See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/222817441

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

CITATIONS READS

67 518

5 authors, including:

Kamiel Gabriel Zhaolin Wang

University of Ontario Institute of Technology University of Ontario Institute of Technology
74 PUBLICATIONS 917 CITATIONS 53 PUBLICATIONS 607 CITATIONS

SEE PROFILE SEE PROFILE

All in-text references underlined in blue are linked to publications on ResearchGate, Available from: Zhaolin Wang
letting you access and read them immediately. Retrieved on: 06 November 2016
 Author's personal copy

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

Available at www.sciencedirect.com

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

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

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

overview of various hydrogen production methods was pre-

Nomenclature sented by Yildiz and Kazimi [18]. Rosen [19], Rosen and Scott [20]
evaluated the thermodynamic efficiency of hydrogen production
cp specific heat (kJ mol1 K1)
from nuclear energy and other sources. Operating temperatures
H enthalpy (kJ)
are key aspects of thermochemical hydrogen production, since
m mass (kg)
effective thermal design is essential for good energy conversion
n number of moles
efficiency (Naterer [21]). In this paper, the heat requirements of
T Temperature
various processes within the Cu–Cl cycle will be analyzed. In
Greek particular, the process of copper oxychloride decomposition to
r density (kg/m3) produce oxygen and molten cuprous chloride will be examined.
3 efficiency Various related components and auxiliary equipment associated
with the process will be investigated.

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]). 2. Heat requirements of the copper–chlorine
JAEA has demonstrated a pilot facility up to 30 L/h of hydrogen cycle
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 A thermochemical cycle performs a series of intermediate
million fuel cell vehicles [5,25]. Japan has a goal to have 5 reactions to achieve the overall splitting of water into
million fuel cell vehicles on the road by 2020 [5]. In Canada, hydrogen and oxygen. It typically forms a closed cycle that
recent Canadian developments in nuclear-based hydrogen uses water as the only input substance, while hydrogen and
production have been outlined by Sadhankar et al. [6]. oxygen are the only two products. The Cu–Cl cycle splits water
After considering various factors like availability and abun- into hydrogen and oxygen through intermediate copper and
dance of materials, simplicity, chemical viability, thermody- chlorine compounds. Chemical reaction steps in the Cu–Cl
namic feasibility and safety issues, the following seven cycles (in cycle and a conceptual schematic of an integrated cycle are
addition to the S–I cycle) were identified in a Nuclear Hydrogen shown in Table 1 and Fig. 1 (based on Ref. [22]), respectively.
Initiative [11] as promising cycles: copper–chlorine (Cu–Cl) [7], Decomposing water into hydrogen and oxygen implies that
cerium–chlorine (Ce–Cl) [8], iron–chlorine (Fe–Cl) [8], magne- sufficient energy must be provided to break the chemical bond
sium–iodine (Mg–I) [9], vanadium–chlorine (V–Cl) [10], copper– of hydrogen and oxygen atoms. From a thermodynamic
sulfate (Cu–SO4) [8] and hybrid chlorine [8]. Proof-of-principle perspective, this energy is expressed in terms of enthalpy. The
demonstrations have been completed for these cycles and minimum enthalpy is equal to the formation enthalpy of
chemical viability has been proven. However, most of the cycles water, i.e., 286 kJ/mol (denoted as DHf) if water, hydrogen and
require process heat at temperatures above 800  C. oxygen are all contained at atmospheric pressure and at
Due to lower temperature requirements around 530  C, the a temperature of 25  C. However, a series of intermediate
Cu–Cl cycle is a promising alternative that could be eventually processes are required to split water. As a consequence, the
linked with a Super-Critical Water Reactor (SCWR), which is energy required to split water will also be a function of the
Canada’s Generation IV reactor. Granovskii et al. [11] have processes, not solely the thermodynamic state alone. There-
examined heat pumps to upgrade heat to higher temperatures fore, to evaluate the total energy required by the copper–
needed by the Cu–Cl cycle. Advantages of the Cu–Cl cycle chlorine cycle, the thermal efficiency, optimization and
include lower process temperatures compared to other ther- complexity of the thermal network become paramount. The
mochemical cycles, higher yields, reasonable kinetics for the energy required by the Cu–Cl cycle includes heat, mechanical
oxygen and hydrogen generation reactions (Serban et al. [12]), energy and electricity. In this paper, a thermodynamic anal-
and less demands on materials of construction because of the ysis will be performed to determine the heat released or
lower temperatures. The cycle has been identified by Atomic absorbed by each step of the Cu–Cl cycle.
Energy of Canada Limited (AECL) as the most promising cycle In order to determine the heating values, enthalpy data is
for thermochemical hydrogen production coupled with needed for the working substances. The calculation proce-
SCWR. dures below will use these typical heating values. The
Unlike Steam-Methane Reforming (SMR) to extract hydrogen following analysis provides a summary of key calculations in
from natural gas, the Cu–Cl cycle utilizes chemical reactions that the overall heat requirements of the Cu–Cl cycle. To calculate
form a closed internal loop, which re-cycles all intermediate the enthalpy change of a substance that is cooled or heated
chemicals on a continuous basis, without emitting any green- over a particular temperature range without phase change, an
house gases externally to the atmosphere. The importance of isobaric process could be assumed and the enthalpy change
hydrocarbon-free production of hydrogen for sustainable devel- can be calculated as follows,
opment has been examined by Bertel [13], Duffey and Miller [14] Z Tfinal
T
and Duffey [15]. Dincer [16] has outlined key technical and envi- ðDHÞTfinal
initial
¼n CP dT (1)
Tinitial
ronmental concerns of existing technologies for hydrogen
production. The recent rise in oil prices and the need to sequester where DH is the enthalpy change of the substance, Cp is the
CO2 are gradually tilting the economic balance away from the specific heat of the substance based on a molar quantity, n is
traditional SMR technology (Mirabal et al. [17]). A comprehensive the molar quantity of the substance, and the subscripts on
 Author's personal copy

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

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
 Author's personal copy

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]).

 Author's personal copy

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

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 in the molten CuCl bath, oxygen ascends through the molten
of CuCl2 at a temperature lower than 750  C (De Micco et al. salt and then leaves the reactor. Simultaneously, another
[27]), as well as reactant particles entrained by the flow of product (liquid CuCl) is formed within the molten bath and
molten CuCl. In the oxygen reactor, copper oxychloride exits separately from the reactor.
particles will decompose to molten salt and oxygen. The Within the reactor, heat is transferred from liquid (molten
reactant particles absorb decomposition heat from the CuCl) to solid CuO$CuCl2 (reactant) particles and the molten
surrounding molten bath. While the particles are descending bath can be sustained by the reaction product itself. The
 Author's personal copy

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
 Author's personal copy

5446 international journal of hydrogen energy 33 (2008) 5439–5450

of pressure, the bubbles may lift part of the liquid up to the top occur. Some CuCl vapor might condense and molten CuCl
of the reactor, which could cause flooding or spouting of might solidify around the CuO$CuCl2 particles, thereby
liquid. This problem can be addressed by a molten salt leading to blockage or confinement of bubbles. If an aggrega-
removal pipe of large diameter that is located on the reactor tion develops with particles, molten salt and bubbles, the
side, with fewer bubbles than the other side, so the liquid level contact area between a reactant particle and heating medium
is kept unchanged. (molten CuCl) will decrease and the aggregations may float
The reactant CuO$CuCl2 does not melt in molten CuCl along the surface of the molten salt. This would deter the
because it is first decomposed to oxygen and molten CuCl at decomposition of reactant particles and potentially lead to
470  C. The reactor to produce oxygen is recommended to choking of the reactor (a major safety concern). Fortunately,
operate at about 530  C. In this temperature range, many this issue can be avoided in several ways: hot feeding of the
metals would be oxidized by oxygen. The reactor and oxygen reactant particles, using an agitator, or protective mixing with
removal equipment must be corrosion resistant to oxygen, hot oxygen (one of the decomposition products).
molten CuCl, dry HCl (or even moist HCl) and possibly Cl2 gas. The ideal reactant feeding temperature is slightly higher
If CuCl2 is entrained in the reactor with CuO$CuCl2 particles, than the melting point of CuCl. In this way, there is no
then chlorine gas may appear and corrode the equipment aggregation of solidified CuCl with entrained bubbles and the
material at a temperature of 530  C. Oxygen cooling in a heat temperature of the liquid surface is lower than the bulk liquid,
exchanger downstream of the reactor requires a wall material which will generate a density difference within the molten
that is also resistant to O2 oxidization at 530  C, as well as dry salt bath to strengthen the convection, mixing and flow of
HCl corrosion at such a high temperature [34]. liquid.
The particle size from the upstream CuCl2 hydrolysis
reactor (step 4) significantly influences the feeding tech-
4. Supply of copper oxychloride particles to nology. If the particle size is very small (like a fine powder), the
the oxygen reactor feeding is very different than the case of larger particles. The
powder would not descend through the molten bath, despite
Solid feed of anhydrous solid CuOOCuCl2 from the CuCl2 a powder density that is greater than the molten salt, because
hydrolysis reaction (step 4) of the Cu–Cl cycle, is supplied to of drag and buoyancy effects. Also, the removal of gas from
the oxygen production reactor. The bulk density of this the reactor will induce a local vortex in the gas stream, which
material depends on the particle size and structure which will add to the difficulty of powder descent if the particles are
influence the volume of the reactor, feeder and discharge fed above the free surface level. Fortunately, this difficulty can
vessels. The structure and shape of solid CuO$CuCl2 are be overcome by using a method of pneumatic feeding that is
formed in the upstream CuCl2 hydrolysis reactor (step 4). conveyed by oxygen gas, which is a product of the chemical
Aggregation into blocks of CuO$CuCl2 particles may occur reaction. Using pneumatic feeding technology, the feeding
during the process of removing, conveying and feeding of pipe can intrude below the level of molten CuCl. The main
particles. The aggregation may choke or clog the feeder and principle of the feeding technology is similar to that of
cause sudden spouting of particles, so appropriate measures pneumatic conveying. The bulk of solid CuO$CuCl2 particles is
are needed to overcome these problems. forced by the O2 gas stream to become a dilute phase and then
It is advantageous that the reactant CuO$CuCl2 particles do the particles are suspended and conveyed, when moving
not have a melting point below the decomposition tempera- through the pipe [32].
ture of 450  C. Unfortunately, there may exist embedded The particle size also has a significant influence on the
particles of CuCl2 from the upstream hydrolysis reactor reactor height. Although the density of CuO$CuCl2 particles is
(step 4). The existence of CuCl2 particles in CuO$CuCl2 would larger than that of molten CuCl [33], the speed of descent
lead to undesirable products and side reactions. For example, (terminal velocity) of particles in a stagnant liquid depends
CuCl2 may decompose to CuCl and Cl2 gas [12,27]. The exis- strongly on the structure/size of particles and the liquid
tence of Cl2 gas is highly corrosive. However, the existence of properties (density and viscosity), considering the reducing
CuCl generated from CuCl2 is not problematic, because molten effect of the presence of bubbles on the descent of particles. It
CuCl is also a product generated from the decomposition of is recommended for the reactor height to provide enough
CuO$CuCl2 particles. residence time for the particles, so they can be completely
The most effective way to remove CuCl2 particles from decomposed before reaching the bottom of the reactor.
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$CuCl2 is as close as possible to 5. Processing of molten salt from the oxygen
100%). The optimal conditions for full completion of the reactor
hydrolysis reaction are still under investigation.
Within the Cu–Cl cycle, the reactant CuO$CuCl2 is The decomposition temperature of CuO$CuCl2 is higher than
a product from an upstream hydrolysis reactor that operates the melting point of CuCl. Therefore, CuCl product will leave
at a temperature of 350–450  C. In the oxygen reactor, the the reactor in molten form. The heat carried by molten CuCl is
operation will be safer if the lowest feeding temperature is high-grade (high temperature) heat that can be recovered to
higher than the melting point of CuCl, i.e., 430  C. If particles supply other endothermic processes, such as evaporating
enter the reactor at a temperature lower than 430  C, a diffi- water to superheated steam for use in the hydrolysis reaction
culty with the presence of bubbles in the molten salt may 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 5447

HCl gas from 375  C to 450  C for use in the hydrogen hydrolysis reaction (step 4). This would lead to a slight
production reaction in step 1. The latter option is less prefer- decrease of the reaction rate of step 4, as well as the product
able because the temperature difference between HCl gas and yield. However, this does not indicate that entrained CuCl
molten CuCl is much smaller than that between water and particles must be removed from water vapor before the vapor
molten CuCl. In addition, the hydrogen generation reaction is enters the hydrolysis reactor (step 4), because in the hydro-
exothermic, which implies that HCl gas could be self-heated. lysis step, the entrained CuCl particles will finally mix with
Also, to heat HCl gas using molten CuCl requires that the CuO$CuCl2 particles that will then move to the oxygen
equipment material must be corrosion resistant to HCl gas at production reactor (step 5), where CuCl is also a desirable
a high temperature of 450  C. HCl gas may react with many product.
common metals and their protective oxide film at a tempera- The second method of recovering heat from molten CuCl
ture of 400  C [34]. In particular, if any moisture is present in is indirect contact. When using a traditional type of shell and
the HCl gas, it will be more corrosive. However, this challenge tube heat exchanger for gas and molten CuCl, it is not rec-
is not as difficult with heating of H2O. ommended that the equipment is operated at a temperature
To recover the heat carried by molten salt, two types of lower than 430  C (melting point of CuCl), otherwise solidi-
contact between gas and molten salt are available: direct or fication of CuCl to solid in the pipe may plug equipment. In
indirect contact. In the former case, the molten salt can be addition, an indirect contact method of the shell and tube
sprayed downward, while counter-current motion of gas is heat exchanger may not be economically feasible, as the
flowing upward. For example, due to the very low solubility of heat quantity released by molten salt without phase change
CuCl in water (6.2  105 g/g water, 20  C), the molten salt can is 3 kJ/mol H2, as shown in Eq. (12), which is much smaller
be first quenched in the quenching cell and the vapor gener- than most values of the heat requirements listed in Table 1.
ated is then heated to a temperature of 375  C. Therefore, an indirect contact method is not recommended
The heat carried by the molten salt is sufficient to heat in the design.
liquid water from 25  C to superheated vapor at 375  C. Due to After the temperature of CuCl becomes equal to or lower
the heat balance, the quantity of water that can be evaporated than 430  C, direct contact methods must be used. A two-step
at ambient temperatures and then heated to 375  C by the cooling process of molten CuCl could be adopted, in order to
heat carried in the molten CuCl (2 mol) is 1.5 mol, which is recover heat from the molten salt. In the auxiliary process of
larger than the stoichiometric value (1 mol) required in the hydrogen production (step 1) the molten CuCl could be cooled
hydrolysis reaction. The heat content of 2 mol of molten CuCl to a temperature slightly higher than 430  C in a heat
from the oxygen generation reactor is recovered from 530  C. exchanger, usually a traditional tube and shell heat
During the process of solidification, this molten salt exchanger. Then in the the exiting CuCl would use direct
undergoes three phase transitions from molten to b-hexag- contact cooling as described previously (spray cooling).
onal crystal (412–423  C, denoted as b) and then cubic (<412  C, The molten CuCl effluent from the oxygen production
denoted as C) crystal forms as shown in Fig. 2. The heat reactor might contain entrained particles of unreacted
released during these phase transitions is calculated as CuO$CuCl2. In addition, fine oxygen bubbles may appear on the
follows: surface of the reactant particles when decomposing. If the
n h bubbles detach slowly from the particles, CuO$CuCl2 particles
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
of their entrainment in the molten CuCl. Some bubbles may be
o entrained by the molten CuCl, so the bubbles may plug the pipe
þ ðDHCuCl Þ25;solid;C
412;solid;C ð12Þ
where molten salt flows out of the reactor. The entrainment of
where reactant particles could also introduce safety issues involving
Z the removal equipment. The particles may continue to
423
423;liquid
ðDHCuCl Þ450;liquid ¼
CuCl;liquid
CP dT ¼ 3:0 kJ (13) decompose in the pipe after leaving the reactor, which would
450 generate gas bubbles in the pipe and simultaneously decrease
h i the temperature of molten salt. Since the decomposition
ðDHCuCl Þ423;solid;b 412;solid;b 412;solid;C
423;liquid þðDHCuCl Þ423;solid;b þðDHCuCl Þ412;solid;b requires heat input, this may result in solidification of molten
¼ 14:5 kJ ð14Þ salt. To prevent the entrainment problems, various potential
Z 25
methods are currently under investigation by the authors.
ðDHCuCl Þ25;solid;C
412;solid;C ¼ CCuCl;solid;C
P dT ¼ 22:92 kJ (15) Molten CuCl product is quenched to solid at a low
412
temperature in the quenching unit. As mentioned in Section 4,
The heat released by 2 mol of molten CuCl is 1.5 times larger the solubility of CuCl in water is very low and CuCl will solidify
than the heat required to evaporate 1 mol of water from 20  C as it descends into liquid water. Simultaneously, part of the
to 375  C. Industrial spraying and powder cooling technology liquid water absorbs the heat released from molten CuCl,
for other molten salts and metals is well established [35–37] which then evaporates to steam. Rapid cooling and solidifi-
and the technology could be used for cooling molten CuCl cation of molten CuCl is desired in the quenching unit. The
through direct contact with low-temperature steam and liquid heat loss in the spray nozzle of molten CuCl must be small to
water. When heating water vapor using a molten salt, some avoid plugging of solid CuCl in the nozzle. The mixture of
CuCl particles may be entrained by water vapor into the water and solid CuCl particles will be used in the electrolysis
reactor, which will result in less contact area between reac- step (step 2), for electrolysis after adding enough HCl to help
tant gas (water vapor) and reactant particles (CuCl2) in the 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 Cooling water from 20  C P (abs) Run time
(molten) to 30  C (solid) (vapor) to 60  C (liquid) (liquid) to 60  C (liquid)

Kg/day mol/h Kg/h mol/h Kg/h m3/h atm h

297 125 2.449 136.0 974.6 0.9746 1–2 2

Another option to quench molten CuCl is that CuCl industrial scale, N2 would not appear). There are two major
descends into an aqueous solution of HCl and possibly CuCl2. reasons to introduce N2: (1) increasing the O2 detection accu-
An advantage of this method is to promote the direct disso- racy, as many O2 detectors perform better at a concentration
lution of CuCl. However, this will introduce other challenges. that is lower than 100% and the flow rate of N2 can be accu-
One challenge is that the mixture of HCl and steam at high rately controlled so that the flow rate of O2 can be accurately
temperatures will exist in the gas phase inside the equipment, calculated from its concentration; (2) preventing the air flow
due to the volatile nature of HCl gas. The mixture is strongly reversal from the oxygen outlet due to the pressure decrease
corrosive to many materials. As a result, the use of steam with in the reactor caused by temperature fluctuations, if O2 gas is
HCl would be more problematic. Therefore, this quenching very slowly produced. However, the introduction of N2 may
method is not recommended in the design. increase the burden on the heat exchanger, so an additional
It should be noted that although the above discussion quantity of cooling water (around 0.8 m3/h) is required in
focuses on the processing of molten salt from the oxygen Table 5, which is calculated on the assumption that the
reactor, the same technology can be adopted in the hydrogen volumetric concentration of N2 varies from 10% to 100%.
production step (step 1), in which there are also 2 mol of Oxygen leaves the reactor at a temperature of 530  C,
molten CuCl produced. Due to the different features of the which is higher than the burning point of many materials
hydrogen production reaction, the molten CuCl produced in such as wood, paper and gasoline. Also, the volume of oxygen
that step can be better recovered in other ways. This will be at 530  C is nearly three times the volume of oxygen at
investigated in future research. 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
6. Processing of other byproducts Cu–Cl cycle.
The removal of oxygen must not be slower than the decom-
A secondary process related to molten salt disposal is the re- position rate of reactant, in order to prevent a sudden rise of
use of steam generated from the quenching cell. At an the reactor pressure due to possible ‘‘flash decomposition’’ of the
industrial scale, the steam could be re-used by other steps reactant particles in the molten salt. A sudden decrease of the
(such as hydrolysis step). In the auxiliary equipment, vapor reactor pressure could also lead to flooding or spouting of bubbles
flowing down through a pipe of a vertical heat exchanger within the liquid. Prior to steady-state continuous operation,
would be cooled to liquid that flows up through the shell side
of the heat exchanger. The condenser should provide rapid 1 mole H2, Cooling water, 0.5 moles O2,
cooling of the vapor and prevention of any toxic gas release to 25ºC heated, 60ºC 25ºC
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
1 mole H2, Cooling water, 0.5 moles O2,
quantity released by O2 is listed in Table 2. Table 5 shows the 450ºC 20ºC 530ºC
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 Fig. 4 – Heat recovery from hydrogen and oxygen
an auxiliary gas for O2 detection in a lab scale (note: in a future production reactors.
 Author's personal copy

international journal of hydrogen energy 33 (2008) 5439–5450 5449

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) P (abs) Run time
3 3
Mol/h Nm /h Mol/h Kg/h m /h atm h
62.5 0.7 31.25 781 0.781 1–2 2

tests should be performed under batch operation of a continuous authors [38,39] These continued improvements will be
flow reactor, in order to assess the dependency of reaction necessary to raise the overall thermal efficiency of the Cu–Cl
kinetics on scale-up, i.e., decomposition rate of reactant particles cycle, relative to other thermochemical cycles that have been
and the removal of oxygen and molten salt. reported in the International Journal of Hydrogen Energy
In the processing of oxygen gas, trace amounts of CuCl [40–42], which have advanced further towards commercial
vapor may be present in the oxygen gas after the oxygen deployment for nuclear-based hydrogen production.
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- 7. Conclusions
ature CuO$CuCl2 particles. In this way, CuCl would condense
and return back to the oxygen production reactor. The copper–chlorine cycle is a promising thermochemical
Further to past studies of Lewis [12,22], the decomposition cycle for nuclear-based hydrogen production. Aspen Plus
of CuCl2 is much slower than the consumption rate of Cl2 by simulations [22,38] have indicated potentially up to 53%
CuO. Since CuO$CuCl2 is a compound rather than a mixture of thermal efficiency of the Cu–Cl cycle, although 43% is more
CuO and CuCl2, the chlorine atoms produced would be realistic, when losses due to engineering equipment operation
consumed at once by the bonded CuO neighbor in a distance are included. Its scientific feasibility has been demonstrated
of nanometers. It is expected that the decomposition process and all thermal reactions go to completion with minimal side
consists of a single two-step reaction, rather than two side reactions. Between each step of the Cu–Cl cycle, heat
reactions. Then significant amounts of chlorine gas may not exchangers are needed for heat input/recovery and fluid
appear during the decomposition of CuO$CuCl2. transport to different parts of the thermochemical cycle. Heat
However, it is also possible that unreacted CuCl2 in the exchangers are typically located before and after each reactor
hydrolysis reaction (step 4) may be introduced into the oxygen to supply fluid temperatures required for each chemical
production reactor, if it is entrained by CuO$CuCl2 particles. reactor.
This unreacted CuCl2 may decompose, producing chlorine gas The oxygen production step has the highest temperature
and CuCl. It would be exceedingly difficult to separate requirement in the cycle (530  C). This paper has examined
CuO$CuCl2 particles from effluent particles arriving from the the heat requirements of the oxygen production and other
upstream reactor. Thus, it is critical to effectively control the steps within the Cu–Cl cycle. Heat supply is required at
yield of CuO$CuCl2 in the upstream hydrolysis reaction various temperatures throughout the cycle, so effective heat
(step 4), so the ratio of CuCl2 to CuO$CuCl2 must be as low as matching between endothermic and exothermic reactors is
possible entering the oxygen production reactor. needed for efficient operation. This paper has examined the
Another two possible impurities in the oxygen gas are trace heat matching between steps of the Cu–Cl cycle, in efforts to
amounts of HCl gas and H2O vapor. They might enter the recover as much heat as possible and minimize the net heat
oxygen production reactor if they are entrained by the reac- supply to the cycle, thereby improving its overall efficiency.
tant particles CuO$CuCl2. In the upstream hydrolysis reactor This paper has also examined the thermal design issues,
(step 4), HCl gas is a product and H2O is a reactant. If the major engineering challenges and corresponding solutions
hydrolysis reaction is not fully completed, H2O steam will mix related to the oxygen production reactor.
with HCl gas to exit the hydrolysis reactor [12,38].
The mixture of HCl and H2O entrained by the reactant
particles CuO$CuCl2 is an engineering concern because of the
strong corrosive nature of the gas mixture and the re-use of Acknowledgements
steam. Particularly, a more corrosive HCl acid mist may form
during the cooling process of oxygen. The best method of Financial support from Atomic Energy of Canada limited
preventing the presence of H2O in the CuO$CuCl2 particles is (particularly Dr. S. Suppiah and Dr. R. Sadhankar) and the
to ensure that H2O is completely consumed in the upstream Ontario Research Excellence Fund is gratefully acknowledged.
reaction to produce CuO$CuCl2. However, the hydrolysis
reaction is not easily controlled to full completion without
references
using excess steam [12,38]. In principle, although the steam
can be internally recycled to the hydrolysis reactor for steady-
state operation, to extract H2O steam from HCl gas is an
[1] Terada A, Kubo S, Okuda H, Kasahara S, Tanaka N,
engineering challenge, and the extent to which steam is re-
Iwatsuki J, et al. Development of hydrogen production
cycled will influence the thermal efficiency. The technology to technology by thermo-chemical water splitting IS process
re-cycle steam and prevent the presence of HCl and H2O in pilot test plan. Journal of Nuclear Science and Technology
CuO$CuCl2 particles is currently the investigation by the 2007;44(3):477–82.
 Author's personal copy

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

[2] Anzieu P, Carles P, Le Duigou A, Vitart X, Lemort F. The Ontario, Canada: University of Ontario Institute of
sulphur–iodine and other thermochemical process studies at Technology; December 8, 2006.
CEA. International Journal of Nuclear Hydrogen Production [23] Wang Z, Naterer GF, Gabriel K. Hydrogen production with
and Applications 2006;1(2):144–53. a Cu–Cl cycle: analysis of thermal efficiency. In: Canadian
[3] Moore R, Parma E. A laboratory-scale sulfuric acid hydrogen workshop on hydrogen production from non-fossil
decomposition apparatus for use in hydrogen production sources. Oshawa, Ontario: University of Ontario Institute of
cycles. In: American nuclear society annual meeting. Boston, Technology; May 30, 2007.
Massachusetts; June 24–28, 2007. [24] Olivier J, Vaxelaire J. The prediction of filter belt press
[4] Schultz K. Thermochemical production of hydrogen from dewatering efficiency for activated sludge by
solar and nuclear energy, technical report for the Stanford experimentation on filtration compression cells.
global climate and energy project. Sandiego, CA: General Environmental Technology 2004;25(12):1423–30.
Atomics; 2003. [25] Suppiah S, Li J, Sadhankar R, Kutchcoskie KJ, Lewis M.
[5] Yamawakia M, Nishiharab T, Inagakib Y, Minatoc K, Study of hybrid Cu–Cl cycle for nuclear hydrogen
Oigawac H, Onukib K, et al. Application of nuclear energy for production. In: Third information exchange meeting on
environmentally friendly hydrogen generation. International the nuclear production of hydrogen. Orai, Japan; October
Journal of Hydrogen Energy 2007;32:2719–25. 2005.
[6] Sadhankar RR, Li J, Ryland D, Suppiah S. Hydrogen generation [26] Tomo O, Etsuro M, Hiroyoshi K, Chikafusa S, Akira K. An
using high-temperature nuclear reactors. In: 55th Canadian empirical model of dewatering efficiency for gravity
chemical engineering conference. Toronto; October 2005. thickened or membrane mechanical thickened sludge.
[7] Lewis MA, Serban M, Basco JK. ANS/ENS exposition; Journal of Japan Water Works Association 2007;76(1):2–14
November 2003. New Orleans. [in Japanese].
[8] Carty RH, Mazumder M, Schreider JD, Panborn JB. GRI report [27] De Micco G, Bohé AE, Pasquevich DM. A thermogravimetric
80-0023. Thermochemical hydrogen production, vol. 1. study of copper chlorination. Journal of Alloys and
Chicago, IL 60616: Gas Research Institute for the Institute of Compounds 2007;437:351–9.
Gas Technology; 1981. [28] Hasuike H, Yoshizawa Y, Suzuki A, Tamaura Y. Study on
[9] Fujii K, Kondo S, Mizuta Y, Oosawa T, Kumagai. Advances in design of molten salt solar receivers for beam-down solar
Hydrogen Energy 1982;3:553–6. concentrator. Solar Energy 2006;80(10):1255–62.
[10] Knoche KF, Schuster P, Ritterbex T. Thermochemical [29] Le Brun C. Molten salts and nuclear energy production.
production of hydrogen by a vanadium/chlorine cycle. II: Journal of Nuclear Materials 2007;360(1):1–5.
experimental investigation of the individual reactions. [32] Klinzing GE, Marcus R, Rizk F, Leung LS. Pneumatic
International Journal of Hydrogen Energy 1984;9:473–82. conveying of solids: a theoretical and practical approach. 2nd
[11] Granovskii M, Dincer I. Rosen MA, Pioro I. Exergy analysis ed. Springer; March 31, 1997.
of a system using a chemical heat pump to link [33] Roberts WL, Campbell TJ, Rapp GR, Wilson WE. Encyclopedia
a supercritical water-cooled nuclear reactor with of minerals. 2nd ed. Van Nostrand Reinhold; 1990.
a thermochemical water splitting cycle. In: 13th [34] Asteman H, Spiegel M. Investigation of the HCl (g) attack on
International conference on emerging nuclear systems pre-oxidized pure Fe, Cr, Ni and commercial 304 steel at
Istanbul. Turkey; June 3–8, 2006. 400  C. Corrosion Science 2007;49:3626–37.
[12] Serban M, Lewis M, Basco J. Kinetic study of the hydrogen [35] Frenken JW, Willems MH. Process for spraying
and oxygen production reactions in the copper–chloride molten material. US Patent 3988398, Issued on October 26,
thermochemical cycle. In: AIChE 2004 spring national 1976.
meeting. New Orleans, LA; April 25–29, 2004. [36] Arana D, Lunas L. Apparatus and process to extract heat and
[13] Bertel E. Nuclear energy the hydrogen economy. Nuclear to solidify molten material particles. US Patent 6349548,
Energy Agency News 2004;22:10–3. Issued on February 26, 2002.
[14] Duffey R, Miller A. From option to solution: nuclear [37] Perry K, Philippe D. Apparatus and method for atomising
contribution to global sustainability using the newest a liquid and granulating a molten substance, Patent WO/
innovations. In: World nuclear association symposium. 2000/016890, Filed on September 23, 1999.
London, UK; September 2002. [38] Lewis M. Recent advances in hydrogen production at the
[15] Duffey R. Green atoms. Power and Energy 2005;2(2):8–12. Argonne National Laboratory. In: ORF workshop: thermo-
[16] Dincer I. Technical, environmental and exergetic aspects of mechanical design of nuclear-based hydrogen production.
hydrogen energy systems. International Journal of Hydrogen Oshawa, Canada: University of Ontario Institute of
Energy 2002;27(3):265–85. Technology; December 20, 2007.
[17] Mirabal ST, Ingley HA, Goel N, Goswami Y. Utilization of [39] Wang ZL, Daggupati VN. Large lab scale design of Cu–Cl
domestic fuels for hydrogen production. International thermochemical H2 production cycle. In: ORF workshop:
Journal of Power and Energy System 2004;24(3):239–45. thermo-mechanical design of nuclear-based hydrogen
[18] Yildiz B, Kazimi MS. Technical report. MA: Massachusetts production. Oshawa, Canada: University of Ontario Institute
Institute of Technology; 2002. of Technology; December 20, 2007.
[19] Rosen MA. Energy and exergy ‘‘Analyses of electrolytic [40] Yildiz B, Kazimi MS. Efficiency of hydrogen production
hydrogen production’’. International Journal of Hydrogen systems using alternative energy technologies. International
Energy 1995;20(7):547–53. Journal of Hydrogen Energy 2006;31:77–92.
[20] Rosen MA, Scott DS. Exergy analysis of hydrogen production [41] Forsberg CW. Hydrogen, nuclear energy and advanced high-
from heat and water by electrolysis. International Journal of temperature reactor. International Journal of Hydrogen
Hydrogen Energy 1992;17(3):199–204. Energy 2003;28:1073–81.
[21] Naterer GF. Heat transfer in single and multiphase systems. [42] Kasahara S, Kubo S, Hino R, Onuki K, Nomura M,
Boca Raton, FL: CRC Press; 2002. Nakao SI. Flowsheet study of the thermochemicalwater-
[22] Lewis M. Cu–Cl cycle research and development at the splitting iodine–sulfur process for effective hydrogen
Argonne National Laboratory, Canadian hydrogen workshop production. International Journal of Hydrogen Energy 2007;
on hydrogen production from non-fossil Sources. Oshawa, 32:489–96.