprehensive review of works
and prior art on HyDesal has been presented elsewhere (Babu
et al., 2018; Englezos, 1993).
In our previous work, we proposed a conceptual hydrate based
desalination (ColdEn-HyDesal) process utilizing waste LNG cold
energy (Babu et al., 2014b). We reported that the specific energy
consumption can be lowered from 65.13 kWh/m3 of potable water
to 0.84 kWh/m3 by utilizing waste LNG cold energy (He et al.,
2018). Our approach is based on the unusual behavior of hydrate
formation in silica sand bed in the presence of propane as co-
guest (Babu et al., 2014b). Propane as a co-guest can draw dis-
persed water present between the interstitial pore spaces between
the sand particles towards the gas phase to form hydrates and
enhance the rate of hydrate formation. We evaluated different
gas mixtures consisting of propane which can enhance the kinetics
of hydrate formation and water recovery in a flatbed configuration.
We reported that 10% propane in carbon dioxide gas mixture is
suitable for the HyDesal process resulting in a water recovery of
about 42% (Nambiar et al., 2019). However, the water quality and
challenges of separation of hydrate crystal from the brine and scal-
ability were not addressed. In this study, we present the design and
demonstration of a prototype for HyDesal process.
2. Experimental
2.1. Materials
The C3H8/CO2 (10/90%) gas mixture employed in this study was
supplied by Soxal Private Ltd. Sodium chloride (CAS 7647-14-5) of
purity 99% and Silica sand of particle size 0.21–0.29 mm were sup-
plied by Sigma Aldrich. The sand used in this study was similar to
the sand used in our previous works (Babu et al., 2013a,b; Yang
et al., 2016). Deionized and distilled water were used to prepare
the NaCl solution. Sodium chloride is the dominant salt in seawater
and hence it is used in this study.
2.2. Flatbed reactor setup and procedure
The detailed description of materials, apparatus, and
procedure employed is given elsewhere (Nambiar et al., 2019;
Zheng et al., 2016).
The procedure to calculate water recovery and the rate of hydrate
formation is given in our previous study (Nambiar et al., 2019).
Briefly,
Volume of water converted to hydrate  Fh
Water recovery % ¼  100
Volume of feed solution
ð3Þ
where Fh is the fraction of hydrate formed that is recoverable at the
hydrate crystal separation step from the brine. Since in our study
with flatbed configuration, the hydrate crystals were not separated
from the brine, Fh of 1 was used in the above equation.
The rate of water recovery (R20) is calculated by fitting the
water recovery growth versus time for the first 20 min from the
nucleation point using the least-squares method.
3. Challenges of flatbed reactor design
In our previous study, we reported that 1.5 cm silica sand bed
height is optimum for the HyDesal process employing a fixed bed
 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563
reactor (Babu et al., 2014b). The gas mixture employed in that
study was CO2/H2/C3H8 (38.1/59.4/2.5%) gas mixture. Recently,
we reported that the suitable gas mixture for the HyDesal process
is C3H8/CO2 (10/90%). To determine the optimum bed height with
C3H8/CO2 (10/90%) gas mixture, experiments were carried out at
different bed heights in a flatbed reactor with silica sand of particle
size 0.21–0.297 mm as porous media.
The effect of bed height on water recovery at 2.6 MPa and
274.2 K in the presence of CO2/C3H8 (90/10%) gas mixture with
3 wt% NaCl solution is shown in Fig. 1. The data for 1.5 cm bed
height is from our previous study (Nambiar et al., 2019). Water
recovery of 41.4 (±7.4) and 13.61 (±0.23) % was achieved in 1 h
after hydrate nucleation for 1.5 and 5.0 cm bed height respectively.
Experiments with 1.5 cm bed height resulted in higher water
recovery than experiments with 5.0 cm bed height and hence
Fig. 1. Effect of different bed height on water recovery at 2.6 MPa and 274.2 K in
presence of CO2/C3H8 (90/10%) gas mixture with 3 wt% NaCl solution.
Fig. 2. Innovative reactor designs.
3
1.5 cm bed height is the optimum. The amount of water used for
1.5 and 5.0 cm bed height was 52.51 and 148.34 ml respectively.
The amount of water recovered for the two bed heights were
21.9 (±3.5), and 20.2 (±0.35) ml for 1.5 and 5.0 cm bed heights
respectively. This suggests that water deep inside the bed is not
participating in hydrate formation and remains occluded in the
sand. Irrespective of the gas mixture employed, the optimum bed
height was found to be 1.5 cm. However, scaling up the flatbed
reactor with a 1.5 cm silica sand bed is a challenge. The hydrate
crystals formed above the silica sand bed also needs to be recov-
ered to produce water. Therefore, an innovative reactor that can
address the above challenges needs to be designed and
demonstrated.
4. Design of innovative reactor
To overcome the challenge of scalability, we designed two dif-
ferent reactors namely cylindrical core bed and cylindrical annular
bed reactor. The apparatus used is the same as a flatbed reactor.
The innovation is the configuration of the silica sand bed inside
the reactor at the annular or core region of the reactor. Fig. 2 shows
the two innovative reactor configurations along with flatbed con-
figuration. A cylindrical mesh (size 80) of length 12 cm holds the
silica sand particles in the innovative reactor configurations. The
size of the mesh is smaller than the sand particle size to prevent
sand from coming out of the cylindrical mesh. The diameter of
the cylindrical mesh can be varied to adjust the thickness of the
bed. Experiments were carried out at 2.6 MPa and 274.2 K with
3 wt% NaCl solution with different bed thickness in cylindrical core
bed and cylindrical annular bed.
The summary of experimental results such as induction time,
water recovery and rate of hydrate formation is given in Table 1.
For comparison of the performance of the cylindrical core bed reac-
tor and annular bed reactor, a bed thickness of 2.55 cm was chosen
since the surface area of the sand-mesh-gas interface will be the
same for both the reactor configurations. The water recovery
4 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563

Table 1
Summary of results with CO2/ C3H8 (90 mol% /10 mol%) gas mixtures and 3 wt% NaCl
solution at 2.6 MPa and 274.2 K.

System Exp. Bed Induction Water recovery R20

No Thickness Time (IT) at 60 min from
(cm) (min) IT (%) (cm3/min)
Cylindrical Core C1 1.50 24.33 38.02 0.9439
Bed C2 1.50 9.00 31.12 0.8120
C3 2.55 0.33 28.68 0.5890
C4 2.55 0.67 24.76 0.7028
Cylindrical A1 1.00 4.67 19.27 1.0506
Annular Bed A2 1.00 3.67 19.08 0.9872
A3 1.50 0.33 29.53 1.3504
A4 1.50 0.33 29.47 1.3579
A5 1.90 0.33 31.18 1.0102
A6 1.90 2.67 31.24 1.2650
A7 2.55 0.33 19.46 0.7785
A8 2.55 0.33 24.08 0.7535

Fig. 3. Effect of annular bed thickness on water recovery at 2.6 MPa, 274.2 K with
MS2 sand bed, CO2/C3H8 (90/10%) gas mixture and 3 wt% NaCl solution.
achieved was 26.72 (±2.77) and 21.77 (±3.27) % respectively for
core bed and annular bed reactor configuration. It has to be noted
that the water recovery is the % water recovered with respect to is 1.5 cm. Although the mechanism of hydrate formation is same
feed water. The actual amount of water recovered for the core (movement of dispersed water towards the gas phase), the
bed reactor and the annular bed reactor were 18.85 (±1.96) and direction of water movement is towards the sides (horizontal) in
46.79 (±7.02) ml. The cylindrical core bed reactor performed better annular bed and upwards (vertical) in the flatbed reactor. The dif-
than the cylindrical annular bed reactor in terms of water recovery. ference in optimum thickness for annular bed reactor is maybe due
However, in terms of the rate of hydrate formation, the cylindrical to direction of gravity.
annular bed reactor performed better than the cylindrical core bed A uniform layer of hydrate crystals formed around the mesh
reactor. The rate of hydrate formation for core bed and annular bed and these hydrate crystals need to be separated to recover water
reactor achieved was 0.65 (±0.09) and 0.77 (±0.02) cm3/min from it. Fig. 4 shows the hydrate crystals formed around the mesh
respectively. in the innovative annular bed reactor design. To remove the
For a given bed thickness, a cylindrical annular bed reactor can hydrate crystals, we designed an innovative scraper attached to a
process more feed water compared to other reactor configurations. magnetic drive. The scrapper can be operated at a fixed interval
The desalination capacity increases 3 times for an annular bed of time to remove the hydrates thereby renewing the gas-liquid
reactor compared to the core bed reactor for a given bed thickness contact. Fig. 5 shows the innovative scraper design employed to
of 2.55 cm. The cooling jacket is in contact with the saturated sand remove the hydrate crystals from the mesh.
bed in cylindrical annular bed. In cylindrical core bed, the cooling Based on the above design to overcome the challenges of scala-
jacket is in contact with the gas phase. The thermal conductivity bility and hydrate separation from brine, we have built a prototype
of saturated sand (around 2–4 W/mK) is higher than the gas. to demonstrate the hydrate based desalination (Linga et al., 2018).
Hence, efficient cooling can be achieved in the annular bed design A cross-sectional view of a novel annular bed reactor design along
compared to cylindrical core design and the hence annular bed is with the scrapper is shown in Fig. 6. The prototype consists of the
most desirable. It has to be noted that with our reactor with a cool- seawater treatment zone, separator valve and desalinated water
ing jacket, the core bed reactor configuration took nearly double recovery zone. The seawater treatment zone consists of an annular
the time to cool down the bed to the experimental temperature bed reactor made up of 316 stainless steel. The internal diameter of
than the annular reactor configuration.
As we reported previously, with propane as co-guest in the
hydrate forming gas mixture, hydrate formation occurs at the
sand-gas-mesh interface and the hydrate grows above the sand
layer towards the gas phase. Water dispersed in the interstitial
pore space of sand particles moves towards the hydrate growth
front for further hydrate formation due to capillary movement.
Apart from the capillary force, the extent of water participating
in hydrate formation depends on the surface area of the cylindrical
mesh (sand-gas-mesh interface). The surface area of the interface
depends on the thickness of the bed. Therefore, the annular bed
thickness needs to be optimized to achieve maximum water recov-
ery and hydrate formation. Experiments with different annular bed
thicknesses of 1.0, 1.5, 1.9, 2.55 cm were carried out at 2.6 MPa,
274.2 K, MS2 sand and 3 wt% NaCl solution to optimize the bed
thickness. Fig. 3 shows the effect of bed thickness on water recov-
ery. The annular bed thickness of 1.9 cm was found to yield higher
water recovery amongst various thicknesses experimented. Water
recovery achieved in 1 hr was 19.2 (±0.1), 29.5 (±0.1), 32.0 (±1.1)
and 21.8 (±3.3) % for annular bed thickness of 1, 1.5, 1.9 and
2.55 cm respectively. It has to be noted that the optimum bed Fig. 4. Hydrate formation around the mesh in the annular bed reactor
thickness for annular bed reactor is 1.9 cm while for flatbed reactor configurations.
 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563 5

Fig. 5. Innovative scraper design.

Fig. 6. Novel cylindrical annular bed reactor design along with the scrapper.
6 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563
the annular bed reactor is 10.2 cm. A metallic mesh holds the silica
sand in the annular region. The diameter of the cylindrical mesh
can be varied to adjust the thickness of the bed. The temperature
of the crystallizer is controlled by the cooling jacket connected to
an external refrigerated circulator. A multipoint thermocouple
(Omega copper-constantan T-type, ±0.1 K) is used to measure tem-
peratures at different locations of 0, 2, 4, 6, 8, 10 cm from the bot-
tom of the sand bed. A gas reservoir is connected to the reactor to
supply gas. A separator valve V1 connects the seawater treatment
zone to the desalinated water recovery zone. The internal diameter
of the separator valve is 6.4 cm. The desalinated water recovery
zone consists of a dissociation reactor of volume 165.8 cm3. The
internal diameter and height of the dissociation reactor are 6.5
and 5 cm respectively. A cooling jacket around the dissociation
reactor connected to an external refrigerated circulator helps to
maintain the temperature of the dissociation reactor. A valve V2
is present at the bottom of the dissociation reactor to collect the
recovered water at the end of dissociation. Three Rosemount smart
pressure transducer (model 3051S, ±20 kPa) measures the pressure
of the reservoir, annular bed reactor and dissociation reactor. The
pressure and temperature data were recorded using a National
Instruments CompactRIO data acquisition system and LabView
software.
The feed seawater enters at the top of the annular bed via mul-
tiple the feed ports. The reactor is pressurized with the gas mixture
consisting of propane as one of the constituents. Hydrate crystals
nucleate at the sand-mesh-gas interface and grow on the surface
of the mesh towards the gas phase. The formed hydrate crystals
stick to the outside of the cylindrical mesh. When the novel scrap-
per attached to a magdrive rotates, it scrapes/removes the hydrates
Fig. 7. Schematic of the Prototype to demonstrate the HyDesal process.
attached to the outside of the cylindrical mesh at a regular interval
of time. The scrapped hydrates are collected at the bottom of the
annular bed reactor. Once hydrates are collected at the bottom of
the reactor, separator valve V1 is opened to collect hydrates in
the desalinated water recovery zone which is maintained at the
same pressure as the seawater treatment zone. Once the hydrates
fall into the desalinated water recovery zone, separator valve V1 is
closed. Hydrates are dissociated by thermal stimulation and
depressurization with the help of a heating jacket in the desali-
nated water recovery zone. Once hydrates are dissociated, valve
V2 is opened and recovered water is allowed to flow downwards
to the collection tank and gas is recycled. The seawater treatment
zone is depressurized and the sand bed is washed to remove the
brine. Brine is collected via the discharge ports present at the bot-
tom of the sand bed. Each modular prototype unit can operate in
series/parallel to produce water continuously.
5. Prototype demonstration
A schematic of the prototype to demonstrate hydrate based
desalination is shown in Fig. 7. Experiments were carried out at
2.6 MPa and 274.2 K with 3 wt% NaCl solution and C3H8/CO2
(10/90%) gas mixture. The thickness of the bed used for experi-
ments were 1.5 and 1.9 cm. Hydrates were allowed to form for
30/60 mins after nucleation. The formed hydrate crystals were
scrapped from the mesh at the end of hydrate formation and then
collected in the dissociation chamber and dissociated. At the end of
the dissociation, the recovered water was collected and weighed to
measure the water recovery. The recovered water is tested using
 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563 7

Table 2
Summary of water recovery and salt rejection experiments in prototype with CO2/ C3H8 (90 mol% /10 mol%) gas mixtures and 3 wt% NaCl solution at 2.6 MPa and 274.2 K.

Exp. No Bed Thickness Hydrate formation time Water recovery (%) Salt rejection rate
(cm) (mins) Na (%) Cl (%)
P1 1.50 60.00 38.8 75.3 72.5
P2 60.00 36.9 80.8 78.2
P3 30.00 37.8 88.1 83.3
P4 30.00 34.1 86.7 82.1
P5 30.00 39.7 86.5 85.3
P6 30.00 33.8 86.4 85.4
P7 1.90 30.00 35.1 86.2 83.9
P8 30.00 34.6 88.8 84.4

ICP and IC to determine the salt rejection rate. The salt rejection The water recovery achieved for different bed thicknesses of 1.5
rate is calculated using the following formula and 1.9 cm was 36.35 (±2.88) and 34.85 (±0.35) % respectively for

Concentration in the feed seawater - Concentration in produced water

Salt rejection % ¼  100
Concentration in the feed seawater

hydrate formation time of 30 mins. As can be seen from the figure,

Rejection % of each individual ion can be calculated from the ion
concentration in the feed seawater and the produced water after
dissociation of the hydrate. The higher the rejection, the better is
the system performance.
Table 2 presents the summary of results such as water recovery,
salt rejection rate in the prototype. It must be noted the water
recovery presented in Table 2 is the amount of water collected
after hydrate dissociation.
Fig. 8 presents the effect of annular bed thickness and hydrate
formation time on water recovery at 2.6 MPa, 274.2 K with
CO2/C3H8 (90/10%) gas mixture and 3 wt% NaCl solution. Hydrate
formation time was varied to study its effect on water recovery.
For annular bed thickness of 1.5 cm, the hydrate formation time
of 30 and 60 mins were used. As can be seen from the figure,
increased hydrate formation time had minimal effect on the water
recovery. Similarly, an increase in bed thickness has a minimal
effect on water recovery. The water recovery achieved for 1.5 cm
bed thickness was 36.35 (±2.88) and 37.85 (±1.34) % respectively
for hydrate formation time of 30 and 60 mins respectively.
the change in water recovery is not significant with an increase in
annular bed thickness. However, an increase in bed thickness
increases the desalination capacity.
Fig. 9 shows the effect of annular bed thickness and hydrate for-
mation time on the salt rejection at 2.6 MPa, 274.2 K with
CO2/C3H8 (90/10%) gas mixture and 3 wt% NaCl solution. For exper-
iments with 1.5 cm bed thickness, 30 mins hydrate formation time,
the salt rejection rate for Na+ and Cl ion were 86.93 (±0.79) and
84.03 (1.61) % respectively. For experiments with 1.5 cm bed thick-
ness, 60 mins hydrate formation time, the salt rejection rate for Na+
and Cl ion were 78.05 (±3.89) and 75.35 (±4.03)% respectively. As
can be seen from Fig. 9, the increase in hydrate formation time
decreased the salt rejection rate for both Na+ and Cl ion. This
can be attributed to the increase in the concentration of salt in
the unreacted water as time progresses during hydrate formation
and increased hydrate formation.
For experiments with 1.9 cm bed thickness, 30 mins hydrate
formation time, the salt rejection rate for Na+ and Cl ion were

Fig. 8. Effect of annular bed thickness and hydrate formation time on water Fig. 9. Effect of annular bed thickness and hydrate formation time on salt rejection
recovery at 2.6 MPa, 274.2 K with CO2/C3H8 (90/10%) gas mixture and 3 wt% NaCl at 2.6 MPa, 274.2 K with CO2/C3H8 (90/10%) gas mixture and 3 wt% NaCl solution in
solution in the HyDesal prototype. the HyDesal prototype.
8 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563
Fig. 10. Transformation of lab scale fixed bed reactor to a scalable and modular prototype.
87.50 (±1.84) and 84.15 (0.35) % respectively. As can be seen from
the figure, the increase in annular bed thickness had minimal effect
on the salt rejection rate. Although salts do not participate in
hydrate formation, it may get adsorbed on to the formed hydrate
crystals resulting in presence of salts in recovered water. These
salts can be removed with secondary treatment steps like washing,
centrifuging etc. after hydrate formation and before dissociation.
However, these secondary steps affect the process efficiency and
economics.
Fig. 10 shows the transformation of our lab-scale fixed bed reac-
tor configuration to scalable and modular prototype design. The
optimum bed height found in the flatbed reactor configuration
was 1.5 cm. Scaling of flatbed reactor configuration will be a chal-
lenge owing to less feed water processing capacity and a number of
such reactors and areas required to process on a commercial scale.
Our novel annular bed design configuration addresses the above
challenges of scalability and separation of hydrate crystals from
brine. The annular bed reactor configuration can process nearly
3 times more feed water compared to the flatbed reactor configu-
ration. The modular prototype can be operated in series and paral-
lel to produce water continuously. The innovative scrapper
effectively and efficiently separates the hydrate crystals from the
brine. The novel prototype can be integrated with LNG regasifica-
tion to utilize and harvest the waste LNG cold energy thereby
addressing the challenge of refrigeration.
6. Conclusions
While the HyDesal process was proposed almost 70 years ago, it
was never commercialized primarily due to the high energy
requirement for low-temperature operation, slow hydrate forma-
tion kinetics and inefficient hydrate crystal separation from brine.
To address the above challenges, we have designed a novel proto-
type and demonstrated the HyDesal process. The novel prototype
consists of a cylindrical annular bed reactor and a physical scrap-
per. The annular cylindrical bed reactor configuration aids in effi-
cient gas-liquid contact and hence resulting in enhanced hydrate
formation. The physical scrapper separates formed hydrate crystals
from brine. With our innovative prototype, we achieved a water
recovery of 34.85 (±0.35) % and salt rejection of 87.5 (±1.84) % with
3 wt% NaCl solution at optimized conditions. Further studies with
actual seawater will be carried out to study the effect of various
salts present in seawater on water recovery and salt rejection rate.
The water distribution system will be automated and two modular
units operating in parallel/series mode will be demonstrated for
continuous HyDesal process.
CRediT authorship contribution statement
Ponnivalavan Babu: Conceptualization, Methodology, Investi-
gation, Writing - original draft, Writing - review & editing, Project
administration. Abhishek Nambiar: Conceptualization, Methodol-
ogy, Investigation. Zheng Rong Chong: Methodology, Investiga-
tion. Nagu Daraboina: Writing - review & editing, Supervision.
Mohammad Albeirutty: Writing - review & editing, Supervision.
Omar A. Bamaga: Writing - review & editing, Supervision.
Praveen Linga: Conceptualization, Methodology, Writing - review
& editing, Supervision, Funding acquisition, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The work was funded in part under the Energy Innovation
Research Programme (EIRP, Award No. NRF2014EWTEIRP003-006),
administrated by the Energy Market Authority (EMA). The EIRP is
a competitive grant call initiative driven by the Energy Innovation
Programme Office, and funded by the National Research Foundation,
Singapore (NRF). The authors would like to acknowledge funding
support from our industry collaborator, Shell Energy Singapore.
 P. Babu et al. / Chemical Engineering Science 218 (2020) 115563
MA and OAB would like to acknowledge the support by NSTIP strate-
gic technologies program in the Kingdom of Saudi Arabia Project No
(11-WAT2007-03) and Science and Technology Unit at King AbdulA-
ziz University, Saudi Arabia.
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