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Thermochemical hydrogen production with a

copper–chlorine cycle. I: oxygen release from
copper oxychloride decomposition

Article in International Journal of Hydrogen Energy · October 2008

DOI: 10.1016/j.ijhydene.2008.05.035

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international journal of hydrogen energy 33 (2008) 5439–5450

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Thermochemical hydrogen production with a

copper–chlorine cycle. I: oxygen release from copper
oxychloride decomposition

G.F. Naterer*, K. Gabriel, Z.L. Wang, V.N. Daggupati, R. Gravelsins

Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario,
Canada L1H 7K4

article info abstract

Article history: A key challenge facing the future hydrogen economy is a sustainable, lower-cost method of
Received 22 February 2008 hydrogen production, with reduced dependence on fossil fuels. Thermochemical water
Received in revised form splitting with a copper–chlorine (Cu–Cl) cycle is a promising alternative that could be linked
12 May 2008 with nuclear reactors to thermally decompose water into oxygen and hydrogen, through
Accepted 13 May 2008 intermediate copper and chlorine compounds. Heat is transferred between various
Available online 11 September 2008 endothermic and exothermic reactors in the Cu–Cl cycle, through heat exchangers that
supply or recover heat from individual processes. This paper examines the heat require-
Keywords: ments of these steps, in efforts to recover as much heat as possible and minimize the net
Thermochemical copper–chlorine heat supply to the cycle, thereby improving its overall efficiency. Also, this paper examines
cycle the thermal design of the oxygen production reactor, which is a key process to split water
Nuclear-based hydrogen production by decomposing an intermediate compound, copper oxychloride (Cu2OCl2), into oxygen gas
and molten cuprous chloride. The equipment design is analyzed to scale-up past work in
small proof-of-principle test tubes, up to larger capacities of oxygen production with
engineering lab-scale equipment.
ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction capacities of hydrogen production. This paper investigates

Adoption of hydrogen as an energy carrier will be one of
several key driving forces for increased hydrogen demand in
the future. Although there are many challenges to make
hydrogen achieve a significant market share in the future, it is
widely believed that it will gradually become a prominent fuel
in the future. This paradigm shift will require a large-scale
sustainable method of hydrogen production, wherein some
role of ‘‘green energy’’, such as nuclear or solar energy, will
have importance. ‘‘Green’’ hydrogen production would not
emit greenhouse gases that contribute to climate change.
Nuclear heat can be supplied abundantly for large-scale
a promising method of sustainable hydrogen production by
thermochemical water decomposition with a copper–chlorine
(Cu–Cl) cycle, driven by nuclear or other sources of industrial
heat.
Over 200 cycles have been identified previously to produce
hydrogen by thermochemical water decomposition from
various heat sources, including nuclear and solar energy. Very
few cycles have progressed beyond theoretical calculations to
working experimental demonstrations that establish scien-
tific and practical feasibility of the thermochemical processes.
The sulfur–iodine cycle is a leading example that has been
scaled up to a pilot plant level, with active work conducted by

* Corresponding author.
E-mail address: greg.naterer@uoit.ca (G.F. Naterer).
0360-3199/$ – see front matter ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.05.035
 Author's personal copy
5440 international journal of hydrogen energy 33 (2008) 5439–5450
Nomenclature
cp specific heat (kJ mol1 K1)
H enthalpy (kJ)
m mass (kg)
n number of moles
T Temperature
Greek
r density (kg/m3)
3 efficiency
the Japan Atomic Energy Agency (JAEA, Japan [1]), Commis-
sariat à l’énergie atomique (CEA, France [2]), Sandia National
Laboratory (SNL, USA [3]), and General Atomics (GA, USA [4]).
JAEA has demonstrated a pilot facility up to 30 L/h of hydrogen
with the S–I cycle. JAEA aims to complete a large S–I plant to
produce 60,000 m3/h of hydrogen by 2020, enough for about 1
million fuel cell vehicles [5,25]. Japan has a goal to have 5
million fuel cell vehicles on the road by 2020 [5]. In Canada,
recent Canadian developments in nuclear-based hydrogen
production have been outlined by Sadhankar et al. [6].
After considering various factors like availability and abun-
dance of materials, simplicity, chemical viability, thermody-
namic feasibility and safety issues, the following seven cycles (in
addition to the S–I cycle) were identified in a Nuclear Hydrogen
Initiative [11] as promising cycles: copper–chlorine (Cu–Cl) [7],
cerium–chlorine (Ce–Cl) [8], iron–chlorine (Fe–Cl) [8], magne-
sium–iodine (Mg–I) [9], vanadium–chlorine (V–Cl) [10], copper–
sulfate (Cu–SO4) [8] and hybrid chlorine [8]. Proof-of-principle
demonstrations have been completed for these cycles and
chemical viability has been proven. However, most of the cycles
require process heat at temperatures above 800  C.
Due to lower temperature requirements around 530  C, the
Cu–Cl cycle is a promising alternative that could be eventually
linked with a Super-Critical Water Reactor (SCWR), which is
Canada’s Generation IV reactor. Granovskii et al. [11] have
examined heat pumps to upgrade heat to higher temperatures
needed by the Cu–Cl cycle. Advantages of the Cu–Cl cycle
include lower process temperatures compared to other ther-
mochemical cycles, higher yields, reasonable kinetics for the
oxygen and hydrogen generation reactions (Serban et al. [12]),
and less demands on materials of construction because of the
lower temperatures. The cycle has been identified by Atomic
Energy of Canada Limited (AECL) as the most promising cycle
for thermochemical hydrogen production coupled with
SCWR.
Unlike Steam-Methane Reforming (SMR) to extract hydrogen
from natural gas, the Cu–Cl cycle utilizes chemical reactions that
form a closed internal loop, which re-cycles all intermediate
chemicals on a continuous basis, without emitting any green-
house gases externally to the atmosphere. The importance of
hydrocarbon-free production of hydrogen for sustainable devel-
opment has been examined by Bertel [13], Duffey and Miller [14]
and Duffey [15]. Dincer [16] has outlined key technical and envi-
ronmental concerns of existing technologies for hydrogen
production. The recent rise in oil prices and the need to sequester
CO2 are gradually tilting the economic balance away from the
traditional SMR technology (Mirabal et al. [17]). A comprehensive
overview of various hydrogen production methods was pre-
sented by Yildiz and Kazimi [18]. Rosen [19], Rosen and Scott [20]
evaluated the thermodynamic efficiency of hydrogen production
from nuclear energy and other sources. Operating temperatures
are key aspects of thermochemical hydrogen production, since
effective thermal design is essential for good energy conversion
efficiency (Naterer [21]). In this paper, the heat requirements of
various processes within the Cu–Cl cycle will be analyzed. In
particular, the process of copper oxychloride decomposition to
produce oxygen and molten cuprous chloride will be examined.
Various related components and auxiliary equipment associated
with the process will be investigated.
2. Heat requirements of the copper–chlorine
cycle
A thermochemical cycle performs a series of intermediate
reactions to achieve the overall splitting of water into
hydrogen and oxygen. It typically forms a closed cycle that
uses water as the only input substance, while hydrogen and
oxygen are the only two products. The Cu–Cl cycle splits water
into hydrogen and oxygen through intermediate copper and
chlorine compounds. Chemical reaction steps in the Cu–Cl
cycle and a conceptual schematic of an integrated cycle are
shown in Table 1 and Fig. 1 (based on Ref. [22]), respectively.
Decomposing water into hydrogen and oxygen implies that
sufficient energy must be provided to break the chemical bond
of hydrogen and oxygen atoms. From a thermodynamic
perspective, this energy is expressed in terms of enthalpy. The
minimum enthalpy is equal to the formation enthalpy of
water, i.e., 286 kJ/mol (denoted as DHf) if water, hydrogen and
oxygen are all contained at atmospheric pressure and at
a temperature of 25  C. However, a series of intermediate
processes are required to split water. As a consequence, the
energy required to split water will also be a function of the
processes, not solely the thermodynamic state alone. There-
fore, to evaluate the total energy required by the copper–
chlorine cycle, the thermal efficiency, optimization and
complexity of the thermal network become paramount. The
energy required by the Cu–Cl cycle includes heat, mechanical
energy and electricity. In this paper, a thermodynamic anal-
ysis will be performed to determine the heat released or
absorbed by each step of the Cu–Cl cycle.
In order to determine the heating values, enthalpy data is
needed for the working substances. The calculation proce-
dures below will use these typical heating values. The
following analysis provides a summary of key calculations in
the overall heat requirements of the Cu–Cl cycle. To calculate
the enthalpy change of a substance that is cooled or heated
over a particular temperature range without phase change, an
isobaric process could be assumed and the enthalpy change
can be calculated as follows,
Z Tfinal
T
ðDHÞTfinal
initial
¼n CP dT (1)
Tinitial
where DH is the enthalpy change of the substance, Cp is the
specific heat of the substance based on a molar quantity, n is
the molar quantity of the substance, and the subscripts on
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international journal of hydrogen energy 33 (2008) 5439–5450 5441

Table 1 – Chemical reaction steps in the Cu–Cl cycle (refer to Refs. [12,22])
Step Reaction Temp ( C) Feed and output

1 Hydrogen production step 450 Feed: Electrolytic Cu(s) þ dry HCl(g) þ Q

2Cu(s) þ 2HCl(g) / 2CuCl(l) þ H2(g)
2 Electrolysis step
4CuCl(aq) / 2CuCl2(aq) þ 2Cu(s)
(in HCl solution)
3 Drying step
2CuCl2(aq) / 2CuCl2(s)
2CuCl2(slurry) / 2CuCl2(s)
2.2H2O (l) / 2.2H2O(g)
0.1HCl(aq) / 0.1 HCl(g)
4 Hydrolysis step
2CuCl2(s) þ H2O(g) /
CuO$CuCl2(s) þ 2HCl(g)
5 Oxygen production step
CuO$CuCl2(s) / 2CuCl(l)
þ 1/2O2(g)
Output: H2(g) þ molten CuCl(l)
Ambient Feed: Granular CuCl(s) and HCl(aq) þ V
(electrolysis) Output: Cu(s) slurry þ HCl(aq), CuCl2 (aq) þ HCl(aq)
70 Feed: CuCl2(aq) solution
containing HCl(aq) þ Q (case 3-A)
CuCl2 slurry containing HCl(aq) þ Q (case 3-B)
Output: Granular CuCl2(s) þ H2O(g) þ HCl(g)
375 Feed: Granular CuCl2(s) þ H2O(g) þ Q
Output: Granular CuO$CuCl2(s) þ 2HCl(g)
530 Feed: Granular CuO$CuCl2(s) þ Q
Output: O2(g) þ Molten CuCl(l)

Q, heat; V, electrical energy; g, gas; l, liquid; s, solid; aq, aqueous solution.

Tinitial and Tfinal are the initial and final temperatures, where nCu is 2 mol, which is the stoichiometric coefficient in
respectively. the hydrogen production reaction (step 1).
For example, the enthalpy change of H2 from 450  C to 25  C The hydrolysis of CuCl2 (step 4) to obtain gaseous HCl is an
is calculated as follows, endothermic reaction. The heat required for this reaction is
hydrolysis
Z 25 equal to the reaction enthalpy change, DHreaction ¼ 116:6 kJ
 25
DHH2 400 ¼ nH2 CH
P dT
2
(2) [22]. The preparation of reactants for the hydrolysis reaction
400
also needs heat. The heat required to supply the steam can be
Eq. (1) cannot be directly applied to substances with phase calculated from
or structure change. The enthalpy change caused by the phase  375;vapor  375;vapor  
or structure change must be added to the value calculated nH2 O DHH2 O 25;liquid z DHH2 O 25;liquid z57:8 kJ for nH2 O ¼ 1 mol
from Eq. (1) to obtain the total enthalpy change for those (5)
substances. Fig. 2 illustrates a typical example of the depen-
The heat required to prepare solid CuCl2 is more complex.
dency of enthalpy change of CuCl on the phases, structures
Similar to the dewatering efficiency adopted for copper
and temperatures [22]. Additional details are provided by
particle drying mentioned above, to obtain 1 mol of dry solid
Wang et al. [23].
CuCl2, about 1.1 mol of H2O must be evaporated from the
In step 2, challenges with the reactor material can be
slurry. The heat required to obtain solid CuCl2 out of its
reduced if the reactant copper particles are dry. In this case,
solution from an ambient temperature to 375  C can be sepa-
heat is required for the electrolysis step (step 2) from the
rated into two parts: (1) heat solid CuCl2 to 375  C and (2)
hydrogen production step (step 1) to dry the copper slurry
evaporate water at 70  C. The sensible heat requirement is
discharged from the electrochemical cell. At the same time,
Z 375
heat is also required to increase the temperature of copper  375  
nCuCl2 DHCuCl2 25 ¼ 2 CCuCl
P
2
dT nCuCl2 ¼ 2 mol (6)
particles from 25  C to the hydrogen production reaction 25

(step 1) temperature of 450  C. The processes can be analyzed The heat carried by the vaporized water may be recycled
for the latent heat and sensible components as follows, back internally, but this may be difficult due to the low-grade
 70;vapor  70;vapor heat with limited utility at a relatively low temperature.
nH2 O DHH2 O 25;liquid ¼ 0:8 DHH2 O 25;liquid (3)
In the electrochemical step (step 2 in Fig. 1),
for drying of the copper particles, where nH2 O is the molar 4CuCl þ 4Cl ¼ 4CuCl 
2 ðin solution at 25 CÞ (7)
quantity of water entrained in the copper particles. The
residual moisture in solid particles lies in the range of 5–15%, 4CuCl  
2 ¼ 2CuCl2 þ 2CuðsÞ þ 4Cl ðin solution at 25 CÞ (8)
roughly in weight, after a dewatering process using gravity
sedimentation and filtration technology [24–26]. The molar The net heat transferred in these steps is [22]
quantity of water in 2 mol of copper particles lies in the range  
Elecrolysis
DHCuCl z0:26 kJ (9)
of 0.35–1.25 mol approximately. Here the average value of 25

nH2 O z0:8 is adopted.  

Elecrolysis
The heat required to increase the temperature of copper DHCuCls z12:25 kJ (10)
25
particles is calculated as follows,
Assembling the heat requirements for all steps in the Cu–Cl
Z 450
cycle, the total heat requirements and thermal efficiency can
nCu ðDHCu Þ450
25 ¼ 2 CCu
P dT (4)
25 be determined. Table 2 summarizes the heat requirements of
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5442 international journal of hydrogen energy 33 (2008) 5439–5450

Fig. 1 – Conceptual schematic of the Cu–Cl cycle (refer to Refs. [12,22,40]).

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international journal of hydrogen energy 33 (2008) 5439–5450
Fig. 2 – Enthalpy of CuCl vs. phases and structures near the
transitional temperatures [12].
each individual step, in terms of the heat required in kJ per
mol of hydrogen produced.
From Table 2, it can be observed that a significant portion
of heat can be re-cycled internally from exothermic to endo-
thermic reactors. In case 3-A, about 116 kJ of heat is released
internally within the cycle (by exothermic reactions, solidifi-
cation and cooling) and 277.4 kJ of heat is required (for endo-
thermic reactions, drying and heating) for each gram of
hydrogen produced by the precipitate slurry drying approach
in the Cu–Cl cycle (case 3-A in Table 2). Thus, if internal heat is
fully re-cycled, then ideally a net heat input of 161.4 kJ/g H2
must be supplied for case 3-A of Table 2, of which 81.7 kJ/g H2
represents the low-grade heat (lower than 70  C) for drying
and vaporizing moisture of low-temperature solid particles
and gas. For 3000 kg/day of hydrogen production from a pilot-
scale Cu–Cl facility, this suggests a low-grade heat require-
ment of about 245.1 GJ/day, or about 2.84 MW. Commercial
SMR plants typically vary between small units of about
5000 kg/day to the largest units of 500,000 kg/day of hydrogen.
This suggests that the low-grade heat requirement lies
between 4.1 MW and 410 MW for a commercial-scale Cu–Cl
facility. If approximately one-third of nuclear heat is trans-
formed to electricity in existing nuclear plants, then the
remaining two-thirds are rejected to the environment as low-
grade waste heat, which exceeds the amount needed by
a single commercial Cu–Cl plant. Thus, the low-grade waste
heat from nuclear reactors could supply the low-temperature
heat requirements of a commercial-scale Cu–Cl facility.
In the Cu–Cl cycle, for case 3-A, the ratio of released heat
(232 kJ/mol H2) to required heat (554.7 kJ/mol H2) is about 4:10,
which indicates the importance of recycling the heat loads
internally within the cycle. However, a portion of released
heat occurs at low temperatures, so re-cycling of this low-
grade heat may be impractical or cost prohibitive. From
a practical engineering perspective, it can be assumed that
part of the low-grade heat cannot be recycled in an industrial
capacity. In efforts to reduce the amount and portion of high-
temperature heat required by the Cu–Cl cycle, a sensitivity
analysis was performed for each chemical reaction and its
5443
heat requirements. Also, different techniques of fluid pro-
cessing were analyzed to reduce the input heat supplies. For
example, for upstream steps 1 (hydrogen production) and 4
(hydrolysis of CuCl2), drying processes are required to produce
dry particles of Cu and CuCl2. A possible way to lower the
amount of required heat is reducing the liquid water content
in CuCl2 and Cu slurry. Between the electrolysis reaction
(step 2) and the drying process (step 3) in Fig. 1, the heat
required to dry water occupies the majority of the total heat.
Therefore, if 50% less liquid water exists in the slurry, then the
total heat required between electrolysis (step 2) and the drying
process (step 3) would decrease by almost 50% as well.
The efficiency of the copper–chlorine cycle can be pre-
dicted using a thermal analysis. In this paper, the efficiency is
defined as follows:
DHf
3¼  100% (11)
DHinput þ DEelectrolysis
where DHf is the formation enthalpy of water with a value of
286 kJ/mol H2O, DEelectrolysis is the electrical energy required in
step 2 for electrolysis with a value of 62.6 kJ/mol H2, and
DHinput is the total heat required by the cycle.
From Table 2, in case 3-A, DHinput is 554.7 kJ/mol H2,
without recycling the released heat internally within the
cycle, which corresponds to an efficiency of 46%, assuming no
heat loss to the environment as a extreme limiting case.
However, if all released heat (232 kJ/mol H2) is recycled inter-
nally within the cycle, then the efficiency becomes 74% for
another limited case.
In practice, assuming 20% of the total energy is lost to the
environment, then the practical efficiency of the copper–
chlorine cycle for case 3-A becomes 41%, assuming that only
1/3rd of the released heat is recycled internally within the
cycle. The detailed results of efficiency are listed in Table 2. It
can be shown that recovery of the heat internally within the
Cu–Cl cycle greatly impacts and increases the cycle efficiency.
If case 3-B is adopted in the Cu–Cl cycle (i.e., the solid
particles of CuCl2 are obtained directly from the drying of
CuCl2 solution rather than precipitate of CuCl2), the heat
requirement and efficiency of the Cu–Cl cycle will be very
different. The heat required in case 3-B (1363.7 kJ/mol H2) is 2.5
times the value of case 3-A (554.7 kJ/mol H2). As a conse-
quence, the efficiency also decreases dramatically. In addi-
tion, to directly dry the solution will also bring a major
engineering challenge to recycle large quantities of water
vapor. Therefore, case 3-B is not recommended or discussed in
detail in this paper.
3. Thermal design of the oxygen reactor
The oxygen production step (step 5; see Table 1 and Fig. 1)
receives solid feed of CuO$CuCl2 and produces O2 gas and
liquid cuprous chloride. The reaction is given by CuO-
CuCl2(s) ¼ 2CuCl (molten) þ 0.5O2 (gas) at 530  C. Gas species
leaving the oxygen reactor include oxygen gas and potentially
impurities of products from side reactions, such as CuCl
vapor, chlorine gas, HCl gas (trace amount) and H2O vapor
(trace amount). The substances exiting the reactor are molten
CuCl, potentially solid CuCl2 from the upstream reaction
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5444 international journal of hydrogen energy 33 (2008) 5439–5450

Table 2 – Heat requirements of individual steps and the efficiency of the Cu–Cl cycle
Step Processes in the step T ( C) Heat in case 3-A drying Heat in case 3-B drying Heat output
(kJ/mol H2) (kJ/mol H2) (kJ/mol H2)

Total Low Total Low

grade grade

1 2Cu(s) þ 2HCl ¼ 2CuCl(l) þ H2(g)

Hydrogen production step
Vaporizing moisture form Cu(s) 35 / 70 29.0 29.0 29.0 29.0
Heating Cu(s) 25 / 450 23.4 0.3 23.4 0.3
Heating HCl(g) 25 / 450 3.0 0.1 3.0 0.1
Heat of reaction 450 46.8
Cooling & solidification of 450 / 25 80.8
molten CuCl
Cooling of H2(g) product 450 / 25 12.2

2 4CuCl (aq) ¼ 2CuCl2(aq) þ 2Cu(s) 35w70 Electrical energy

Electrolysis step in HCl solution 62.6 kJ/mol H2

3 2CuCl2(aq) / 2CuCl2(s)
Drying step

3-A Vaporizing water from 35 / 70 122.0 122.0

CuCl2 precipitate
2.2H2O(l) / 2.2H2O(g)
3-B Vaporizing water from 35 / 70 931 931
CuCl2 solution
16.7H2O(l) / 16.7H2O(g)

4 2CuCl2(s) þ H2O(g) ¼
CuOCuCl2(s) þ 2HCl(g)
Hydrolysis step
Heating CuCl2(s) 25 / 375 54.2 8.5 54.2 8.5
Heat of reaction 375 116.6 116.6
Steam production H2O(l) 25 / 375 57.1 3.4 57.1 3.4
¼ H2O(g)

5 CuOCuCl2(s) / 2CuCl(l)
þ 1/2O2(g)
Oxygen production step
Heating CuOCuCl2(s) 375 / 530 20.2 20.2
Heat of reaction 530 129.2 129.2
Cooling and solidification of 530 / 25 84.8
molten CuCl
Cooling of O2(g) product 530 / 25 7.4

Sum kJ/mol H2 554.7 163.3 1363.7 972.3 232

kJ/g H2 277.4 81.7 681.9 486.2 116

Percentage of low-grade heat 29.5% 71.3%

Efficiency of Cu–Cl cycle

Percentage of heat loss to environment (%) 0 0 20 20 20 20 20 20

Percentage of recycled heat internally 0 100 0 30 50 70 90 100
within the cycle (%)
Practical efficiency of Cu–Cl cycle (%) 46 74 37 41 44 47 51 53

Low-grade heat: the heat transfer at a temperature that is lower than 70 C.

(CuCl2 hydrolysis step), due to the incomplete decomposition
of CuCl2 at a temperature lower than 750  C (De Micco et al.
[27]), as well as reactant particles entrained by the flow of
molten CuCl. In the oxygen reactor, copper oxychloride
particles will decompose to molten salt and oxygen. The
reactant particles absorb decomposition heat from the
surrounding molten bath. While the particles are descending
in the molten CuCl bath, oxygen ascends through the molten
salt and then leaves the reactor. Simultaneously, another
product (liquid CuCl) is formed within the molten bath and
exits separately from the reactor.
Within the reactor, heat is transferred from liquid (molten
CuCl) to solid CuO$CuCl2 (reactant) particles and the molten
bath can be sustained by the reaction product itself. The
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international journal of hydrogen energy 33 (2008) 5439–5450 5445

oxygen product will leave the reactant particles immediately,

due to buoyancy of gas in the molten salt. This fast separation molten salt
aids to minimize heat transfer resistance to the reactant heat reservoir
Reactant (CuO*CuCl2)
particles, which then helps make the overall reaction rate
particles inlet
closer to the intrinsic reaction rate itself. The design of the Oxygen outlet
reactor requires a high efficiency of heat exchange and sepa-
ration of reactant from products, as well as product (oxygen)
from product (molten salt). Table 3 summarizes the required
production rates of reactants in the oxygen production step
(step 5) for a lab scale of 3 kg/day of hydrogen production
(10,000 times scaled up beyond the proof-of-principle testing) Secondary molten Molten
in the Cu–Cl cycle. salt flow CuCl outlet
A suitable method to heat the reactor is needed. A heated
Molten CuCl
inert gas could be introduced but there are two disadvantages
with this approach: poor heat transfer and enhanced Insulation layer
entrainment of undecomposed CuO$CuCl2 (reactant) parti-
cles. To re-cycle these entrained CuO$CuCl2 particles using
sieves or cyclone/centrifugal separation would require
significant power input. Also, the entrainment of fine particles
would clog and corrode the equipment, especially compo- molten CuCl
heat reservoir
nents like flanges and screws. Another alternative is radiation,
but again this is challenging because the process is more
Reactant (CuO*CuCl2)
difficult to control, especially if the power input is high. particles inlet
Oxygen outlet
A more practical and efficient option is to heat the molten
salt from the wall with a double shell structure without using
electricity. Flowing in the double shell, a secondary flow of
molten salt provides heat to the reactor. The secondary flow of
molten salt could be provided from a solar energy storage Secondary flow of
molten CuCl
reservoir or nuclear heat exchanger, which uses molten salt as
the heat storage and transferring medium [28,29]. Since Molten
molten CuCl itself can be the heat storage medium used in the CuCl outlet
solar energy reservoir, the molten CuCl can also be pumped Molten CuCl
out of the oxygen production reactor to a solar energy reser-
voir and pumped back into the reactor (preferred option; see Insulation layer
Fig. 3). If necessary, agitation could be introduced into the
bath. This approach would take advantage of both free and
forced convection with heterogeneous mixing that facilitates
both heat and mass transfer. Fig. 3 – (1) Conceptual schematic of the molten salt vessel
A difficulty is bubble spouting and separation of solid and (Double shell reactor), (2) Conceptual schematic of the
molten salt. To address this issue, techniques used in iron- molten salt vessel (CuCl is heated outside the reactor).
making or steel-making furnaces could be adopted, which
commonly handle the removal of high-temperature molten
iron, floating impurities/dross, slag and the feeding of iron ore. descending particles. The aggregation of CuO$CuCl2 (reactant)
The presence of bubbles in the molten bath has several particles will reduce the contact area between particles and
advantages. For example, they enhance the local rates of heat liquid, but fortunately the oxygen (product) bubbles can help
transfer. The contact area between the CuO$CuCl2 (reactant) to break these aggregations. Also, the upflow of oxygen
particles and molten CuCl (product bath) increases when they (product) bubbles will resist the descent of solid particles
are more heterogeneously mixed by ascending bubbles and which will help to increase the residence time of CuO$CuCl2
(reactant) particles in the molten salt, hence they help
decrease the reactor size. Due to the large density difference
between oxygen and molten CuCl, the oxygen bubbles formed
Table 3 – Flow capacities of reactants (lab scale, 3 kg H2/ at the surface of the reactant particles will leave the surface
day) immediately after the bubbles form, which ensures that the
H2 CuOCuCl2 O2 reaction is driven towards the direction of oxygen production.
3
The liquid level within the reactor may abruptly change
mol/h kg/h mol/h Nm /h mol/h
with a sudden increase of bubbles due to flash decomposition,
62.5 13.37 62.5 0.7 31.25
which may result in the entrainment of bubbles in the exit
CuCl (molten) T P (abs) Run time flow of molten CuCl, upon which the pipe could become

kg/h mol/h C atm h
choked by these bubbles. The liquid level may also change due
12.375 125 530 1–4 2
to a sudden pressure fluctuation. If there is a sudden decrease
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5446 international journal of hydrogen energy 33 (2008) 5439–5450
of pressure, the bubbles may lift part of the liquid up to the top
of the reactor, which could cause flooding or spouting of
liquid. This problem can be addressed by a molten salt
removal pipe of large diameter that is located on the reactor
side, with fewer bubbles than the other side, so the liquid level
is kept unchanged.
The reactant CuO$CuCl2 does not melt in molten CuCl
because it is first decomposed to oxygen and molten CuCl at
470  C. The reactor to produce oxygen is recommended to
operate at about 530  C. In this temperature range, many
metals would be oxidized by oxygen. The reactor and oxygen
removal equipment must be corrosion resistant to oxygen,
molten CuCl, dry HCl (or even moist HCl) and possibly Cl2 gas.
If CuCl2 is entrained in the reactor with CuO$CuCl2 particles,
then chlorine gas may appear and corrode the equipment
material at a temperature of 530  C. Oxygen cooling in a heat
exchanger downstream of the reactor requires a wall material
that is also resistant to O2 oxidization at 530  C, as well as dry
HCl corrosion at such a high temperature [34].
4. Supply of copper oxychloride particles to
the oxygen reactor
Solid feed of anhydrous solid CuOOCuCl2 from the CuCl2
hydrolysis reaction (step 4) of the Cu–Cl cycle, is supplied to
the oxygen production reactor. The bulk density of this
material depends on the particle size and structure which
influence the volume of the reactor, feeder and discharge
vessels. The structure and shape of solid CuO$CuCl2 are
formed in the upstream CuCl2 hydrolysis reactor (step 4).
Aggregation into blocks of CuO$CuCl2 particles may occur
during the process of removing, conveying and feeding of
particles. The aggregation may choke or clog the feeder and
cause sudden spouting of particles, so appropriate measures
are needed to overcome these problems.
It is advantageous that the reactant CuO$CuCl2 particles do
not have a melting point below the decomposition tempera-
ture of 450  C. Unfortunately, there may exist embedded
particles of CuCl2 from the upstream hydrolysis reactor
(step 4). The existence of CuCl2 particles in CuO$CuCl2 would
lead to undesirable products and side reactions. For example,
CuCl2 may decompose to CuCl and Cl2 gas [12,27]. The exis-
tence of Cl2 gas is highly corrosive. However, the existence of
CuCl generated from CuCl2 is not problematic, because molten
CuCl is also a product generated from the decomposition of
CuO$CuCl2 particles.
The most effective way to remove CuCl2 particles from
CuO$CuCl2 is to ensure that the upstream CuCl2 hydrolysis
reaction (step 4) to produce CuO$CuCl2 is fully completed
(conversion of CuCl2 to CuO$CuCl2 is as close as possible to
100%). The optimal conditions for full completion of the
hydrolysis reaction are still under investigation.
Within the Cu–Cl cycle, the reactant CuO$CuCl2 is
a product from an upstream hydrolysis reactor that operates
at a temperature of 350–450  C. In the oxygen reactor, the
operation will be safer if the lowest feeding temperature is
higher than the melting point of CuCl, i.e., 430  C. If particles
enter the reactor at a temperature lower than 430  C, a diffi-
culty with the presence of bubbles in the molten salt may
occur. Some CuCl vapor might condense and molten CuCl
might solidify around the CuO$CuCl2 particles, thereby
leading to blockage or confinement of bubbles. If an aggrega-
tion develops with particles, molten salt and bubbles, the
contact area between a reactant particle and heating medium
(molten CuCl) will decrease and the aggregations may float
along the surface of the molten salt. This would deter the
decomposition of reactant particles and potentially lead to
choking of the reactor (a major safety concern). Fortunately,
this issue can be avoided in several ways: hot feeding of the
reactant particles, using an agitator, or protective mixing with
hot oxygen (one of the decomposition products).
The ideal reactant feeding temperature is slightly higher
than the melting point of CuCl. In this way, there is no
aggregation of solidified CuCl with entrained bubbles and the
temperature of the liquid surface is lower than the bulk liquid,
which will generate a density difference within the molten
salt bath to strengthen the convection, mixing and flow of
liquid.
The particle size from the upstream CuCl2 hydrolysis
reactor (step 4) significantly influences the feeding tech-
nology. If the particle size is very small (like a fine powder), the
feeding is very different than the case of larger particles. The
powder would not descend through the molten bath, despite
a powder density that is greater than the molten salt, because
of drag and buoyancy effects. Also, the removal of gas from
the reactor will induce a local vortex in the gas stream, which
will add to the difficulty of powder descent if the particles are
fed above the free surface level. Fortunately, this difficulty can
be overcome by using a method of pneumatic feeding that is
conveyed by oxygen gas, which is a product of the chemical
reaction. Using pneumatic feeding technology, the feeding
pipe can intrude below the level of molten CuCl. The main
principle of the feeding technology is similar to that of
pneumatic conveying. The bulk of solid CuO$CuCl2 particles is
forced by the O2 gas stream to become a dilute phase and then
the particles are suspended and conveyed, when moving
through the pipe [32].
The particle size also has a significant influence on the
reactor height. Although the density of CuO$CuCl2 particles is
larger than that of molten CuCl [33], the speed of descent
(terminal velocity) of particles in a stagnant liquid depends
strongly on the structure/size of particles and the liquid
properties (density and viscosity), considering the reducing
effect of the presence of bubbles on the descent of particles. It
is recommended for the reactor height to provide enough
residence time for the particles, so they can be completely
decomposed before reaching the bottom of the reactor.
5. Processing of molten salt from the oxygen
reactor
The decomposition temperature of CuO$CuCl2 is higher than
the melting point of CuCl. Therefore, CuCl product will leave
the reactor in molten form. The heat carried by molten CuCl is
high-grade (high temperature) heat that can be recovered to
supply other endothermic processes, such as evaporating
water to superheated steam for use in the hydrolysis reaction
in step 4 at a temperature of 375  C. Another option is to heat
 Author's personal copy
international journal of hydrogen energy 33 (2008) 5439–5450
HCl gas from 375  C to 450  C for use in the hydrogen
production reaction in step 1. The latter option is less prefer-
able because the temperature difference between HCl gas and
molten CuCl is much smaller than that between water and
molten CuCl. In addition, the hydrogen generation reaction is
exothermic, which implies that HCl gas could be self-heated.
Also, to heat HCl gas using molten CuCl requires that the
equipment material must be corrosion resistant to HCl gas at
a high temperature of 450  C. HCl gas may react with many
common metals and their protective oxide film at a tempera-
ture of 400  C [34]. In particular, if any moisture is present in
the HCl gas, it will be more corrosive. However, this challenge
is not as difficult with heating of H2O.
To recover the heat carried by molten salt, two types of
contact between gas and molten salt are available: direct or
indirect contact. In the former case, the molten salt can be
sprayed downward, while counter-current motion of gas is
flowing upward. For example, due to the very low solubility of
CuCl in water (6.2  105 g/g water, 20  C), the molten salt can
be first quenched in the quenching cell and the vapor gener-
ated is then heated to a temperature of 375  C.
The heat carried by the molten salt is sufficient to heat
liquid water from 25  C to superheated vapor at 375  C. Due to
the heat balance, the quantity of water that can be evaporated
at ambient temperatures and then heated to 375  C by the
heat carried in the molten CuCl (2 mol) is 1.5 mol, which is
larger than the stoichiometric value (1 mol) required in the
hydrolysis reaction. The heat content of 2 mol of molten CuCl
from the oxygen generation reactor is recovered from 530  C.
During the process of solidification, this molten salt
undergoes three phase transitions from molten to b-hexag-
onal crystal (412–423  C, denoted as b) and then cubic (<412  C,
denoted as C) crystal forms as shown in Fig. 2. The heat
released during these phase transitions is calculated as
follows:
n h
423;liquid
2ðDHCuCl Þ25;solid;C 423;solid;b
450;liquid ¼2 ðDHCuCl Þ450;liquid þ ðDHCuCl Þ423;liquid
i would not descend properly, thereby enhancing the likelihood
þ ðDHCuCl Þ412;solid;b 412;solid;C
423;solid;b þðDHCuCl Þ412;solid;b
o entrained by the molten CuCl, so the bubbles may plug the pipe
þ ðDHCuCl Þ25;solid;C
412;solid;C
where
Z the removal equipment. The particles may continue to
423
423;liquid
ðDHCuCl Þ450;liquid ¼
CuCl;liquid
CP dT ¼ 3:0 kJ
450
h i
ðDHCuCl Þ423;solid;b 412;solid;b 412;solid;C
423;liquid þðDHCuCl Þ423;solid;b þðDHCuCl Þ412;solid;b
¼ 14:5 kJ
Z 25
ðDHCuCl Þ25;solid;C
412;solid;C ¼ CCuCl;solid;C
P dT ¼ 22:92 kJ
412
The heat released by 2 mol of molten CuCl is 1.5 times larger
than the heat required to evaporate 1 mol of water from 20  C
to 375  C. Industrial spraying and powder cooling technology
for other molten salts and metals is well established [35–37]
and the technology could be used for cooling molten CuCl
through direct contact with low-temperature steam and liquid
water. When heating water vapor using a molten salt, some
CuCl particles may be entrained by water vapor into the
reactor, which will result in less contact area between reac-
tant gas (water vapor) and reactant particles (CuCl2) in the
5447
hydrolysis reaction (step 4). This would lead to a slight
decrease of the reaction rate of step 4, as well as the product
yield. However, this does not indicate that entrained CuCl
particles must be removed from water vapor before the vapor
enters the hydrolysis reactor (step 4), because in the hydro-
lysis step, the entrained CuCl particles will finally mix with
CuO$CuCl2 particles that will then move to the oxygen
production reactor (step 5), where CuCl is also a desirable
product.
The second method of recovering heat from molten CuCl
is indirect contact. When using a traditional type of shell and
tube heat exchanger for gas and molten CuCl, it is not rec-
ommended that the equipment is operated at a temperature
lower than 430  C (melting point of CuCl), otherwise solidi-
fication of CuCl to solid in the pipe may plug equipment. In
addition, an indirect contact method of the shell and tube
heat exchanger may not be economically feasible, as the
heat quantity released by molten salt without phase change
is 3 kJ/mol H2, as shown in Eq. (12), which is much smaller
than most values of the heat requirements listed in Table 1.
Therefore, an indirect contact method is not recommended
in the design.
After the temperature of CuCl becomes equal to or lower
than 430  C, direct contact methods must be used. A two-step
cooling process of molten CuCl could be adopted, in order to
recover heat from the molten salt. In the auxiliary process of
hydrogen production (step 1) the molten CuCl could be cooled
to a temperature slightly higher than 430  C in a heat
exchanger, usually a traditional tube and shell heat
exchanger. Then in the the exiting CuCl would use direct
contact cooling as described previously (spray cooling).
The molten CuCl effluent from the oxygen production
reactor might contain entrained particles of unreacted
CuO$CuCl2. In addition, fine oxygen bubbles may appear on the
surface of the reactant particles when decomposing. If the
bubbles detach slowly from the particles, CuO$CuCl2 particles
of their entrainment in the molten CuCl. Some bubbles may be
ð12Þ
where molten salt flows out of the reactor. The entrainment of
reactant particles could also introduce safety issues involving
(13) decompose in the pipe after leaving the reactor, which would
generate gas bubbles in the pipe and simultaneously decrease
the temperature of molten salt. Since the decomposition
requires heat input, this may result in solidification of molten
ð14Þ salt. To prevent the entrainment problems, various potential
methods are currently under investigation by the authors.
(15) Molten CuCl product is quenched to solid at a low
temperature in the quenching unit. As mentioned in Section 4,
the solubility of CuCl in water is very low and CuCl will solidify
as it descends into liquid water. Simultaneously, part of the
liquid water absorbs the heat released from molten CuCl,
which then evaporates to steam. Rapid cooling and solidifi-
cation of molten CuCl is desired in the quenching unit. The
heat loss in the spray nozzle of molten CuCl must be small to
avoid plugging of solid CuCl in the nozzle. The mixture of
water and solid CuCl particles will be used in the electrolysis
step (step 2), for electrolysis after adding enough HCl to help
dissolve CuCl.
 Author's personal copy
5448 international journal of hydrogen energy 33 (2008) 5439–5450
Table 4 – Condensation of steam generated from the quenching cell (lab scale, 3 kg H2/day)
CuCl from 530  C Vapor from 120  C
(molten) to 30  C (solid) (vapor) to 60  C (liquid)
Kg/day mol/h Kg/h mol/h
297 125 2.449 136.0
Another option to quench molten CuCl is that CuCl
descends into an aqueous solution of HCl and possibly CuCl2.
An advantage of this method is to promote the direct disso-
lution of CuCl. However, this will introduce other challenges.
One challenge is that the mixture of HCl and steam at high
temperatures will exist in the gas phase inside the equipment,
due to the volatile nature of HCl gas. The mixture is strongly
corrosive to many materials. As a result, the use of steam with
HCl would be more problematic. Therefore, this quenching
method is not recommended in the design.
It should be noted that although the above discussion
focuses on the processing of molten salt from the oxygen
reactor, the same technology can be adopted in the hydrogen
production step (step 1), in which there are also 2 mol of
molten CuCl produced. Due to the different features of the
hydrogen production reaction, the molten CuCl produced in
that step can be better recovered in other ways. This will be
investigated in future research.
6. Processing of other byproducts
A secondary process related to molten salt disposal is the re-
use of steam generated from the quenching cell. At an
industrial scale, the steam could be re-used by other steps
(such as hydrolysis step). In the auxiliary equipment, vapor
flowing down through a pipe of a vertical heat exchanger
would be cooled to liquid that flows up through the shell side
of the heat exchanger. The condenser should provide rapid
cooling of the vapor and prevention of any toxic gas release to
the environment.
Table 4 shows the operating parameters for a lab-scale
cycle of 3 kg/day of hydrogen production in the Cu–Cl cycle.
The vapor quantity at 120  C that can be generated by molten
CuCl is calculated. In the lab-scale design, the vapor is
condensed to 60  C by cooling water in a heat exchanger for
recovery of heat. The temperature of 60  C is selected in the
lab-scale design because this temperature is fairly standard
and the requirement for cooling water is not too low, so the
heat exchanger can work normally in different seasons.
Oxygen is another product that is the predominant gas
exiting the reactor. A cooling process designated by O2 from
530  C to 25  C must be designed to cool the exiting O2 and
recover this heat to reduce the operating temperature and
oxidization degradation of wall materials. For example, hot
oxygen flows within a pipe through a heat exchanger and it is
cooled to a lower temperature by cooling water that is flowing
in the shell side of the heat exchanger (see Fig. 4). The heat
quantity released by O2 is listed in Table 2. Table 5 shows the
typical operating parameters for a lab-scale cycle of 3 kg/day
of hydrogen in the Cu–Cl cycle. In the table, N2 is introduced as
an auxiliary gas for O2 detection in a lab scale (note: in a future
Cooling water from 20  C P (abs) Run time
(liquid) to 60  C (liquid)
Kg/h m3/h atm h
974.6 0.9746 1–2 2
industrial scale, N2 would not appear). There are two major
reasons to introduce N2: (1) increasing the O2 detection accu-
racy, as many O2 detectors perform better at a concentration
that is lower than 100% and the flow rate of N2 can be accu-
rately controlled so that the flow rate of O2 can be accurately
calculated from its concentration; (2) preventing the air flow
reversal from the oxygen outlet due to the pressure decrease
in the reactor caused by temperature fluctuations, if O2 gas is
very slowly produced. However, the introduction of N2 may
increase the burden on the heat exchanger, so an additional
quantity of cooling water (around 0.8 m3/h) is required in
Table 5, which is calculated on the assumption that the
volumetric concentration of N2 varies from 10% to 100%.
Oxygen leaves the reactor at a temperature of 530  C,
which is higher than the burning point of many materials
such as wood, paper and gasoline. Also, the volume of oxygen
at 530  C is nearly three times the volume of oxygen at
ambient temperature. This underlies the critical importance
of properly cooling the oxygen to ambient temperature, then
recovering the heat for other endothermic processes in the
Cu–Cl cycle.
The removal of oxygen must not be slower than the decom-
position rate of reactant, in order to prevent a sudden rise of
the reactor pressure due to possible ‘‘flash decomposition’’ of the
reactant particles in the molten salt. A sudden decrease of the
reactor pressure could also lead to flooding or spouting of bubbles
within the liquid. Prior to steady-state continuous operation,
1 mole H2, Cooling water, 0.5 moles O2,
25ºC heated, 60ºC 25ºC
1 mole H2, Cooling water, 0.5 moles O2,
450ºC 20ºC 530ºC
Fig. 4 – Heat recovery from hydrogen and oxygen
production reactors.
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international journal of hydrogen energy 33 (2008) 5439–5450
Table 5 – Cooling of oxygen from the molten salt reactor ( lab scale, 3 kg H2/day)
H2 Oxygen from 530  C to 25  C Cooling water from 20  C (liquid) to 60  C (liquid)
3 3
Mol/h Nm /h Mol/h Kg/h
62.5 0.7 31.25 781
tests should be performed under batch operation of a continuous
flow reactor, in order to assess the dependency of reaction
kinetics on scale-up, i.e., decomposition rate of reactant particles
and the removal of oxygen and molten salt.
In the processing of oxygen gas, trace amounts of CuCl
vapor may be present in the oxygen gas after the oxygen
bubbles ascend and leave the molten CuCl bath. The concep-
tual technology would not remove CuCl from the oxygen gas.
Instead, it would use hot oxygen gas to purge lower temper-
ature CuO$CuCl2 particles. In this way, CuCl would condense
and return back to the oxygen production reactor.
Further to past studies of Lewis [12,22], the decomposition
of CuCl2 is much slower than the consumption rate of Cl2 by
CuO. Since CuO$CuCl2 is a compound rather than a mixture of
CuO and CuCl2, the chlorine atoms produced would be
consumed at once by the bonded CuO neighbor in a distance
of nanometers. It is expected that the decomposition process
consists of a single two-step reaction, rather than two side
reactions. Then significant amounts of chlorine gas may not
appear during the decomposition of CuO$CuCl2.
However, it is also possible that unreacted CuCl2 in the
hydrolysis reaction (step 4) may be introduced into the oxygen
production reactor, if it is entrained by CuO$CuCl2 particles.
This unreacted CuCl2 may decompose, producing chlorine gas
and CuCl. It would be exceedingly difficult to separate
CuO$CuCl2 particles from effluent particles arriving from the
upstream reactor. Thus, it is critical to effectively control the
yield of CuO$CuCl2 in the upstream hydrolysis reaction
(step 4), so the ratio of CuCl2 to CuO$CuCl2 must be as low as
possible entering the oxygen production reactor.
Another two possible impurities in the oxygen gas are trace
amounts of HCl gas and H2O vapor. They might enter the
oxygen production reactor if they are entrained by the reac-
tant particles CuO$CuCl2. In the upstream hydrolysis reactor
(step 4), HCl gas is a product and H2O is a reactant. If the
hydrolysis reaction is not fully completed, H2O steam will mix
with HCl gas to exit the hydrolysis reactor [12,38].
The mixture of HCl and H2O entrained by the reactant
particles CuO$CuCl2 is an engineering concern because of the
strong corrosive nature of the gas mixture and the re-use of
steam. Particularly, a more corrosive HCl acid mist may form
during the cooling process of oxygen. The best method of
preventing the presence of H2O in the CuO$CuCl2 particles is
to ensure that H2O is completely consumed in the upstream
reaction to produce CuO$CuCl2. However, the hydrolysis
reaction is not easily controlled to full completion without
using excess steam [12,38]. In principle, although the steam
can be internally recycled to the hydrolysis reactor for steady-
state operation, to extract H2O steam from HCl gas is an
engineering challenge, and the extent to which steam is re-
cycled will influence the thermal efficiency. The technology to
re-cycle steam and prevent the presence of HCl and H2O in
CuO$CuCl2 particles is currently the investigation by the
5449
P (abs) Run time
m /h atm h
0.781 1–2 2
authors [38,39] These continued improvements will be
necessary to raise the overall thermal efficiency of the Cu–Cl
cycle, relative to other thermochemical cycles that have been
reported in the International Journal of Hydrogen Energy
[40–42], which have advanced further towards commercial
deployment for nuclear-based hydrogen production.
7. Conclusions
The copper–chlorine cycle is a promising thermochemical
cycle for nuclear-based hydrogen production. Aspen Plus
simulations [22,38] have indicated potentially up to 53%
thermal efficiency of the Cu–Cl cycle, although 43% is more
realistic, when losses due to engineering equipment operation
are included. Its scientific feasibility has been demonstrated
and all thermal reactions go to completion with minimal side
reactions. Between each step of the Cu–Cl cycle, heat
exchangers are needed for heat input/recovery and fluid
transport to different parts of the thermochemical cycle. Heat
exchangers are typically located before and after each reactor
to supply fluid temperatures required for each chemical
reactor.
The oxygen production step has the highest temperature
requirement in the cycle (530  C). This paper has examined
the heat requirements of the oxygen production and other
steps within the Cu–Cl cycle. Heat supply is required at
various temperatures throughout the cycle, so effective heat
matching between endothermic and exothermic reactors is
needed for efficient operation. This paper has examined the
heat matching between steps of the Cu–Cl cycle, in efforts to
recover as much heat as possible and minimize the net heat
supply to the cycle, thereby improving its overall efficiency.
This paper has also examined the thermal design issues,
major engineering challenges and corresponding solutions
related to the oxygen production reactor.
Acknowledgements
Financial support from Atomic Energy of Canada limited
(particularly Dr. S. Suppiah and Dr. R. Sadhankar) and the
Ontario Research Excellence Fund is gratefully acknowledged.
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