Energy Technology: Generation, Conversion, Storage, Distribution

Energy Technology
Generation, Conversion, Storage, Distribution
Accepted Article
Title: Techno-economic Evaluation of Cyclopentane Hydrate-Based
Desalination with LNG Cold Energy Utilization
Authors: Tianbiao He, Zheng Rong Chong, Ponnivalavan Babu, and Praveen
Linga
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To be cited as: Energy Technol. 10.1002/ente.201900212
Link to VoR: http://dx.doi.org/10.1002/ente.201900212
www.entechnol.de
Energy Technology 10.1002/ente.201900212
Techno-economic Evaluation of Cyclopentane Hydrate-Based Desalination with LNG

Cold Energy Utilization
Tianbiao He[a]*, Zheng Rong Chong[b], Ponnivalavan Babu[b], Praveen Linga[b]*
[a] Dr. Tianbiao He

Department of Gas Engineering, College of Pipeline and Civil Engineering, China University
of Petroleum (East China), Qingdao 266580, China
E-mail: hetianbiao@upc.edu.cn
[b] Dr. Zheng Rong Chong, Dr. Ponnivalavan Babu, Dr. Praveen Linga
Department of Chemical and Biomolecular Engineering, National University of Singapore,
Accepted Manuscript
Singapore 117585, Singapore
E-mail: praveen.linga@nus.edu.sg (P. Linga)
Keywords: gas hydrates, LNG cold energy, desalination, cyclopentane, hydrate based
desalination
The clathrate hydrate-based desalination process coupling with LNG cold energy (ColdEn-
HyDesal) can strengthen energy-water nexus by integrating two energy intensive processes into
one. A typical HyDesal process that employs a gas as hydrate former requires elevated pressure
for hydrate formation that results in a higher specific energy consumption (SEC). The efficiency
of the ColdEn-HyDesal process can be improved by adopting hydrate formers with milder
hydrate formation condition, such as cyclopentane (CP). In this study, the ColdEn-HyDesal
process utilizing cyclopentane as the hydrate former is modeled and investigated. The results
show that the SEC of the ColdEn-HyDesal process using CP is 0.35 kWh/m3. The effects of
three process parameters, namely water recovery rate, hydrate formation temperature, and
heating seawater pressure on key performance indicators, namely SEC, volumetric flow rate,
exergy efficiency, and fixed capital investment (FCI) are investigated. The water recovery rate
is found to have significant effect on the SEC, volumetric flow rate, exergy efficiency, and FCI;
whereas hydrate formation temperature has pronounced impact on FCI, while small impacts on
SEC, volumetric flow rate, and exergy efficiency. With a lower operating pressure and the
elimination of compressor for recycle, the ColdEn-HyDesal process using CP as the hydrate
This article is protected by copyright. All rights reserved.

former can further reduce SEC by 58% when compared to gas like propane as a hydrate forming
guest.
1. Introduction
The lack of clean and fresh water has been one of the most pervasive problems all over the
world because of the global population growth and water pollution[1]. The ocean covers around
Accepted Manuscript
70.8% of the total surface area of our planet, and ways to gain fresh water from the ocean in a
cost-effective way has drawn significant attentions in the past decades. Desalination is a process
that removes the mineral components from seawater and is regarded as one of the most
promising technologies to solve the pressing issue of freshwater scarcity[1]. Desalination
technologies are mainly classified into distillation, ion exchange, membrane process, freezing
process, and clathrate hydrate-based process[2]. The clathrate hydrate-based desalination
(HyDesal) excludes the salt and dissolved ions from the hydrate crystals during the hydrate
[3].
formation Afterward, the hydrate crystals can be separated from the aqueous solution by
using a solid-liquid separator. Then the dissociated hydrate crystals become guest component
and freshwater using the method of pressure reduction or heat stimulation.
The studies on the clathrate hydrate-based desalination (HyDesal) have been widely and
intensively conducted since the 1960s[4-8]. Propane[9-11] and refrigerant[12-14] are the most
common hydrate formers applied on hydrate-based desalination process. Moreover, some
experimental studies on carbon dioxide hydrate formation and dissociation in seawater were
also conducted[15-22]. However as reviewed by Babu et al. [23], the key challenges to overcome
to realize commercialization of HyDesal process are: high specific energy consumption, slow
kinetics of hydrate formation, and difficulty in separating the crystals from the brine. In our
previous work[24], a novel clathrate hydrate-based desalination process by utilizing LNG cold
energy (ColdEn-HyDesal) was proposed to reduce the specific energy consumption. The results
showed that the specific energy consumption could be reduced to 0.84 kWh/m 3 of pure water
2

when propane was used as the hydrate former. The ColdEn-HyDesal process was attractive
when compared to multistage flash distillation, freezing desalination, and reverse osmosis
desalination processes due to its lower specific energy consumption by using LNG cold energy
to replace the external refrigeration cycle. However, the pressure of the propane hydrate
formation was 400 kPa, which necessitated the hydrate generator to operate at high pressure
and increased the capital cost of the process. Moreover, the energy consumption of the propane
Accepted Manuscript
recycling compressor contributed 29.4% of the total energy consumption in the process when
the recycle pressure was 390 kPa. If the pressure of the recycled stream decreased, the propane
recycling compressor would reqyure more energy to pressurize the propane to the hydrate
formation pressure. Thus, adopting alternative hydrate formers with milder hydrate formation
condition can further improve the energy and economic performance of the ColdEn-HyDesal
process[25-26].
Cyclopentane (CP) is considered as the most promising hydrate former for HyDesal
process[27] because it is immiscible in water and can form sII hydrate at around 7.1 oC at
atmosphere pressure[28-30]. Cyclopentane hydrate formation and dissociation performance in
freshwater and brine solution have received significant research attention from the community.
Fan et al.[31] reported the hydrate equilibrium data for cyclopentane and a 98.40% purity
cyclopentane mixture containing three impurities in water by adopting a pressure-search
method. Corak et al. [32] investigated the effect of the degree of subcooling and the amount of
cyclopentane on the formation of hydrate in 3 wt% NaCl. The experimental study on
thermodynamics, kinetics, and the purity of the water recovered from the hydrates were
conducted. The results showed that the subcooling of 5.6 K had faster kinetics of hydrate
formation and better purification of the water. Xu et al. [33] performed the cyclopentane hydrate
formation for desalination at various subcooling for aqueous solutions with different salinities
at atmosphere pressure. They applied a three-step separation method, including gravitational
separation, filtration, and a washing step resulting in a desalination efficiency of 81%. Li et al.
3

[34] utilized separated graphite particles to promote the cyclopentane hydrate formation rate for
desalination. The hydrate formation rate of 32.5% in 5 hours was achieved by using 1.6 μm
[35-36]
diameter of graphite. Han et al. adopted the post-treatment methods, namely washing,
centrifuging, and sweating, to improve salt removal efficiency when hydrate-based desalination
technology was used to obtain fresh water. The results indicated that centrifuging leads to the
highest salt removal efficiency of 96%. While utilizing CP as the hydrate former has been
Accepted Manuscript
experimentally proven to desalinate saline water, an inherent challenge in CP-hydrate research
is to develop in-situ characterization of the kinetics of CP-hydrate formation. This is because
unlike gaseous phase hydrate formers, pressure drop cannot be obtained during the formation
of CP hydrate at atmospheric pressure. In many studies, the water conversion is quantified by
measuring the amount of water recovered from hydrate crystals isolated after hydrate formation
[32-33, 37].
for a certain period of time (e.g. 1 hr, 8 hr or 12 hrs) and upon the evaporation of CP
The rate of hydrate growth has also been inferred from the temperature profiles during hydrate
formation, whereby the duration and amplitude of exothermic signals were used to infer the
extent of hydrate growth [30, 32]. However, direct measurement of the rate of hydrate growth is
still an on-going research gap, which needs further investigation.
Cha and Seol[38] presented the utilization of CO2 and cyclopentane as the hydrate formers
to increase the hydrate formation temperature for the desalination of high salinity produced
water. The study demonstrated that the upper limit temperature of CO 2 and cyclopentane mixed
hydrate reached 16 oC, and the hydrate formation rate was 22 times higher than that of the
simple CO2. Such mild hydrate formation condition indicated that the energy efficiency of
HyDesal process can be improved significantly by using a binary mixture of carbon dioxide
[39-40]
and cyclopentane. Cai et al. conducted the clathrate hydrate formation of cyclopentane
and methane binary mixtures in fresh water and brine solutions. They found out that the hydrate
formation rate in salt water was 2~3 times slower than that in fresh water when the subcooling
[41]
degree was less than 4 K. Zheng et al. measured the thermodynamic data of cyclopentane
4

as a co-guest on CO2 hydrate formation and dissociation for desalination. The results inferred
that the CO2-cyclopentane guest strengthened the hydrate stability, which enabled moderate
hydrate phase equilibrium conditions for hydrated-based desalination. As evident from various
research, cyclopentane hydrate can be formed at a mild condition and could improve the hydrate
formation rate as a co-guest with the other hydrate guests.
There are many literatures focusing on the experimental studies on cyclopentane hydrate
Accepted Manuscript
formation for desalination. However, the research of CP-based HyDesal process from the
process system aspect is rare. In addition, although cyclopentane hydrate formation condition
is milder than that of propane, the energy efficiency of HyDesal process using cyclopentane as
the hydrate former can further be improved by utilizing LNG cold energy[42-44]. In this study,
we present an energetic and techno-economic evaluation of cyclopentane hydrate-based
desalination process with LNG cold energy utilization (ColdEn-HyDesal) to quantify the
improvement in energetic and techno-economic performance. Firstly, the process is designed
and built by using the heat exchanger network proposed in the previous work[24]. Then, the
specific energy consumption and fresh water production are obtained and compared with the
ones using propane in the previous work[24]. Later, the exergy analysis is adopted on the
ColdEn-HyDesal process to show the direction of future improvement. Afterward, the techno-
economic evaluation is applied on the ColdEn-HyDesal process using CP as the hydrate former.
Finally, the effects of the water recovery rate, hydrate formation temperature, and heating
seawater pressure on specific energy consumption, water production, exergy efficiency, and
cost are studied.
2. Process Design
2.1. Concept of the ColdEn-HyDesal Process Using Cyclopentane
Cyclopentane is a promising hydrate former for hydrate-based desalination due to its mild
hydrate formation condition. However, the external refrigeration cycle is still needed to keep

the formation reactor at around 7 oC if LNG cold energy is not utilized. The schematic diagram
of the ColdEn-HyDesal process using cyclopentane as the hydrate former is illustrated in
Figure 1. LNG cold energy is utilized to cool the cyclopentane and seawater to the reaction
temperature in the hydrate reactor, which can significantly reduce the energy consumption of
the desalination process by replacing the refrigeration cycle.
Cyclopentane can be enclathrated by water molecules to form sII hydrate at atmosphere
Accepted Manuscript
pressure. The formula of cyclopentane hydrate formation is shown in Equation (1):
C5 H10 +17 H 2O → C5 H10 ( H 2O)17 (1)
As seen from Equation (1), cyclopentane hydrate has a similar structure to propane hydrate,
which also has a hydration number of 17. The reaction heat of cyclopentane hydrate is -115.4
kJ/mole[45].
The cyclopentane hydrate can be dissociated with heat stimulation. The dissociation
formula of cyclopentane hydrate is shown in Equation (2):
C5 H10 ( H 2O)17 → C5 H10 +17 H 2O (2)
After dissociation, one mole of cyclopentane hydrate can produce 17 moles of fresh water.
The dissociation heat of cyclopentane hydrate is 115.4 kJ/mole based on experimental data [45].
The hydrate equilibrium curve of cyclopentane in seawater is calculated by Multiflash ®, as
illustrated in Figure 2. The main advantage of cyclopentane based HyDesal is that the hydrate
formation pressure can be lowered to the atmospheric pressure with a relatively high formation
temperature. Thus, the cyclopentane hydrate formation pressure is selected as 0.101 MPa in this
work. The subcooling degree is required to increase the hydrate formation rate. Here the
cyclopentane hydrate formation condition is selected as 0.101 MPa, 277.15 K, whereas the
dissociation condition is selected as 0.101 MPa, 283.15 K with heat stimulation.
2.2. Simulation Assumptions and Parameters

In this section, the simulation assumptions and parameters applied are presented. Aspen
HYSYS V9.0 is used to simulate the ColdEn-HyDesal process. In addition, the Peng-Robinson
equation of state is used to calculate the thermodynamic properties of the components. In order
to simulate CP hydrate in HYSYS, a hypothetical component in HYSYS is defined by providing
essential physical properties as shown in Table 1. As the experimental data for the heat capacity
of cyclopentane hydrate is not available in the published literature, we approximated the data
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with the other sII hydrates, namely tetrahydrofuran (THF) and propane, which were available
in the literature[46-47].
The following assumptions are proposed as the basis of the process design and simulation
performed in the current work:
(1) The heat exchanger network in this study is the same as the one in our previous work[24]
where propane was applied as the hydrate former.
(2) The water recovery rate is 10% in one hour.
(3) The dissociation conversion rate is 100%.
(4) The pressure drop in the heat exchanger is 5 kPa.
(5) The adiabatic efficiency of the pump and compressor is 75%.
(6) The outlet temperature of natural gas (NG) from the process is higher than 288.15 K.
(7) The inlet and outlet temperatures of the coolant in the hydrate formation reactor is 266.15
K and 273.15 K, respectively.
(8) The calculation basis of this study is the LNG flow rate of 1000 kg/h, which is the same
basis in the previous work [24].
(9) The stoichiometric flow rate ratio of cyclopentane and water is 1 kmole/h to 17
kmole/h, as shown in Equation (1). In order to ensure that the amount of cyclopentane is
sufficient in the formation reactor, CP flow rate is increased by 10% from the stoichiometric
ratio.

2.3. ColdEn-HyDesal Process Description
To compare the current work with the ColdEn-HyDesal process using propane as the
hydrate former[24], the same heat exchanger network is used in this study. However, the
flowsheet of the ColdEn-HyDesal process using cyclopentane as the hydrate former is different
from the one using propane[24]. That is because at the operating conditions of hydrate formation
and dissociation reactors, cyclopentane is in the liquid phase, while propane is in the gaseous
Accepted Manuscript
phase, making the hydrate separation section totally distinctive. The flowsheet of the ColdEn-
HyDesal process using cyclopentane is illustrated in Figure 3. Cyclopentane (CP1) is cooled to
277.15 K by LNG in HEX-2 and then enters the reactor to form hydrate with the seawater
(SW10). The feed seawater (SW1) is firstly pumped, and then pre-cooled by LNG (LNG7) and
the recycled cyclopentane from S-1 and S-3 in HEX-7 and HEX-6, respectively. Subsequently,
seawater (SW4) is split into two sections, one section (SW5) is cooled by the pure water (PW2)
in HEX-4, the other one (SW7) is cooled by the brine (B1) from the vapour-liquid-solid
separator (S-2) in HEX-5. Then the combined seawater stream (SW9) is cooled to 277.15 K
by LNG (LNG4) in HEX-3 and flows into the hydrate formation reactor.
In the hydrate formation reactor, a part of cyclopentane and seawater form sII hydrate at the
formation condition. The formation of CP hydrate releases heat, which should be removed by
the coolant to maintain the formation temperature. The coolant (C2) is cooled by LNG in HEX-
1 and then flows into the formation reactor to remove the heat. After the hydrate formation, the
hydrates with the unreacted cyclopentane and seawater goes into a three-phase separator (S-1),
in which the unreacted cyclopentane (CP3) is separated, and then mixed with the cyclopentane
dissociated from CP hydrate (CP4) for recycling. The hydrate slurry and brine enters the liquid-
solid separator (S-2) for separation. After the separation, a washing column is used to wash the
hydrate crystals if the separation of the hydrate crystals and brine is not clear. The separated
brine (B1) with low temperature goes back to HEX-5 to pre-cool a part of seawater.
Subsequently, the hydrate is dissociated in the dissociation reactor with heat stimulation by
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exchanging heat with the seawater (SW12), yielding a stream (PW1) comprising CP entrapped
within hydrates (CP4) and pure water (PW2). Then the pure water (PW2) is separated from S-
3 and provides its cold energy to pre-cool seawater in HEX-4. In addition, LNG provides its
cold energy in HEX-1, HEX-2, HEX-3, and HEX-7 successively.
3. Process Performance Indexes
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3.1. Specific Energy Consumption
Specific energy consumption is the key indicator to appraise the energy performance of the
desalination process, which is defined as the ratio of the total energy consumption to the
volumetric flow rate of the produced pure water, as shown in Equation (3):
Wtotal
SEC = (3)
VPW
Where SEC is the specific energy consumption (in kWh/m3), Wtotal is the total energy
consumption (in kW) and VPW is the volumetric flow rate of the produced pure water (in
m3/h).
3.2. Water Recovery Rate
Water recovery rate is an index representing the amount of pure water recoverable from the
desalination process at the given seawater flow rate. In this work, it is assumed that the hydrate
crystal is 100% recovered from the liquid-solid separator (S-2). Thus, the water recovery rate
of the ColdEn-HyDesal process is the ratio of the volumetric flow rate of the pure water (PW3)
to the feed seawater (SW1), as given in Equation (4):
VPW
WRR = 100 (4)
VSW
Where WRR is the water recovery rate. VPW is the volumetric flow rate of pure water,
m3/h. VSW is the volumetric flow rate of feed seawater, m3/h.

3.3. Exergy Efficiency
Exergy can be defined as the magnitude of the minimum theoretical work input required to
bring the system from the dead state to the given state [48]. Exergy efficiency of the ColdEn-
HyDesal process is the ratio of the utilized LNG cold exergy to the input LNG cold exergy. In
any non-ideal process, there are exergy destructions occurring in the equipment. Thus,
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investigation of the exergy efficiency and destruction on the ColdEn-HyDesal process is
essential to provide a deep insight of the process and give the direction of the future energy
improvement. The specific exergy is defined in Equation (5):
ex = (h − h0 ) − T0 (s − s0 ) (5)
Where ex is the specific exergy, kJ/mole. h is the specific enthalpy, kJ/mole. s is the
specific entropy, kJ/(mole-K). The subscription 0 refers to the dead state. Here 298.15 K and
0.101325 MPa is chosen as the dead state for exergy calculation.
The exergy efficiency of the ColdEn-HyDesal process using cyclopentane as the hydrate
former is given in Equation (6):
ex = Eu (6)
Ei
Where η is the efficiency. E refers to the exergy, kJ. The subscripts ex, u, and i refer to
exergy, utilized, and input respectively.
The exergy destructions of the heat exchangers related to LNG cold energy are
investigated, as shown in Equation (7):
Ed =  Ei −  Eo (7)
Where the subscripts d, i, o refer to destruction, input, and output respectively.
3.4. Techno-economic Performance
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Techno-economic performance of the ColdEn-HyDesal process using cyclopentane as
hydrate former is the key index to make the process commercialized. In this section, the fixed
capital investment (FCI), the sum of bare module cost of different equipment, is investigated,
as shown in Equation (8)[49]:
FCI =  CBM (8)
Where FCI refers to fixed capital investment. CBM is the bare module cost of equipment in
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the process, as given in Equation (9)[49]:
CBM = C 0p FBM (9)
Where Cp0 is the purchased cost of the equipment, which can be illustrated as the form in
Equation (10):
log10 C 0p = K1 + K 2 log10 ( A) + K3[log10 ( A)]2 (10)
Where A is the capacity or size parameter for the equipment. The data for K1, K2, and K3
can be found in reference[49].
In Equation (9), FBM is the bare module factor, which can be described in Equation (11):
FBM = B1 + B2 FM FP (11)
Where B1, B2 are the constants for bare module factor. FM is the material factor. The
values of B1, B2, and FM can be found in reference[49].
In Equation (11), FP refers to pressure factor, which reflects the effect of pressure on the
cost. For the thickness of process vessels larger than 0.0063 m, pressure factor is given as
Equation (12):
PD
+ 0.00315
2(850 − 0.6 P)
FP,vessel = (12)
0.0063
If FP,vessel is less than 1 (corresponding to the thickness is smaller than 0.0063 m), then
FP,vessel = 1. In this study, as the operating pressure is atmospheric pressure, the thickness is
less than 0.0063 m, hence the pressure correction factor is taken as 1.

11

For other process equipment, pressure factor is described in Equation (13):
log10 FP = C1 + C2 log10 P + C3 (log10 P)2 (13)
Where P is the bar gauge, D is the diameter. C1, C2, C3 are the constants for pressure
factor, which can be found in reference[49].
4. Results and Comparison
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4.1. Simulation Results
In this section, the simulation results of the ColdEn-HyDesal process using cyclopentane as
the hydrate former are presented. The water recovery rate is assumed to be 10% in one hour.
The specific energy consumption (SEC), energy consumption of four pumps, and volumetric
flow rate of pure water are shown in Table 2. As we can see, the specific energy consumption
of the CP-based ColdEn-HyDesal process is 0.35 kWh/m3, which is much lower than the
specific energy consumption of the other desalination technologies [23]. Moreover, the
volumetric flow rate of produced water by the process is 0.75 m3/h based on the cold energy
contained in 1000 kg/h of LNG.
It can be found out that the energy consumption (W-3) of the heating seawater pump (P-3)
is 0.16 kW, which contributes 61.53% of the total power to supply the pressure of the heating
seawater at 200 kPa, as shown in Figure 4. The specific energy consumption and the total power
can be further reduced when the pressure is reduced. The energy consumption (W-1) of the feed
seawater pump (P-1) is 0.05 kW only contributing 19.23% of the total power. The reason is that
the hydrate formation pressure decreased to atmospheric pressure by using cyclopentane,
therefore the pressure rise of P-1 is very small. In addition, the cyclopentane recycling pump
only shares 3.84% of the total power, which indicates that the recycle of cyclopentane has a
very small influence on the total power.
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The reason why the energy consumption of P-3 is one order of magnitude higher than others
is that the low hydrate formation pressure leading to small energy consumptions of P-1 and P-
4. Since the pressure increase of P-1 and P-4 only need to overcome the pressure drop of the
heat exchangers, the energy consumptions of P-1 and P-4 can be reduced significantly. It can
be found that the energy consumption of P-3 is close to the energy consumption of P-1 and C-
1 in the reference[24] when the hydrate formation pressure is 400 kPa. Thus, the benefit by using
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CP as hydrate former is the reduction in the energy consumption of the feed seawater pump and
the CP recycling pump. In addition, it should be noted that the seawater (used for heating)
pressure could be decreased which would reduce its contribution to the total energy
consumption, as discussed in Section 5.3.
4.2. Comparison of Cyclopentane and Propane as Hydrate Former
The comparison of cyclopentane and propane as the hydrate former in the ColdEn-HyDesal
process is conducted in this section. Figure 5 compares the process performance of both
processes in terms of the equipment power consumption, total power, volumetric flow rate of
pure water, and SEC.
The comparison of the energy consumptions of pumps and compressor is illustrated in
Figure 5 (a). W-1 represents the energy consumption of the feed seawater pump. The energy
consumption of W-1 is 0.05 kW when cyclopentane is used as the hydrate former, while that is
0.38 kW when propane is adopted. That is because cyclopentane can form hydrate at
atmospheric pressure and the pressure rise only needs to overcome the pressure drops in heat
exchangers. However, seawater is pumped to 400 kPa to form hydrate in the reference [24]. In
addition, the energy consumption of the coolant pump (W-2) is 0.04 kW in this study, which is
around 50% lower than that of using propane as the hydrate former. There are two reasons
which accounted for the difference: firstly, the water recovery rate of cyclopentane hydrate is
only 10%, while that of propane hydrate is 40%; secondly, the formation heat of cyclopentane
13

hydrate is also lower than that of propane hydrate. Thus, the removal of the reaction heat in this
study is significantly lower than that of using propane resulting a smaller recycle flow rate of
the coolant, which leads to the lower energy consumption of W-2. Furthermore, the energy
consumption of heating seawater pump (W-3) in this study is 0.16 kW, about 50% lower than
that of using propane which is 0.31 kW. The reason is that less hydrate is produced in this study
when compares to that of using propane, which causes a smaller heating capacity in the
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dissociation reactor. Moreover, the pump is used to recycle cyclopentane in this study, while
the compressor is used to recycle propane in reference[24], resulting in significant differences in
the power consumption in the former recycling equipment (W-4). The energy consumption of
W-4 is 0.01 kW in this study, around 97% lower than that consumed in propane recycling
compressor which is 0.32 kW. As a consequence, the total power consumption of using
cyclopentane is 0.26 kW, nearly 76% lower than that of using propane which is 1.09 kW, as
shown in Figure 5 (b).
The volumetric flow rate of pure water in this study is 0.75 m3, almost 42% lower than that
of using propane which is 1.30 m3, as illustrated in Figure 5 (c). That is because the water
recovery rate of cyclopentane hydrate is only 10% in one hour, while propane hydrate can reach
40% in one hour.
As seen from Figure 5 (d), the specific energy consumption (SEC) using cyclopentane as
hydrate former is 0.35 kWh/m3, while that applying propane is 0.84 kWh/m3, which indicates
that the SEC of using cyclopentane is around 58% lower than that of using propane. Although
the volumetric flow rate of pure water in reference[24] is higher than that in this study, the effect
of lower total power consumption has more influences on the SEC.
According to the comparison results, using cyclopentane to replace propane as the hydrate
former in the ColdEn-HyDesal process can reduce the total power and SEC significantly.
However, the pure water production when using cyclopentane as hydrate former is lower than
that of using propane due to its low water recovery rate. On the other hand, it also indicates that
14

increasing the water recovery rate and the kinetics of cyclopentane hydrate in the future will
aid in increasing the water production and decrease SEC at a system level. Apart from reducing
the operation temperature during hydrate formation which has been well-known as a mean to
improve hydrate formation kinetics[32-33, 37], various process configuration has been proposed to
[33]
enhance the kinetics of CP-hydrate formation. For example, Xu et al. demonstrated that
increasing agitation speed from 300 rpm to 600 rpm can result in almost five-fold increase in
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[37].
water conversion from 3.92% to 18.93%, which corroborated the results from Lv et al.
Further, the group also demonstrated that the application of spray injection to deliver CP
droplets (<5 μm) can further increase the water conversion from 18.93% to 34.98%. These
configuration sheds light on further research in enhancing mass transfer as a mean to improve
the kinetics of CP-hydrate formation.
4.3. Exergy Analysis
The total inlet exergy of LNG to the ColdEn-HyDesal process is 142 kW, according to the
calculation based on Equation (5). The exergy analysis results are given in Table 3. It can be
seen that the total exergy destruction is 126.81 kW, in which the exergy destruction of HEX-1
contributes 56.10%. Moreover, the exergy destruction of HEX-3 is 51.88 kW which also
contributes to 40.91% of the total exergy destruction. According to Equation (6), the exergy
efficiency of the ColdEn-HyDesal process using cyclopentane as hydrate former is 10.71%. It
indicates that nearly 90% of the LNG exergy is wasted during the heat transfer process in the
ColdEn-HyDesal process.
The heat transfer curves between LNG and the hot streams can reveal the reason for the low
exergy efficiency, as illustrated in Figure 6. The temperature difference between LNG and the
coolant in HEX-1 is huge since the coolant is cooled from 273.15 K to 266.15 K, while LNG
is heated from 113 K to 180 K, which makes the gap between the coolant and LNG heat transfer
curve enormous. In addition, LNG is regasified from liquid phase to gas phase during the heat
transfer process to cool the cyclopentane and feed seawater in HEX-2 and HEX-3. The total
15

exergy destruction of HEX-2 and HEX-3 is 55.22 kW. Thus, the broad gap between the hot
streams and cold stream causes the large exergy destruction and low exergy efficiency in the
ColdEn-HyDesal process. It should be noted that improving the heat transfer performance
between LNG and hot streams is the future research direction to increase the pure water
production and decrease the specific energy consumption.
Accepted Manuscript
4.4. Economic Analysis
In this section, the economic analysis is based on the LNG flow rate of 100 tonne/h, which
is 100 times scale-up version of the LNG flow rate used in the previous sections to make it
closer to the operation condition of a real LNG regasification terminal. The FCI of the specific
equipment in the ColdEn-HyDesal process is shown in Figure 7 and Table 4. As shown in Table
4, the total FCI of the ColdEn-HyDesal process using cyclopentane as the hydrate former is
$6,113,751.
The heat exchangers are the main contributor to the total FCI, which is estimated to be
$4,144,440, accounting for 67.79% of the total FCI. Among the heat exchangers, the FCI of
HEX-5 is the largest, reaching $1,808,575, as illustrated in Figure 7 (b). That is because the
heat load of HEX-5 is 9505 kW and the log mean temperature difference is 12.24 oC, resulting
in a huge heat transfer area. The heat exchanger with the second highest FCI is HEX-3, which
is estimated at $1,219,696. It should be noted that the heat load of HEX-3 is the largest among
the seven heat exchangers, reaching 13408 kW. However, the log mean temperature difference
between LNG and seawater is 30.50 oC, resulting in a smaller heat transfer area than that of
HEX-5. Similarly, while the heat load of HEX-1 is comparable to HEX-3 and HEX-5, the
temperature difference is the largest in HEX-1 (as shown in Figure 6), necessitating a very small
heat transfer area. Thus, the FCI of HEX-1 is several times smaller than that of HEX-3 and
HEX-5.
16

Besides heat exchangers, the FCI of reactors is $1,701,118, which contributes to 27.82% of
the total FCI. The FCI of the hydrate formation reactor is $971,127 and that of the dissociator
is $729,991. Moreover, the FCI of pumps and separators has very small impacts on the total
FCI. The reason is that the cyclopentane hydrate can form at the atmospheric pressure without
the requirement to increase the cyclopentane and seawater to the high pressure.
Accepted Manuscript
5. Sensitivity Study
5.1. Effects of Water Recovery Rate on Process Performance
The water recovery rate of cyclopentane hydrate has a significant influence on the
performance of the ColdEn-HyDesal process. In the previous section, the water recovery rate
is selected as 10% in one hour. The effect of the water recovery rate on the specific energy
consumption (SEC) is illustrated in Figure 8 (a). In this section, the fraction of CP converted to
hydrate increases from 10% to 40%. As the cold energy available remains constant, the flow
rate of feed seawater and CP decreased at higher water recovery rate. The other simulation
parameters keep constant as shown in section 2.2. As the water recovery rate increases from
10% to 40%, we observe that the SEC decreases from 0.35 kWh/m 3 to 0.29 kWh/m3, around
18.12% decrease. The reason is that the increase of the water recovery rate necessitates the
formation of more cyclopentane hydrate in the reactor to enable a higher volumetric flow rate
of pure water, as shown in Figure 8 (b). It can be seen that the volumetric flow rate of pure
water increases from 0.75 m3/h to 1.41 m3/h, resulting 89.45% of increment, when the water
recovery rate increases from 10% to 40%. As mentioned in Section 4.1, the energy consumption
of the heating seawater pump contributes 60.55% of the total energy consumption. The increase
of water recovery rate will increase the energy consumption of the heating seawater pump due
to the increase of dissociation heat. However, the increase of volumetric flow rate of pure water
surpasses the effect of the total energy consumption rising leading to the decrease of SEC,
17

however, the decreasing amplitude of SEC is smaller than the increasing amplitude of
volumetric flow rate of pure water.
The effect of the water recovery rate on the exergy efficiency is shown in Figure 8 (c). With
the increase of the water recovery rate from 10% to 40%, the exergy efficiency increases from
10.71% to 13.44%. It is because the increase of the water recovery rate will increase the exergy
destruction in HEX-1, while decrease the exergy destruction in HEX-3 and HEX-7. The exergy
Accepted Manuscript
destruction of HEX-1 increases from 71.14 kW to 104.5 kW with an increase of 33.36 kW.
However, the total exergy destruction of HEX-3 and HEX-7 decreases from 55.22 kW to 17.34
kW with a decrease of 37.88 kW. These factors combine to increase the exergy efficiency when
the water recovery rate increases.
Figure 8 (d) illustrates the effect of the water recovery rate on FCI. It should be noted that
the FCI value in Section 5 is also based on 100 tonne/h of LNG flow rate, which is the same
flow rate in Section 4.4. It can be seen that the FCI decreases from $6,113,751 to $4,525,631
with a decreasing ratio of 25.98% when the water recovery rate increase from 10% to 40%. The
reason is that the increase of the water recovery rate will decrease the flow rate of the
cyclopentane and feed seawater which results in a smaller heat load of the heat exchangers and
smaller heat transfer area. As mentioned in Section 4.4, the FCI of heat exchangers contributes
the largest ratio of the total FCI. Thus, the FCI can decrease significantly when the water
recovery rate increases.
According to the above discussions, the increase of the water recovery rate of the
cyclopentane hydrate can decrease the SEC and FCI, and increase the volumetric flow rate of
pure water and exergy efficiency of the ColdEn-HyDesal process.
5.2. Effects of Hydrate Formation Temperature on Process Performance
The effects of hydrate formation temperature on specific energy consumption (SEC), the
volumetric flow rate of pure water, exergy efficiency, and fixed capital investment (FCI) are
18

investigated, as illustrated in Figure 9. The hydrate formation temperature is 277.15 K for the
previous sections. From Figure 9 (a), it can be seen that the SEC increases minimally from 0.35
kWh/m3 to 0.36 kWh/m3 with an increasing ratio of 2.86% when the hydrate formation
temperature decreases from 277.15 K to 273.15 K. The lower hydrate formation temperature
needs more cooling capacity to cool the cyclopentane and feed seawater from the inlet
temperature to hydrate formation temperature, which results in smaller flow rates of the
Accepted Manuscript
cyclopentane and feed seawater based on the same available LNG cold energy. Furthermore,
the decrease of the hydrate formation temperature leads to the increase of the dissociation heat
load since the dissociation temperature still keeps at 283.15 K. Thus, the SEC of the ColdEm-
HyDesal process increases slightly with the decrease of the hydrate formation temperature.
Figure 9 (b) illustrates the variation of the volumetric flow rate of pure water with the change
of the hydrate formation temperature. It can be found out that the volumetric flow rate of pure
water decreases from 0.75 m3/h to 0.74 m3/h when the hydrate formation temperature decreases
from 277.15 K to 273.15 K. The reason is that the specific cooling requirements of the
cyclopentane and feed seawater increase, and the same amount of LNG cold energy can cool
less flow rate of the cyclopentane and feed seawater. Thus, the amount of the cyclopentane
hydrate formed in the reactor decreases which causes less flow rate of pure water after the
dissociation.
The effect of the hydrate formation temperature on the exergy efficiency is depicted in
Figure 9 (c). It can be seen that the exergy efficiency increases from 10.71% to 12.08% with an
increasing ratio of 12.79% when the hydrate formation temperature decreases from 277.15 K
to 273.15 K. That is because the exergy destructions of HEX-1, HEX-3, and HEX-7 decrease
with the smaller temperature difference due to the decrease of the hydrate formation
temperature.
The hydrate formation temperature affects the FCI of the ColdEn-HyDesal process
significantly, as shown in Figure 9 (d). The FCI increases from $6,113,751 to $9,559,668 with
19

an increasing ratio of 56.36% when the hydrate formation temperature decreases from 277.15
K to 273.15 K. The reason is that the heat load of the heat exchangers increases with the
decrease of the hydrate formation temperature resulting in the increase of heat transfer area.
In conclusion, the hydrate formation temperature has the greatest impact of the FCI of the
process, while does not have significant influence over the SEC and volumetric flow rate of
pure water. However, one point not considered in this study was the effect of temperature on
Accepted Manuscript
the kinetics of CP-hydrate formation. While it is well known that higher degree of subcooling
can enhance the kinetics of CP-hydrate generation, the kinetic information is limited and shall
be further examined in the future research.
5.3. Effects of Heating Seawater Pressure on Process Performance
As the major contributor to power consumption in the current system is the pressure
generation units, the pressure of the heating seawater is expected to affect the energy
consumption of P-3 significantly. As shown in Table 2, the energy consumption of P-3
contributes 60.55% of the total energy consumption in this study. Thus, the effects of the
heating seawater pressure between 140 kPa to 200 kPa on the process performance are
conducted. The effect of the heating seawater pressure on SEC is shown in Figure 10 (a). The
SEC reduces from 0.35 kWh/m3 to 0.22 kWh/m3, a reduction of 36.81%, was observed when
the heating seawater pressure decreased from 200 kPa to 140 kPa. That is because of the energy
consumption of P-3 declines with the decrease of the heating seawater pressure. In addition, the
volumetric flow rate of pure water and exergy efficiency remain unchanged when the heating
seawater pressure varies, as illustrated in Figure 10 (b) and (c). Furthermore, the heating
seawater pressure has a slight impact on FCI, as shown in Figure 10 (d). The FCI decreases
from $6,113,751 to $6,106,867 when the heating seawater pressure decreases from 200 kPa to
140 kPa. The reason is that the heating seawater pressure only affects the FCI of the dissociation
reactor.
20

6. Conclusion
To improve the energy performance of the ColdEn-HyDesal process, cyclopentane was
adopted as the hydrate former due to its mild hydrate formation condition. The results showed
that the specific energy consumption of the ColdEn-HyDesal process using cyclopentane was
0.35 kWh/m3, which was 58% lower than that of using propane. However, the volumetric flow
rate of fresh water was 0.75 m3/h, which was 42% lower than that using propane as hydrate
Accepted Manuscript
former. It was because of the low water recovery rate of the cyclopentane hydrate, which was
10% in one hour. The volumetric flow rate of fresh water could be increased to 1.41 m 3/h
surpassing the value of 1.30 m3/h using propane when the water recovery rate of the
cyclopentane hydrate reached 40% in one hour. Moreover, the exergy efficiency of the ColdEn-
HyDesal process using cyclopentane was 10.71%, which indicated that further improvement of
the heat transfer performance between LNG and hot streams was required. Furthermore, the
fixed capital cost (FCI) of the process was evaluated. The results showed that the FCI of the
process was $6,113,751 when the LNG flow rate was 100 tonne/h. Finally, the effects of the
water recovery rate, hydrate formation temperature, and heating seawater pressure on SEC,
volumetric flow rate of fresh water, exergy efficiency, and FCI were also investigated. The
sensitive study results indicated that the water recovery rate affected the SEC, volumetric flow
rate of fresh water, exergy efficiency, and FCI significantly. The hydrate formation temperature
had an obvious impact on FCI due to the larger area required to cool the reactants, while had a
minimal impact on SEC, volumetric flow rate, and exergy efficiency. The heating seawater
pressure influenced SEC dramatically due to the energy consumption of P-3 contributed the
largest of the total energy consumption. In conclusion, using cyclopentane as hydrate former
could improve the energy efficiency of the ColdEn-HyDesal process remarkably. We also
identified that improving the water recovery rate of cyclopentane hydrate in the future
21

experimental study is the key technology breakthrough to enable fresh water production from
CP hydrate based desalination process.
Acknowledgements
The authors would like to acknowledge funding supported by “the Fundamental Research
Funds for the Central Universities” (No. 19CX02011A), the China University of Petroleum
(East China) (No. 05Y18150010) and the Energy Innovation Research Programme (EIRP,
Accepted Manuscript
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 (NRF).
Received: ((will be filled in by the editorial staff))

Revised: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
Nomenclature
Nomenclature
Symbols
V Volumetric flow rate [m3/h]
W Energy consumption [kW]
Acronyms
B Brine
C Coolant/Compressor
CP Cyclopentane
FCI Fixed capital investment
H Hydrate
22

HEX Heat exchanger
LNG Liquefied natural gas
P Pump
PW Pure water
SEC Specific energy consumption
SW Seawater
Accepted Manuscript
WRR Water recovery rate
Greek symbol
η Exergy efficiency
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24

Accepted Manuscript
Figure 1. The schematic diagram of the ColdEn-HyDesal process using cyclopentane as the
hydrate former
25

Accepted Manuscript
Figure 2. The hydrate equilibrium curve of cyclopentane in water with 3.5%wt NaCl
26

Accepted Manuscript
Figure 3. The flowsheet of the ColdEn-HyDesal process using cyclopentane as the hydrate
former
Figure 4. The percentage of energy consumption by the four pumps
27

Accepted Manuscript
Figure 5. Comparison results of cyclopentane and propane[24] as the hydrate former in
ColdEn-HyDesal process
Figure 6. Heat transfer curves of LNG and hot streams
28

Accepted Manuscript
Figure 7. FCI of the specific equipment: (a) Pumps; (b) Heat Exchangers; (c) Separators; (d)
Reactors
29

Accepted Manuscript
Figure 8. The effects of the water recovery rate on: (a) Specific Energy Consumption (SEC),
(b) Volumetric flow rate (VFR); (c) Exergy efficiency, (d) Fixed Capital Investment (FCI)
30

Accepted Manuscript
Figure 9. The effects of hydrate formation temperature on: (a) SEC, (b) Volumetric flow rate;
(c) Exergy efficiency, (d) FCI
31

Accepted Manuscript
Figure 10. The effects of heating seawater pressure on: (a) SEC, (b) Volumetric flow rate; (c)
Exergy efficiency, (d) FCI
32

Table 1. The physical properties of cyclopentane hydrate
Item Number
Molecular weight (kg/kmole) 376.39
Heat of formation (kJ/kmole) at 25℃ -5.098×106
Heat capacity (kJ/kmole-K)* -124.33+3.2592T+2×10-6T2
-4×10-9T3
Accepted Manuscript
* Approximation from the heat capacities of THF and propane hydrate.
Table 2. SEC and volumetric flow rate of pure water
Item Value
W-1 (kW) 0.05
W-2 (kW) 0.04
W-3 (kW) 0.16
W-4 (kW) 0.01
Total power (kW) 0.26
Volumetric flow rate of PW1 (m3/h) 0.75
SEC (kWh/m3) 0.35
Table 3. Exergy destruction of heat exchangers related to LNG
Item Exergy destruction (kW) Exergy destruction percentage
HEX-1 71.14 56.10%
HEX-2 3.34 2.63%
HEX-3 51.88 40.91%
HEX-7 0.45 0.36%
Total 126.81 100%
33

Table 4. Fixed capital investment based on 100 tonne/h of LNG flow rate
Equipment FCI ($) FCI percentage
Pumps 76,546 1.25%
Heat exchangers 4,144,440 67.79%
Separators 191,647 3.13%
Reactors 1,701,118 27.82%
Accepted Manuscript
Total 6,113,751 100.00%
34

This paper proposes a cyclopentane hydrate-based desalination process with LNG cold energy
utilization. The specific energy consumption (SEC) of the proposed process is 0.35 kWh/m 3
of fresh water, which is 58% lower than that of using propane as hydrate former. Moreover,
the fixed capital investment of the process is $6,113,751 when the flow rate of LNG is 100
tonne/h.
Keywords: gas hydrates, LNG cold energy, desalination, cyclopentane, hydrate based
desalination
Tianbiao He[a]*, Zheng Rong Chong[b], Ponnivalavan Babu[b], Praveen Linga[b]*
Title: Techno-economic Evaluation of Cyclopentane Hydrate-Based Desalination with
Accepted Manuscript
LNG Cold Energy Utilization
ToC figure ((Please choose one size: 55 mm broad × 50 mm high or 110 mm broad × 20 mm
high. Please do not use any other dimensions))
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To be cited as: Energy Technol. 10.1002/ente.201900212

Link to VoR: http://dx.doi.org/10.1002/ente.201900212

Techno-economic Evaluation of Cyclopentane Hydrate-Based Desalination with LNG

Tianbiao He[a]*, Zheng Rong Chong[b], Ponnivalavan Babu[b], Praveen Linga[b]*

[a] Dr. Tianbiao He

This article is protected by copyright. All rights reserved.

promising technologies to solve the pressing issue of freshwater scarcity[1]. Desalination

process, and clathrate hydrate-based process[2]. The clathrate hydrate-based desalination

and freshwater using the method of pressure reduction or heat stimulation.

common hydrate formers applied on hydrate-based desalination process. Moreover, some

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atmosphere pressure[28-30]. Cyclopentane hydrate formation and dissociation performance in

cyclopentane mixture containing three impurities in water by adopting a pressure-search

cyclopentane on the formation of hydrate in 3 wt% NaCl. The experimental study on

at atmosphere pressure. They applied a three-step separation method, including gravitational

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is to develop in-situ characterization of the kinetics of CP-hydrate formation. This is because

of CP hydrate at atmospheric pressure. In many studies, the water conversion is quantified by

still an on-going research gap, which needs further investigation.

This article is protected by copyright. All rights reserved.

formation rate as a co-guest with the other hydrate guests.

we present an energetic and techno-economic evaluation of cyclopentane hydrate-based

improvement in energetic and techno-economic performance. Firstly, the process is designed

cost are studied.

2.1. Concept of the ColdEn-HyDesal Process Using Cyclopentane

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of the ColdEn-HyDesal process using cyclopentane as the hydrate former is illustrated in

the desalination process by replacing the refrigeration cycle.

Cyclopentane can be enclathrated by water molecules to form sII hydrate at atmosphere

C5 H10 +17 H 2O → C5 H10 ( H 2O)17 (1)

formula of cyclopentane hydrate is shown in Equation (2):

C5 H10 ( H 2O)17 → C5 H10 +17 H 2O (2)

The hydrate equilibrium curve of cyclopentane in seawater is calculated by Multiflash ®, as

dissociation condition is selected as 0.101 MPa, 283.15 K with heat stimulation.

2.2. Simulation Assumptions and Parameters

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to simulate CP hydrate in HYSYS, a hypothetical component in HYSYS is defined by providing

performed in the current work:

where propane was applied as the hydrate former.

(2) The water recovery rate is 10% in one hour.

(3) The dissociation conversion rate is 100%.

(4) The pressure drop in the heat exchanger is 5 kPa.

(5) The adiabatic efficiency of the pump and compressor is 75%.

K and 273.15 K, respectively.

basis in the previous work [24].

This article is protected by copyright. All rights reserved.

2.3. ColdEn-HyDesal Process Description

HyDesal process using cyclopentane is illustrated in Figure 3. Cyclopentane (CP1) is cooled to

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cold energy in HEX-1, HEX-2, HEX-3, and HEX-7 successively.

3. Process Performance Indexes

3.2. Water Recovery Rate

to the feed seawater (SW1), as given in Equation (4):

m3/h. VSW is the volumetric flow rate of feed seawater, m3/h.

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3.3. Exergy Efficiency

improvement. The specific exergy is defined in Equation (5):

0.101325 MPa is chosen as the dead state for exergy calculation.

former is given in Equation (6):

exergy, utilized, and input respectively.

investigated, as shown in Equation (7):

Tianbiao He[a], Zheng Rong Chong[b], Ponnivalavan Babu[b], Praveen Linga[b]