Energy Conversion and Management 205 (2020) 112387

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Analysis and assessment of the integrated generation IV gas-cooled fast T

nuclear reactor and copper-chlorine cycle for hydrogen and electricity
production
Maan Al-Zareera,b, Ibrahim Dincerb, Marc A. Rosenb
a
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario M5S 3G8, Canada
b
Clean Energy Research Laboratory, Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario
L1H 7K4, Canada

ARTICLE INFO ABSTRACT

Keywords: This paper proposes the conceptual integration of a Generation IV nuclear reactor, the gas-cooled fast nuclear
Hydrogen reactor, and the thermo-electrochemical copper-chlorine cycle, a Brayton cycle, and a Rankine cycle for hy-
Nuclear drogen and electricity production. This paper analyzes the developed system thermodynamically, and energy
Copper-chlorine cycle and exergy efficiencies are used to measure the system performance. Here, the four-step thermo-electrochemical
Efficiency
copper-chlorine cycle produces hydrogen through thermochemical water decomposition, and electricity via the
Energy
Exergy
Rankine and Brayton cycles. The produced hydrogen is then compressed to reduce its storage volume. The
proposed system uses a heat exchanger network, which is incorporated within the hydrogen producing copper-
chlorine cycle. With the heat recovery network, the heat from the nuclear reactor is delivered to only two
reactors of the four-step copper-chlorine cycle. The proposed system is modeled and simulated with engineering
process simulation software (Aspen Plus). The overall energy and exergy efficiencies of the system are 14.1% and
20.7%, respectively.

1. Introduction clean energy storage if it is produced from clean energy sources [7].
Hydrogen has one of the highest energy densities (mass basis) of all
Maintaining a high living standard isdirectly linked to providing substances. Hydrogen can be utilized to produce other useful chemicals,
electricity, hot and cold water and maintaining a comfortable space for example ammonia and other hydrocarbons. Dincer and Zamfirescu
through conditioning air plus other commodities. Most of these are [8] conducted a comparative life cycle assessment of several fueled
generated using fossil fuels, where the use of fossil fuels has reached vehicles, including hydrogen and gasoline types, to assess the clean
85.7% of the total world energy consumption in 2018 [1]. Fossil fuels energy carrier benefits, hydrogen in terms of the environmental impact.
use is a major contributor to the increase in the atmospheric con- Dincer and Zamfirescu [8] concluded that hydrogen fuel cell vehicles
centration of carbon dioxide, which is one of the main contributors to have the lowest life cycle emissions if the hydrogen fueling these ve-
global warming [2]. The increase in electrical energy demand fore- hicles is produced from clean sources.
casted by the US Department of Energy for 2025 is 250 GW compared to Of carbon free fuels and energy sources, nuclear energy has the
2005 [3]. Even though it is estimated by the International Energy energy density and technology to potentially replace fossil fuels [9].
Agency that out of the 250 GW, 80 GW will be generated from coal, Systems that are based on these fuels have net zero carbon emissions
recent studies have focused on energy system integrations that are during operation [10]. The use of hydrogen produced from carbon-free
based on nuclear energy and renewable energies [4,5]. energy sources helps reduce carbon emissions to the environment, since
One of the main advantages of nuclear energy over conventional hydrogen is a carbon free energy carrier like electricity. However hy-
fossil fuels in terms of environment impact is its zero or near-zero drogen is a chemical energy medium that can be used directly or stored
carbon operational emissions (like many renewable energy sources) [11]. Hydrogen can be used to produce power through internal com-
[6]. One of the problems with nuclear and renewable energy is bustion engines [12], or electrochemically through fuel cells [13].
matching the power demand curve. This can be addressed by using an Having a chemical energy medium such as hydrogen has advantages;
energy storage technology. Hydrogen production can be viewed as a for instance, it can be converted to other useful chemicals such as

E-mail addresses: maan.al-zareer@uoit.ca (M. Al-Zareer), ibrahim.dincer@uoit.ca (I. Dincer), marc.rosen@uoit.ca (M.A. Rosen).

https://doi.org/10.1016/j.enconman.2019.112387
Received 18 July 2019; Received in revised form 5 December 2019; Accepted 6 December 2019
Available online 06 January 2020
0196-8904/ © 2019 Elsevier Ltd. All rights reserved.
M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

Nomenclature f Formation
gen Generation
cp Specific heat capacity (kJ/kg K) H2 Hydrogen
ex Specific exergy (kJ/kg) H2CS Hydrogen compression system
Ex Exergy rate (kW) is Isentropic
h Specific enthalpy (kJ/kg) in Input (flowing into system across boundary)
m Mass flow rate (kg/s) max Maximum
P Pressure (kPa) net Net result
Q Heat rate (kW) ov Overall
R Universal gas constant (kJ/mol K) out Output (flowing out of system across boundary)
s Specific entropy (kJ/kg K) o Reference environment conditions
T Temperature (oC) Q Heat flow rate
W Work rate (kW) SRC Supporting Rankine cycle
ST Steam turbine
Greek letters bs Boundary where heat transfer occurs
W Work
Energy efficiency P&T At pressure P and temperature T
Exergy efficiency
Acronyms
Subscripts
GFR Gas-cooled fast reactor
Cu-Cl Copper-chlorine cycle H2CS Hydrogen compression system
C Compressor SRC Supporting Rankine cycle
d Destruction
e Electrical

methane, ethanol, ammonia and methanol [8]. The combination of [14], by being able to operate the system at the optimum operation
electrical energy production and energy storage helps in matching en- point for the entire operation time.
ergy supply curves with demand curves. One of the advantages of in- As mentioned earlier hydrogen production from nuclear energy can
tegrating an energy system with a hydrogen based energy storage help match the demand curve as well as avoid over designing the nu-
system is being able to increase the capacity factor of the energy system clear reactor. This can increase the competitiveness of nuclear reactors,

Fig. 1. Schematic of the proposed nuclear based hydrogen and electricity production system.

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M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

since hydrogen can serve as an energy storage medium and energy Cl cycle is fed with heat and electricity, both of which are produced by a
carrier [15]. There are various methods for hydrogen production, and a gas-cooled fast nuclear reactor (a Generation IV reactor). This work is
recent and appealing one for nuclear reactors is the copper-chlorine part of the ongoing research on the Cu-Cl cycle in the Clean Energy
cycle, which is a hybrid thermochemical electrical cycle, which splits Research Laboratory at the University of Ontario Institute of
water to produce hydrogen [2]. There are other types of hybrid and Technology (UOIT). One of the important requirements of integrating
thermochemical cycles for water splitting, such as the magnesium- the Cu-Cl cycle in an energy system is defining the heat transfer circuit
chlorine (Mg-Cl) cycle [16]. However, the copper-chlorine cycle has an for the cycle reactors. The heat transfer circuit proposed earlier by the
advantage over Mg-Cl cycle in having lower operating temperatures, present authors [17] showed how it is important to consider the heat
making it more suitable for current and Generation IV nuclear reactors. distribution circuit for copper chlorine hydrogen production based in-
The integration of the copper-chlorine cycle to any of the current or the tegrated system. Al-Zareer et al. [17] highlighted the fact that the
Generation IV nuclear reactors is often assessed in the literature proposed heat circuit is specific for the heat source supplying the Cu-Cl
without considering the heat distribution circuit, which is the set of cycle with heat as well as responsible for producing the copper chlorine
heat exchangers used to distribute the heat from the nuclear reactor to cycle power requirement. In this paper, the heat source being one of the
the various reactors in the copper-chlorine cycle. generation IV nuclear reactor, the gas-cooled fast reactor, a new heat
The aim of this paper is to assess the performance of an integrated circuit is proposed to accommodate the for the gas based coolant and
electrical energy and hydrogen production system. The four-step Cu-Cl other operating conditions of selected nuclear reactor to deliver the
cycle produces the hydrogen in the proposed integrated system. The Cu- heat and power to the Cu-Cl cycle. The proposed system is modeled

Fig. 2. Aspen Plus flow sheet of the proposed electricity and hydrogen production system.

3
M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

with Aspen Plus process simulation software and the performance is main parameters. In the proposed system the heat is used to cogenerate
assessed through energy and exergy efficiencies accordingly. clean energy carries hydrogen and electrical power, with the hydrogen
generated by the copper-chlorine cycle. Canada Nuclear Laboratories
2. System Description (previously Atomic Energy of Canada Limited) has identified that the
four-step copper-chlorine water splitting cycle is a promising hydrogen
The proposed system schematic diagram is given in Fig. 1 where production technology [19,20]. The copper-chlorine cycle that is under
connections are shown between the system components including the development by Canada Nuclear Laboratories and University of Ontario
heat transfer circuit. Being nuclear based, the proposed system uses the Institute of Technology is considered here in the proposed integrated
gas-cooled fast reactor (GFR), which is one of the Generation IV re- system. It is a four-step cycle, with the main reactions as follows [2]:
actors. The GFR uses helium as the coolant to cool the reactor core. The CuCl2 (s) + H2 O(g) Cu2 OCl2 (s) + 2HCl(g) (1)
nuclear reactor is the source of the thermal energy in the cycle; there
also are several other subsystems: gas turbine cycle, water splitting Cu2 OCl2 (s) 2CuCl(l) + 0.5O2 (g) (2)
hybrid thermochemical copper-chlorine cycle, Rankine cycle and hy-
drogen compression system. The proposed integrated system is modeled CuCl(aq) + HCl(g) 0.5H2 (g) + CuCl2 (aq) (3)
and simulated using the Aspen Plus, which is a chemical and energy
process simulation software. The integrated system model developed in CuCl2 (aq) CuCl2 (s) + H2 O(g) (4)
Aspen Plus is shown in Fig. 2. The GFR is usually integrated with a gas
turbine in which the helium exiting the reactor core expands to gen- The reaction presented in equation (1) is referred to as the hydro-
erate electrical power. The exhausts of the gas turbine are then directed lysis reaction; the reaction is complete if the temperature of the reactor
to the boiler of a bottoming Rankine cycle and finally the helium is is maintained between 370 °C and 400 °C. The copper oxychloride
compressed back to the reactor core. The helium exits the nuclear re- (Cu2OCl2) resulting from the hydrolysis reaction goes to a decomposi-
actor core at a temperature of 850 °C, which is much higher than the tion reaction (equation (2)). The reactor used to model the decom-
required maximum temperature of the copper-chlorine cycle, and using position reactions is based on the assumption of complete decomposi-
it directly to heat the reactors leads to large exergy losses, so the system tion at a temperature of 500 °C to 530 °C, where the complete
starts by using a gas turbine to reduce the temperature and pressure of decomposition is based on the minimization of Gibbs free energy. The
the helium as well as produce power. second component leaving the hydrolysis reaction is hydrogen chloride
The GFR is a fast neutron spectrum reactor, which uses an inert gas. It is dissolved in water in the electrolysis reactor to produce hy-
coolant, helium [18]. The considered GFR is based on the reactor of the drogen from the hydrochloric acid and aqueous copper (I) chloride
nuclear power plant concept presented by the US Department of Energy through electrical separation. The electrolysis reactor consumes 41.6 kJ
as a Generation IV reactor concept, which is modeled to have a net of electricity per each mole of hydrogen generated [21]. The electro-
thermal energy of 600 MW [18]. Table 1 presents the integrated system lyzer generates hydrogen gas and aqueous copper (II) chloride, the
latter of which is dried to regenerate the main compound in the hy-
drolysis reaction to regenerate the cycle.
Table 1 The copper-chlorine cycle reactor receives thermal energy from the
Main operating parameters of the proposed hydrogen and electricity production GFR reactor through a steam heat distributing circuit as shown in
system, with a GFR nuclear reactor as the electricity and heat sources. Figs. 1 and 2. The helium exiting the gas turbine is directed to the
Subsystem Parameter Value Cu2OCl2 decomposition reactor heating jacket B24 as shown in Fig. 2.
The helium exiting the B24 heat exchanger goes to provide the required
GFR [25] Coolant temperature exiting reactor 850 °C heat to the hydrolysis reactor through its heating jacket as shown in
Coolant temperature entering 490 °C
Fig. 1, which is modeled as a heat exchanger (B26) that determines the
reactor
Coolant high/low pressures 9.0/2.9 MPa required heat through its connection with the hydrolysis reactor as
Thermal energy output rate 600 MW shown in Fig. 2. The heating distribution circuit is designed to recover
Coolant flow rate 320 kg/s as much as possible from the copper-chlorine cycle, and the developed
Copper-chlorine cycle Electrolysis reactor circuit is designed to deliver thermal energy only for the Cu2OCl2 de-
Moles of H2O required to dissolve 10 mol
composition reactor and the hydrolysis reactor, while the required heat
1 mol of CuCl2
Electricity consumption per mole of 41.6 kJ for the dryer and other heaters throughout the cycle is recovered
H2 produced [21] throughout the heat circuit as shown in Figs. 1 and 2. Unlike the heat
Hydrolysis reactor circuit proposed by the authors earlier [17], the heat transfer fluid in
Operating temperature 400 °C
this case is helium. The electrolyzer in the copper-chlorine cycle re-
Temperature of steam entering 400 °C
reactor ceives the required electrical energy from the power produced by the
Cu2OCl2 decomposition reaction gas turbine at the exit of the nuclear reactor and the heat recovery
Operating temperature 530 °C Rankine cycle. This Rankine cycle recovers the remaining heat from the
Dryer helium exiting the heat circuit of the copper-chlorine cycle as shown in
Operating temperature 110 °C
Fig. 1, where the helium exiting the boiler is sent back to the com-
Drying temperature 100 °C
Hydrogen compression Produced hydrogen pressure [23] 250 bar pressor before entering the nuclear reactor core. Finally, the produced
system hydrogen is compressed for storage and delivery at a pressure of
Number of compression stages 4 250 bar using a compression system made of three compressors and a
is,C [13] 0.72
heat recovery system that preheats the water of the heat recovery
Heat recovery Rankine High pressure point 20 bar
Rankine cycle as shown in Fig. 1. The performance of the proposed
cycle
Low pressure point 0.1 bar system is analyzed by simulating the proposed system on Aspen Plus
is,ST [13] 0.72 and assessed using the first and the second laws of thermodynamics.
The assessment methodology and equations are presented next.

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M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

3. Analysis Here, ex ch denotes the specific chemical exergy of the flowing mass
chemical substance, while the specific physical exergy associated with
The thermodynamic modeling and analysis are carried out for the the flowing mass due to its temperature, pressure and flow energy is
proposed system under the following assumptions: denoted by ex ph . The final term in the equation (7) is the exergy de-
struction rate. It is present since, unlike energy and mass, exergy can be
• The operation of the proposed integrated system considered in the destroyed. An irreversible (or non-ideal) process will always have a
assessment is the steady state portion of the operation of the system. positive exergy destruction, which causes the system to deviate from
Since the transient portion duration is negligible compared to the ideality.
steady state portion is the first reason for neglecting the transient The performance of the overall system, as well as its subsystems and
analysis in this paper. In addition, the purpose of the proposed components, is assessed with energy and exergy efficiencies. The
system is to increase the operation capacity of the nuclear reactor, overall system energy and exergy efficiencies can be expressed re-
which is also support the steady state assessment of the integrated spectively as follows:
system.
•
m H2 h H2 + Wnet,out m9h 9 + WSRC WH2 CS We
The variations in kinetic and potential energies are neglected = =
(10)
ov
throughout the system QGFR mS43hS43 mS48hS48

• The electrical generators convert 95% of the input shaft work to

m H2 ex H2 + Wnet,out m 9ex 9 + WSRC WH2 CS We
electrical energy = =
•
ov
The heat losses from turbines and heat exchangers are neglected due
Ex QGFR mS43exS43 mS48exS48 (11)
to their small values compared to the heat exchange duties of the Here, m H2 is the mass flow rate of the produced hydrogen com-
heat exchangers and the high power production of the turbines pressed at a pressure of 250 bar, hH2 is the specific enthalpy and ex H2 is
• The reference environment conditions for the exergy analysis are the specific exergy of hydrogen. Also, Wnet,out is the net produced power,
taken to be a temperature of 25 °C and a pressure of 1 atm. QGFR is heat rate released by the GFR, and the exergy rate of that heat
• The Aspen Plus uses the SOLIDS method for all materials properties, rate is Ex QGFR .
except Steamnbs is used for water and Cu-Cl compounds are adapted The performance of the main subsystems of the proposed system,
from the correlations published by Zamfirescu et al. [22]. which are the copper-chlorine cycle, the heat recovery Rankine cycle
and the compression system, are assessed as follows. For the four-step
As mentioned earlier, the proposed system performance is assessed copper-chlorine cycle, with Cu2OCl2 decomposition reactor and the
through the first and second laws of thermodynamics, which express hydrolysis reactor receiving external heat and the electrolyzer receiving
the balances for mass, energy and exergy rates. These can be expressed power from the gas turbine and the heat recovery Rankine cycle, the
respectively as follows: energy and exergy efficiencies are calculated as follows:
min = m out (5) m H2 LHVH2 mS17 LHVH2
Cu Cl = =
Q net,in + We (mS43hS43 mS46hS46) + We (12)
Q in + m(h@PT h o + hf ) + Win = m(h@PT h o + hf ) + Qout + Wout
in out mH2 ex H2 mS17ex S17
= =
(6)
Cu Cl
Ex Qnet,in + We (mS43exS43 mS46exS46) + We (13)
Ex Qin + Win + min exin = m out ex out + Ex Qout + Wout + Ex d Here, in the calculation of the efficiencies of the Cu-Cl cycle the
in out (7) produced hydrogen is considered to be at ambient pressure (stream S17
Equation (5) presents the mass rate balance for an open in Fig. 2), which is the operating pressure of the copper-chlorine cycle
steady state system, which applies to all of the components in the electrolyzer. Since the produced hydrogen from the electrolyzer is at
proposed system presented in Figs. 1 and 2; here m denotes the mass the ambient pressure and temperature then the lower heating value is
flow rate and the subscripts in and out refers to entering and leaving considered in the energy efficiency equation of the copper-chlorine
the control volume of the system. Equation (6) presents the energy cycle, where the subscripts refer to the names of the components in the
rate balance equation for an open steady state system; here Q denotes Aspen Plus flow sheet of the proposed system in Fig. 2. The energy and
the heat rate, h denotes the specific enthalpy of a flowing mass, and W exergy efficiencies of the heat recovery Rankine cycle are calculated as
denotes work rate. Note that ho denotes the specific enthalpy of the follows:
flowing mass at the reference environment conditions, while hf de-
WST1 WP1
notes the specific enthalpy of formation of the chemical substance of =
(14)
HRRC
(mR3hR3 mR2 hR2) + (mS46hS46 mS48hS48)
the flowing mass.
Equation (7) expresses the exergy rate balance equation for an open WST1 WP1
steady state device; here the exergy rate content of the heat rate is =
(15)
HRRC
(mR3 exR3 mR2 exR2) + (mS46exS46 mS48exS48)
denoted by Ex Q and is calculated as follows:
Again, the subscripts refer to the component and stream names in
To the Aspen Plus simulation flow sheet in Fig. 2. The collective energy
Ex Q = 1 dQ
Tbs (8) recovered from the compression system represents the difference be-
Here, Tbs denotes the surface temperature of the control volume tween the energy supplied to the compressors of the compression
boundary, which is where the heat crosses. In equation (7), the specific system and the received by the steam of the heat recovery Rankine
exergy of a flowing mass is denoted by ex and is calculated as follows: cycle. The second source of energy for the Rankine cycle is the energy
recovered from the helium before it is compressed and returned to the
ex = exch + ex ph = exch + ((h ho) To (s so )) (9) reactor core. Note that the design parameters presented in Table 1 and
used to set the conditions for the heat exchanger B25 ensure the helium

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M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

Table 2 4. Results and discussion

Main thermodynamic results of analysis the proposed integrated hydrogen and
power production system. The performance of the proposed integrated system is assessed in
Parameter Value terms of the operating parameters in Table 1. The main performance
measures of the overall system as well as its main subsystems are pre-
Overall hydrogen production rate [mol/s] 1 sented in Table 2. The overall net power production presented in
Temperature of product hydrogen [oC] 25
Table 2 is presented per unit of molar hydrogen production per second,
Pressure of product hydrogen [bar] 250
Overall net power produced [kJ/mol H2] 698 at a pressure of 250 bar and ambient temperature, where one mole of
Integrated system overall energy efficiency [%] 14.1 hydrogen is produced and stored for each 3.7 kg/s of coolant helium
Integrated system overall exergy efficiency [%] 20.7 exiting the reactor. The overall energy and exergy efficiencies of the
Four-step Cu-Cl cycle energy efficiency [%] 41.1
system are 14.1% and 20.7% respectively. The energy system can
Four-step Cu-Cl cycle exergy efficiency [%] 60.9
Four-step Cu-Cl cycle unit exergy destruction [kJ/mol H2] 151.9
produce 1 mol of compressed hydrogen at a pressure of 250 bar and
Hydrogen compression system energy efficiency [%] 95.0 ambient temperature, and 698 kW of electrical power, for each 3.7 kg/s
Hydrogen compression system exergy efficiency [%] 55.3 of coolant helium exiting the nuclear reactor. The above results indicate
Hydrogen compression system unit exergy destruction [kJ/mol H2] 11.7 that if the proposed 600 MW GFR is used for power and hydrogen
production it will be able to produce a total of 86.5 mol/s of hydrogen
and 60.4 MW of electrical energy. The low hydrogen production rate
return to the reactor core at the reactor design inlet coolant tempera- can be increased by increasing the exhaust pressure of the gas turbine
ture after being compressed in compressor B28 based on the DOE de- and using steam for the heat distribution circuit. The energy and exergy
sign, which is also presented in Table 1. efficiencies of the Cu-Cl cycle are 41.1% and 60.9% respectively and the
The compression system compresses hydrogen to a pressure of unit exergy destruction of the Cu-Cl cycle is 151.9 kJ/mol H2. The hy-
250 bar (see Table 1), which is the pressure usually used to transport drogen compression system energy and exergy efficiencies are 95.0%
hydrogen. The compression of hydrogen is important to reduce the and 55.3% respectively. The hydrogen compression system is re-
required storage space and the energy and exergy efficiencies of the sponsible for a unit exergy destruction of 11.7 kJ/mol H2.Table 3.
hydrogen compression system are calculated as follows: The proposed integrated hydrogen and power production system is
able to achieve an overall 14.1% conversion of the energy transferred
m9 h9 + mR3hR3
= by the helium coolant exiting the nuclear reactor core with the help of
(16)
H2 CS
mS17 hS17 + mR2 hR2 + WC1 + WC2 + WC3 + WC4 its subsystems. The copper-chlorine cycle, which produces hydrogen via
thermochemical water splitting, achieves an energy efficiency of
m 9ex 9 + mR3 exR3
= 41.1%. The resulting energy efficiency is validated against other stu-
H2CS
mS17 exS17 + mR2 exR2 + WC1 + WC2 + WC3 + WC4 (17) dies, where Ref. [21] have compared the energy efficiency of various
Here, the subscripts refer to the component and stream names in the copper chlorine cycles and found that they ranged from 41% for the
Aspen Plus flow sheet in Fig. 2. considered three-step to 44% for the considered four-step cycle and

Table 3
Exergy efficiency and exergy destruction rate expressions for reactors, water jackets and heat exchangers (internal heat recovery network) of the four-step Cu-Cl
cycle.
Device Description Exergy efficiency Exergy destruction rate

B1 Hydrolysis reactor =
m S3ex S3 Ex d,B1 = (mS1exS1 + mS2 exS2 + Ex QS47) mS3exS3
B1 m S1ex S1 + mS2 ex S2 + ExQ
S47
B6 Cu2OCl2 decomposition reactor =
m S9ex S9 Ex d,B6 = mS8exS8 + Ex QS45 mS9 exS9
B6 mS8ex S8 + Ex Q
S45
B11 Electrolysis reactor =
mS16ex S16 Ex d,B11 = We + mS15exS15 + mS7 exS7 + mS14 exS14 mS16exS16
B11 We + m S15 ex S15 + m S7 ex S7 + m S14 ex S14
B14 Dryer =
m S21ex S21 + mS20 ex S20 Ex d,B14 = Ex QS40 + mS19 exS19 mS21exS21 mS20 exS20
B14 ExQ + mS19 ex S19
S40
B22 Water jacket for dryer B14 ExQ
S40 Ex d,B22 = (mS36ex36 m 41exS41) Ex QS40
B22 =
m S36 ex S36 m S41ex S41
B26 Heat exchanger for hydrolysis reactor Ex Q
S47 Ex d,B26 = (mS44 exS44 m 46exS46) Ex QS47
B26 =
m S44 ex S44 mS46 ex S46
B24 Heat exchanger for the Cu2OCl2 decomposition reactor Ex Q
S45 Ex d,B24 = (mS43exS43 m 44 exS44) Ex QS45
B24 =
m S43ex S43 mS44 ex S44
B18 Water jacket for CuCl solidifier Ex Q
S29 Ex d,B19 = (mS28exS28 mS22exS22) Ex QS29
B19 =
m S28ex S28 mS22 ex S22
B15B5 Heat exchanger between Cu2OCl2 entering oxygen =
m S8ex S8 mS6 ex S6 Ex d,B15B5 = (mS28exS28 mS32 ex32) (mS8exS8 mS6 exS6)
B15B5
production reactor and internal heat recovery network mS28ex S28 mS32 ex S32

B16B2 Superheating steam to hydrolysis reaction temperature mS1ex S1 mS65ex S65

= Ex d,B16B2 = (mS32 exS32 mS33ex33) (mS1exS1 mS65exS65)
B16B2 mS32 ex S32 mS33ex S33
B39B40 Recovering thermal energy from generated steam from m S65 ex S65 m S4 ex S4 Ex d,B16B2 = (mS60 exS60 mS63ex 63) (mS65exS65 mS4 exS4)
B39B40 = m
dryer S60 ex S60 m S63ex S63
B20B3 Heating CuCl2 to hydrolysis reaction temperature =
mS2 ex S2 mS5 ex S5 Ex d,B20B3 = (mS33exS33 mS36 ex36) (mS2exS2 mS5exS5)
B20B3 mS33ex S33 mS36ex S36
B17B10 Recovering thermal energy from molten CuCl, and heating =
mS27 ex S27 mS26 ex S26 Ex d,B17B10 = (mS13exS13 mS14 exS14) (mS27 exS27 mS26exS26)
B17B10
water in thermal energy recovery network m S13 ex S13 m S14 ex S14

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M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

Fig. 3. Unit thermal energy (a) and exergy (b) interactions throughout the Cu-Cl cycle and its heat circuit heat exchangers, presented based on the name of the
reactor, heat exchanger or a combination of both with alphanumeric indicators, where these alphanumeric indicators can be found in Fig. 2 for the location of these
components.

similar values were reported in Ref. [19]. A breakdown of the unit the copper-chlorine cycle and its heat distribution circuit are further
thermal energy input and release of the various reactors (excluding the explained through the exergy efficiencies and the unit exergy destruc-
electrolyzer, since it does not use or release thermal energy and requires tions given in Fig. 4(a) and (b) respectively. The bar chart of the exergy
electrical energy) and all heat exchanger in the copper-chlorine cycle is destruction provides more details of how much potential is being lost in
presented in Fig. 3(a). In Fig. 3(a) the sign convention is positive for the cycle.
heat required by the cycle (input) and negative for heat released by The second subsystem in the integrated hydrogen and power pro-
reactors of heat exchangers. It is seen in Fig. 3(a) that, if there is no heat duction system is the hydrogen compression system. Based on the en-
recovered from the copper-chlorine cycle, the resulting energy effi- ergy and exergy efficiency definitions in equations (16) and (17), the
ciency of the considered four steps copper chlorine cycle is 12.4%; resulting values are 95% and 55.3% respectively. The hydrogen com-
however, the achieved energy efficiency with proposed heat recovery pression system consumes 25.5 kJ of compression energy per mole of
circuit is 41.1%. Fig. 3(a) shows that the step with the highest energy hydrogen compressed from 1 bar to 250 bar. A breakdown of the energy
use is the dryer. Assuming the heat delivered to the dryer was com- interactions in the compression system are shown in Fig. 5(a). Of the
pletely recovered will lead to increases the energy efficiency from four compressors of the compression system, compressor C4 consumes
12.4% to 24.1%, doubling the efficiency of the cycle by recovering the the most energy. Of the four intercoolers the last intercooler cools the
low temperature dryer energy. This is one of the main advantages of the most energy. By comparing the performance of the compression system
proposed steam circuit. to that for other hydrogen storage technologies. Other hydrogen storage
Further understanding of the copper-chlorine cycle can be obtained technologies such as chemical storage in ammonia. The use of ammonia
through analyzing the exergy interactions of the cycle. The unit thermal as a hydrogen storage medium will result in a consumption varies from
exergy interactions through the cycle are shown in Fig. 3(b). In 34.2 kJ of work energy to store and recover one mole of hydrogen by
Fig. 3(b), the sign convention is positive for exergy input to the cycle the newly proposed cooled ammonia production [23] to 59.5 kJ of
(input) and negative for exergy that is released by reactors of heat ex- work energy to store and recover one mole of hydrogen through high
changers. The achieved exergy efficiency of the cycle including the heat temperature and pressure ammonia production and electrolysis hy-
distribution circuit is 60.9%. Note that the exergy efficiency of the cycle drogen recovery [23]. The compression system exhibits lower energy
if no thermal energy is recovered, which is calculated by neglecting all input. A commercial hydrogen compression system, Linde on the other
the negative exergies, is equal to 28.2%. The exergy interactions of the hand can compress 1 mol of hydrogen with 7.5 kJ of work, which is
copper-chlorine cycle highlight the component with the highest exergy 30% of the proposed system. However, the input 7.5 kJ is 64.3% of the
consumption: the Cu2OCl2 decomposition reactor. Note that a large input energy of the proposed system considering the recovered energy
portion of this exergy is recovered by the heat distribution circuit as the through the intercooler that is later translated into work in the heat
heat exchanger combined between the B9 solidification reactor and the recovery Rankine cycle. In addition, based on the working principle of
heat exchanger B18. However, as shown in Fig. 2, none of the exergy the Linde system, it is expected to be slower than the proposed com-
provided to the hydrolysis reactor is recovered and in addition it re- pression system [24]. The exergy interactions through the hydrogen
quires more by the heat exchanger B15. The exergy interactions within compression system are shown in Fig. 5(b). The trend of the variation of

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M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

Fig. 4. (a) Exergy efficiencies of components of the copper-chlorine cycle and its heat distribution circuit, and (b) unit exergy destructions of components of the
copper-chlorine cycle and its heat distribution circuit. (Refer to Fig. 2 for the location of the components).

the exergy input for the compressors and the intercoolers is similar to exergy efficiencies and unit exergy destruction rates are shown in
the input energy bars mainly due to the similarity of the parameters set Fig. 6(a) and (b) respectively for the work producing and consuming
to the compressors and the intercoolers. devices in the integrated hydrogen compression system and the heat
Finally, the total net power production achieved by the system is recovery Rankine cycle. The steam turbine is responsible for the highest
698 kW of electrical power when each 1 mol/s of hydrogen is produced exergy destruction per mole of hydrogen produced from all of the
at a pressure of 250 bar. The heat recovery Rankine cycle takes ad- power producing or consuming devices in the hydrogen compression
vantage of the compression by preheating the pressurized water leaving and heat recovery Rankine cycle.
the cycle pump before it enters the heat recovery heat exchanger. The

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M. Al-Zareer, et al. Energy Conversion and Management 205 (2020) 112387

Fig. 5. Unit work and thermal energy (a) and exergy (b) interactions throughout the hydrogen compression system, presented based on the name of the reactor, heat
exchanger or a combination of both with alphanumeric indicators. (Refer to Fig. 2 for the location of the components).

Fig. 6. Exergy results for work producing and consuming devices in the integrated hydrogen compression system and the heat recovery Rankine cycle. (a) exergy
efficiency, and (b) unit exergy destruction rate. (Refer to Fig. 2 for the location of the components).

5. Conclusions assessments, considering operational, life cycle, safety, storage space

and other important parameters.
The conceptual integration is proposed and assessed of a Generation
IV nuclear reactor, the gas-cooled fast nuclear reactor, and the thermo- CRediT authorship contribution statement
electrochemical copper-chlorine cycle, a Brayton cycle, and a Rankine
cycle for electricity and hydrogen production. The developed cycle is Maan Al-Zareer: Investigation, Software, Validation, Formal ana-
analyzed thermodynamically and its performance is investigated lysis, Writing - original draft. Ibrahim Dincer: Supervision,
through energy and exergy efficiencies. The four-step thermo-electro- Conceptualization, Writing - review & editing, Funding acquisition.
chemical copper-chlorine cycle produces hydrogen through water de- Marc A. Rosen: Methodology, Writing - review & editing, Funding
composition, and the electricity is produced by the Rankine and acquisition.
Brayton cycles. The product hydrogen is compressed to reduce its sto-
rage space. The proposed system uses a heat exchanger network. The Declaration of Competing Interest
overall energy and exergy efficiencies of the system are 14.1% and
20.7% respectively. To improve understanding of system sensitivities, The authors declare that they have no known competing financial
further study is needed of the variation of the energy and exergy effi- interests or personal relationships that could have appeared to influ-
ciencies and the hydrogen production rate with the operating condi- ence the work reported in this paper.
tions of the electricity producing Rankine cycle and the discharge
pressure of the gas turbine. Further investigation is merited to in- Acknowledgement
vestigate the hydrogen storage technology in the proposed or hydrogen
production systems from compression system to chemical storage The authors acknowledge the support provided by the Natural
technologies. This should include cost and energy consumption Sciences and Engineering Research Council of Canada.

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