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Article history: Energy and exergy analyses are reported of hydrogen production via an ocean thermal
Received 10 August 2012 energy conversion (OTEC) system coupled with a solar-enhanced proton exchange
Received in revised form membrane (PEM) electrolyzer. This system is composed of a turbine, an evaporator,
29 October 2012 a condenser, a pump, a solar collector and a PEM electrolyzer. Electricity is generated in the
Accepted 4 November 2012 turbine, which is used by the PEM electrolyzer to produce hydrogen. A simulation program
Available online 17 December 2012 using Matlab software is developed to model the PEM electrolyzer and OTEC system. The
simulation model for the PEM electrolyzer used in this study is validated with experimental
Keywords: data from the literature. The amount of hydrogen produced, the exergy destruction of each
Energy component and the overall system, and the exergy efficiency of the system are calculated.
Exergy To better understand the effect of various parameters on system performance, a para-
Hydrogen production metric analysis is carried out. The energy and exergy efficiencies of the integrated OTEC
OTEC system are 3.6% and 22.7% respectively, and the exergy efficiency of the PEM electrolyzer is
Water electrolysis about 56.5% while the amount of hydrogen produced by it is 1.2 kg/h.
Solar energy Crown Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All
rights reserved.
which boils a working fluid such as ammonia to generate Rabas et al. [14] studied a non-condensable gas removal
a vapour which turns the turbine to generate electricity, and system for a particular 10-MW hybrid power plant. More
then is condensed back into a liquid in a continuous process. recently, Kazim [15] proposed a hydrogen production cycle
Eighty percent of the energy the Earth receives from the sun is using ocean thermal energy, and Ikegamia et al. [7,16]
stored in the Earths oceans [1,2], and many regions of the proposed desalination using an integrated hybrid cycle and
world have access to this OTEC resource. OTEC can produce an open OTEC cycle.
fuels by using its product electricity to create hydrogen, which Energy analysis, which is based on the first law of ther-
can be used in hydrogen fueled cars as well as in the devel- modynamics, often does not provide a clear picture of ther-
opment of synthetic fuels. For a small city, millions of tons of modynamic efficiency and losses. Exergy is not subject to
CO2 are generated annually through fossil fuel use while with a conservation law, but is destroyed due to irreversibilities
OTEC the value is zero, during the operation of devices. OTEC during any process [17]. Exergy analysis overcomes such
has a potential to replace some fossil fuel use, perhaps via deficiencies and can help improve efficiency and sustain-
OTEC ships travelling the seas of the world. ability [18]. Exergy is a useful tool for determining the location,
An OTEC system utilizes low-grade energy and has low type and true magnitude of exergy losses, which appear in the
energy efficiency (about 3e5%). Therefore, achieving a high form of either exergy destruction or waste exergy emission
electricity generating capacity with OTEC requires the use of [19]. Therefore, exergy methods can assist in developing
large quantities of seawater and a correspondingly large strategies and guidelines for more effective use of energy
amount of pumping energy. These factors impact negatively resources and technologies. Sun et al. [20] report an optimi-
on the cost-effectiveness of this technology and OTEC is not zation design and exergy analysis of an organic Rankine cycle
commercially viable today. To improve the effectiveness and in ocean thermal energy conversion, and show that ammonia
economics of OTEC cycles, it is proposed that they being is a good working fluid for an ORC cycle in OTEC from a net
integrated with industrial operations so that, apart from power output point of view. Also, from an exergy viewpoint, it
generating electricity, they could be used for fresh water has been shown that a larger scale ORC in OTEC can justify the
production, air conditioning and refrigeration, cold water use of a heat exchanger with a higher effectiveness to
agriculture, aquaculture and mariculture, and hydrogen decrease the exhaust loss, which accounts for a large
production [1]. Potential markets for OTEC have been identi- proportion of the exergy loss of an ORC in an OTEC system [20].
fied, most of which are in Pacific Ocean, and about 50 coun- In this paper, a novel OTEC system equipped with a solar
tries are examining its implementation as a sustainable collector and PEM electrolysis to produce hydrogen is ther-
source of energy and fresh water, including India, Korea, modynamically modelled and assessed with energy and
Palau, Philippines, the U.S. and Papua New Guinea [3]. In 2001, exergy analyses. The primary objective is to improve under-
as a result of cooperation between Japan and India a 1-MW standing of this system. The following specific tasks are
OTEC plant was built in India [3], and others are planned to performed:
be constructed in the near future [4].
Considerable research has been directed to the develop- Model and simulate (using Matlab software) the integrated
ment of OTEC recently. Uehara [5e8] conducted numerous system.
theoretical and experimental studies on the major compo- Validate each part of the model and simulation.
nents of an OTEC plant, and showed that ammonia is a suit- Perform energy and exergy analyses of the integrated
able working fluid for an OTEC plant employing a closed system to determine the exergy destruction rate and energy
organic Rankine cycle (ORC). The energy efficiency of the and exergy efficiencies of each component and the entire
Rankine cycle in an OTEC plant is usually limited to around 5% system.
due to the small temperature difference between surface Determine the sustainability index for the system and
water and deep water of the ocean. So, to improve the effi- quantify its variation with exergy destruction, and examine
ciency of OTEC, other thermodynamic cycles like the Kalina the relation between exergy efficiency, exergy destruction
cycle and the Uehara cycle that use an ammoniaewater and sustainability index.
mixture as the working fluid are being considered [9]; they are Conduct a comprehensive parametric study to determine
reported to have better energy efficiencies rather than the effect of major design parameters on system
a Rankine cycle at the same temperature difference [9]. performance.
Increasing in the temperature difference between the hot
heat source and the cold heat sink can improve the efficiency
of OTEC plants, as can the integration of OTEC with other
energy technologies. Saitoh and Yamada [10] proposed 2. Modelling and energy analysis
a conceptual design of a multiple Rankine cycle system using
both solar thermal energy and ocean thermal energy in order For thermodynamic modelling purposes, the integrated OTEC
to improve the cycle efficiency. In addition, Owens [11] opti- system for hydrogen production considered here (Fig. 1) is
mized OTEC plants using ammonia as the working fluid in divided into three parts: flat plate solar collector, ocean
closed cycles. Uehara and Ikegamia [6] performed an optimi- thermal energy conversion (OTEC) unit and PEM electrolyzer.
zation study using the power method for a closed-cycle OTEC Fig. 1 shows a schematic diagram of an integrated OTEC
plant. Later, Uehara and Ikegamia [12] studied the perfor- system equipped with a flat plate solar collector and PEM
mance of OTEC using the Kalina cycle and proposed a new electrolyzer. This integrated system uses the warm surface
OTEC cycle with an absorption and extraction process [13]. seawater to evaporate a working fluid like ammonia or a Freon
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 7 9 5 e1 8 0 5 1797
Fig. 1 e Schematic of ocean thermal energy conversion (OTEC) with a flat plate solar collector and PEM electrolyzer for
hydrogen production.
Fig. 2 e TeS diagram of the ocean thermal energy conversion (OTEC) for hydrogen production.
2.1.2.1. Turbine generator power. The turbine power output is here, LE is the length of the evaporator plate and lE is taken
calculated by writing the energy balance for a control volume from Ref. [23]. Also, Deq is the equivalent diameter, which is
around a turbine which is the product of working fluid mass calculated as:
_ F and the adiabatic heat loss between the evapo-
flow rate, m
Deq 2d (14)
rator and the condenser, as follows:
where d is the clearance.
_Gm
W _ F hT hG h5 h6 (7)
here, hT and hG are the turbine isentropic efficiency and 2.1.2.3. Cold seawater pumping power. The cold seawater
generator mechanical efficiency. pumping power is expressed as:
_
2.1.2.2. Warm seawater pumping power. The warm seawater _ CS mCS DHCW g
W (15)
hCSP
pumping power can be written as:
where hCSP is the cold seawater pump efficiency and DHCW is
_ WS DHWS g
_ WS m
W (8) the total pump head of the cold seawater piping, given as:
hWSP
where DHWS is the total pump head difference of the warm DHCS DHCS P DHCS C DHCS d (16)
seawater piping:
here DHCS P is the pump head of the cold seawater pipe [23]:
DHWS DHWS P DHWS E (9)
DHCS P DHCS SP DHCS B (17)
here, DHWS P is the pump head of the warm seawater pipe,
These two terms are similar to terms in Eqs. (11) and (12). Also,
which can be given as [23]:
DHCS C is the cold seawater pressure difference in the
DHWS P DHWS SP DHWS B (10) condenser, defined as:
shown in Fig. 1, liquid water is fed to the PEM electrolyzer at where x is the distance in the membrane measured from the
ambient temperature. Liquid water enters a heat exchanger cathode-membrane interface and lx is the water content at
that brings it to the PEM electrolyzer temperature and it then a location x in the membrane. The value of lx can be
enters the electrolyzer. Leaving the cathode, the H2 produced calculated in terms of the water content at the membrane-
dissipates heat to the environment and cools to the reference electrode edges:
environment temperature. The oxygen gas produced at the
la lc
anode is separated from the water and oxygen mixture and lx x lc (26)
D
then cooled to the reference environment temperature. The
remaining water is then returned to the water supply stream where D is the membrane thickness, and la and lc are the
for the next hydrogen production cycle. The overall PEM water contents at the anode-membrane and the cathode-
electrolysis reaction is simply water splitting, i.e., electricity membrane interfaces, respectively. The overall ohmic resis-
and heat are used to separate water into produce hydrogen tance can thus be expressed as [25]:
and oxygen. Hydrogen is stored in a tank for later usage.
ZD
dx
RPEM (27)
2.1.3.1. Thermochemical modeling of a PEM electrolyzer. sPEM lx
0
Energy and exergy analyses of a PEM electrolyzer can be per-
formed in conjunction the electrochemical modeling. The Based on Ohms law, the following equation can be written
total energy needed by the electrolyzer can be obtained for the ohmic overpotential:
noting:
Vohm;PEM JRPEM (28)
Turbine isentropic efficiency, hT 0.80 Warm seawater mass flow rate (kg/s) 150
Generator mechanical efficiency, hG 0.90 Cold seawater mass flow rate (kg/s) 150
Working fluid pump isentropic efficiency, hWFP 0.78 Cold seawater pipe length (m) 1000
Seawater pumps isentropic efficiency, hP 0.80 Cold seawater pipe inner diameter (m) 0.70
Ambient temperature ( C) 25 Warm seawater pipe length (m) 50
Solar radiation incident on collector surface, I (W/m2) 500 Warm seawater pipe length (m) 0.70
Warm seawater temperature, TWSI ( C) 22 Solar collector effective area (m2) 5000
Cold seawater temperature at depth of 1000 m, TCSI ( C) 4 Electrolyzer working temperature ( C) 80
$ X X $ $
ExQ _ i exi
m _ e exe ExW ExD
m (31) W_ net
h (38)
i e _
Q EVP
where the subscripts e and i denote the inlet and outlet of
$
_ net is given in Eq. (6), and Q_ EVP is expressible as
where W
a control volume, ExD is the exergy destruction and other
terms are as follows [28e31]: Q_ EVP m
_ WF h1 h4 (39)
$ T0 _
ExQ 1 Qi (32) 3.1.2. Exergy efficiency
Ti The exergy efficiency is defined as the product exergy output
divided by the exergy input [23]. According to Nag and Dai
$
_
Exw W (33) [34,35], the exergy efficiency of the ORC power generation
cycle in an OTEC system is given as:
ex exph exch (34)
_ net
W _ net
W
J $ $ $ (40)
exph h h0 T0 s s0 (35) Exin Exin;WS Exin;CS
$ $
Here, ExQ and Exw respectively are the corresponding exergy $
_ in;WS hWS;in h0 T0 sWS;in s0
Exin;WS m (41)
rates associated with heat transfer and work across the
boundary of a control volume, T is the absolute temperature
$
and the subscript o refers to the reference environment _ in;CS hCS;in h0 T0 sCS;in s0
Exin;CS m (42)
conditions. The reference environment considered in our
here, the reference environment state is taken to be
study is T0 20 C and P0 1 bar. The specific chemical exergy
P0 1.01 bar and T0 298.15 K.
for gas mixtures is defined as follows [28,29]:
X X
exch xk exkch RT0 xk lnxk (36)
Further details about each term in this equation are given in 4. Results and discussion
Refs. [28e31].
To improve environmental sustainability, it is necessary 4.1. Modelling validation and simulation code results
not only to use sustainable or renewable sources of energy,
but also to utilize non-renewable sources like natural gas To model the integrated OTEC system for hydrogen produc-
more efficiently, while minimizing environmental damage. In tion, a simulation code using Matlab software is developed.
this way, society can reduce its use of limited resources and
extend their lifetimes. Here, a sustainability index SI is used to
relate exergy with environmental impact [30,32,33]:
0.6
Ohmic activation
0.5 Cathode activation
Overpotential(V)
Anode activation
0.4
0.3
0.2
0.1
0
0 1000 2000 3000 4000 5000 6000 7000 8000
Current density, J (A/m2)
Fig. 5 e Exergy destruction rate and dimensionless exergy
Fig. 4 e Variation of electrolyzer overpotentials at various destruction ratio for each component of the ocean thermal
current densities. energy conversion (OTEC) system for hydrogen production.
1802 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 7 9 5 e1 8 0 5
0.36 60 1.6 60
Sustainability index, SI
Exergy efficiency
0.32 1.5
50 50
0.3 1.45
45
45
1.4
0.28
40
40 1.35
0.26
1.3 35
0.24 35 400 440 480 520 560 600
400 440 480 520 560 600
Solar radiation intensity (W/m2)
Solar radiation intensity (W/m2)
Fig. 8 e Variation with solar radiation intensity of the
Fig. 6 e Variation with solar radiation intensity of the OTEC
sustainability index and total exergy destruction rate.
exergy efficiency and total exergy destruction rate.
4.2. Exergy analysis results destruction ratio are higher in the condenser than in other
components, suggesting that it would likely be worthwhile to
Results of the thermodynamic modelling and exergy analysis focus improvement efforts on this component.
are presented here, including assessments of the effects of Since the solar radiation intensity changes during the day,
varying several design parameters on the cycle performance. the variation of system performance is investigated with solar
As already discussed, the inputs of the simulation program radiation. Fig. 6 shows the variation of exergy efficiency and
are transferred to the developed code in order to calculate the exergy destruction rate of the OTEC system for various values
outputs. The results of the simulation program are listed in of solar radiation intensity. Increasing solar radiation inten-
Table 3. The net power output is seen to be around 101 kW, sity results in an increase in the exergy efficiency of the OTEC
which leads to a hydrogen production rate of about 1.2 kg/h. In system, suggesting that during such a day, the solar intensity
addition, the exergy efficiency of the integrated OTEC system increases the inlet temperature entering the evaporator,
is much higher than the energy efficiency, mainly due to the which leads to an increase in enthalpy at point 3 entering the
fact that the work is produced using a low-grade (in terms of turbine to produce work. The higher the temperature differ-
a temperature near to that of the reference environment) heat ence between cold and hot surfaces the more the work. Since
at the ocean surface. the cold surface temperature is almost constant at the depth
The exergy analysis results are presented in Fig. 5 and of the ocean, an increase in evaporator inlet temperature
show that the highest exergy destruction occurs in the results in an increase in the output power. Also, Fig. 6 shows
condenser, which is mainly due to the temperature difference that an increase in solar radiation leads to a decrease in total
between two fluid streams passing through it, but also due to exergy destruction.
the pressure drop across the device. Another important result The effect of solar radiation intensity on exergy destruction
relates to the dimensionless exergy ratio, which is useful for rate for each component is shown in Fig. 7. As shown in this
prioritizing exergy losses in an intuitive manner. Both the figure, an increase in solar radiation intensity has major
exergy destruction rate and the dimensionless exergy effects on the exergy destruction rates of turbine and
condenser while the changes in exergy destruction rate for the
130 2
mH2(kg/hr) Wnet(kW)
1.9
120
1.8
mH2 (kg/hr)
110
1.7
Wnet (kW)
1.6
100
1.5
90
1.4
80 1.3
400 440 480 520 560 600
Fig. 7 e Variation with solar radiation intensity of the Fig. 9 e Variation with solar radiation intensity of the OTEC
exergy destruction rate of components. net power output and hydrogen production rate.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 7 9 5 e1 8 0 5 1803
0.28 1.4 50
ex
0.22
42
1.28
0.2
1.24
0.18 38
1.2
0.16
34
0.14 1.16
0.12 1.12 30
280 284 288 292 296 300 280 284 288 292 296 300
T 0 (K) T0 (K)
Fig. 10 e Variation with ambient temperature of the exergy Fig. 12 e Variation with ambient temperature of the total
efficiency and sustainability index. exergy destruction rate.
evaporator and the pump are not drastic. So, since the sustainability index, due to an increase in the fluid tempera-
decrease in the exergy destruction rate of the condenser is ture entering the evaporator which increases the work of the
much higher than that for the turbine, the total exergy turbine. Above 285 K the exergy efficiency decreases because
destruction rate decreases with an increase in solar radiation the exergy input to the system, which is the denominator of
intensity. Fig. 8 shows the effect of solar radiation intensity on Eq. (33), increases, so two different effects occur and the effect
both sustainability index (SI) and total exergy destruction rate. of an increase in inlet exergy values dominates so the exergy
The results are similar to those in Fig. 6, i.e., the overall exergy efficiency of the OTEC system decreases. The variation of
destruction of the cycle decreases and the sustainability index exergy destruction rate of each component of the OTEC with
increases with increasing solar radiation intensity. The exergy ambient temperature is shown in Fig. 11, which demonstrates
efficiency, exergy destruction and sustainability are thus the same trend as Fig. 10. An increase in T0 has major effects on
observed to be linked in such systems, supporting the utility of the exergy destruction rate for the turbine and the condenser,
exergy and environmental analyses. while for the evaporator and working fluid pump it is almost
Fig. 9 shows the effect of solar radiation intensity on constant. An increase in temperature for the condenser first
hydrogen production mass flow rate. As the solar intensity leads to an increase in exergy destruction rate and then above
increases the hydrogen production increases since the turbine 285 K the exergy destruction rate decreases. However, the
work increases and correspondingly the electrical input to exergy destruction rate always increases for the turbine. The
PEM electrolysis increases. summation of these two effects results in an increase in the
Another major parameter in an OTEC plant is ambient total exergy destruction rate first then it leads to a decrease in
temperature because it affects the surface temperature and the total exergy destruction as shown in Fig. 12.
also the value for inlet exergy at each point of the plant. Hence, To enhance the analysis, the effect of condenser temper-
this temperature is an important parameter. Fig. 10 shows the ature on the exergy efficiency of the OTEC system is also
variation of exergy efficiency and sustainability index with investigated (see Fig. 13). An increase in condenser tempera-
ambient temperature. As can be seen, an increase in ambient ture is seen to reduce the exergy efficiency of the system.
temperature first leads to an increase in exergy efficiency and Increasing condenser temperature leads to an increase in
enthalpy at point 2 and results in a reduction in turbine work,
30
Turbine Condenser
0.32 60
Exergy destruction rate (kW)
25
50
0.28
20
Exergy efficiency
40
0.24
15
30
0.2
10 20
0.16
5 10
0 0.12 0
280 284 288 292 296 300 5 7 9 11 13 15
T0 (K) Condenser temperature (0C)
Fig. 11 e Variation with ambient temperature of the exergy Fig. 13 e Variation with condenser temperature of the total
destruction rate of each component. exergy efficiency and exergy destruction rate.
1804 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 7 9 5 e1 8 0 5
which lowers the exergy efficiency. Since the exergy J0 exchange current density (A/m2)
destruction rate in the condenser is much higher than in other Jref
i pre-exponential factor (A/m2)
components, any changes in the input exergy flow to the L length (m)
condenser leads to an increase in its exergy destruction, so an m_ mass flow rate (kg/s)
increase in condenser temperature leads to an increase in N_ molar mass flow rate (mol/s)
exergy flow at point 2 keeping other parameters constant. P pressure (kPa)
Q_ heat transfer rate (kW)
R gas constant (kJ/kg K)
5. Conclusions RPEM proton exchange membrane resistance (U)
s specific entropy (kJ/kg K)
The comprehensive thermodynamic modeling and exergy S radiation flux (W/m2)
analysis of an integrated OTEC system for hydrogen produc- T temperature ( C or K)
tion has provided useful insights. A complete thermodynamic V velocity (m/s)
simulation is performed for an OTEC cycle equipped with a flat V0 reversible potential (V)
plate solar collector and PEM electrolysis for hydrogen Vact activation overpotential (V)
production. Also, an exergy analysis is conducted and the Vact;a anode activation overpotential (V)
results show that the exergy efficiency of the integrated OTEC Vact;c cathode activation overpotential (V)
W_ work rate (kW)
system is about 22%. Other significant conclusions follow:
W_G turbine generator power (kW)
W_ CS cold seawater pumping power (kW)
An increase in solar radiation intensity decreases the total
W_ WF working fluid power (kW)
exergy destruction rate of the system and raises the exergy
W_ WS warm seawater pumping power (kW)
efficiency of the cycle and the hydrogen production rate.
An increase in solar intensity results in a drastic reduction
in condenser exergy destruction rate, which ultimately Greek letters
leads to a reduction in total exergy destruction rate of the h energy efficiency
cycle. hT turbine efficiency
An increase in ambient temperature has two different hG generator efficiency
effects on exergy efficiency: an increase in both exergy hWFP working fluid pump efficiency
efficiency and sustainability index below T0 292 K, and hCSP cold surface pump efficiency
a reduction of both exergy efficiency and SI above T0 292 K. hWSP warm surface pump efficiency
Increasing the condenser temperature reduces the exergy la water content at the anode-membrane interface
efficiency of the cycle because this increase raises the (U1)
enthalpy of the turbine outlet which reduces the net power lc water content at the cathode-membrane interface
output. (U1)
lx water content at location x in the membrane (U1)
r density (kg/m3)
sPEM proton conductivity in PEM (s/m)
Acknowledgement sx local ionic PEM conductivity (s/m)
J exergy efficiency
The authors acknowledge the support provided by the Natural
Sciences and Engineering Research Council of Canada. Subscripts
act activation
Nomenclature G generator
CS cold surface
C condenser
A surface area (m2) D destruction
CP specific heat at constant pressure (kJ/kg K) E evaporator
d diameter (m) eq equivalent
Deq equivalent diameter (m) in inlet condition
DP depletion number net net power
Eact;i activation energy in cathode or anode (kJ) ohm ohmic
$
Ex exergy flow rate (kW) out outlet condition
$
ExD exergy destruction rate (kW) PEM polymer exchange membrane
$
Exelectric electric exergy input rate (kW) T turbine
F Faraday constant (C/mol) p pump
g gravitational acceleration (m/s2) WF working fluid
G Gibbs free energy (J/mol) WS warm surface
h specific enthalpy (kJ/kg)
I solar radiation intensity (W/m2) Superscripts
J current density (A/m2) $ rate
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 7 9 5 e1 8 0 5 1805