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Solar thermochemical plant analysis for hydrogen production

with the copperechlorine cycle

S. Ghandehariun, G.F. Naterer*, I. Dincer, M.A. Rosen

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: In this article, a solar-based method of generating hydrogen from the copperechlorine
Received 6 February 2010 water-splitting cycle is developed and evaluated. An analysis is performed for solar plants
Received in revised form with different hydrogen production capacities at three locations across Canada. Operating
6 May 2010 parameters of the solar field and the storage units are presented. The thermal efficiency
Accepted 7 May 2010 and cost parameters of the hydrogen plant are also examined. A binary mixture of 60%
Available online xxx NaNO3 and 40% KNO3 is used as the molten salt for solar energy storage. Different
hydrogen production rates are analyzed. Since the solar irradiation in Calgary is much less
Keywords: than Toronto and Sarnia in the winter, it is found that a larger storage unit is required. The
Solar energy size of the storage unit increases for larger hydrogen production rates. The results support
Hydrogen production the feasibility of solar thermochemical CueCl cycle as a promising and efficient pathway
Thermochemical copperechlorine for large-scale production of hydrogen.
cycle ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction thermochemical cycle development about four decades ago,

Worldwide energy demands and environmental concerns
regarding greenhouse gas emissions have motivated the
increasing utilization of renewable energy sources. Hydrogen
production from water splitting, powered by solar energy, is
an attractive energy pathway and has the potential to be
sustainable. Current industrial production technologies have
mainly focused on steam methane reforming (SMR) using
natural gas [1]. However, SMR plants emit large quantities of
greenhouse gases [2]. Alternative pathways for the production
of hydrogen that have the potential to be clean and sustain-
able include thermochemical water splitting cycles and water
electrolysis [3,4]. Thermochemical cycles are potentially more
efficient than electrolysis for hydrogen production, since they
avoid the intermediate process of generating electricity prior
to producing hydrogen. Since the inception of
a large number of water splitting cycles have been conceptu-
alized, but few have been extensively investigated. This paper
examines the linkage of solar energy with the coppere-
chlorine (CueCl) thermochemical cycle, which is one of the
prominent cycles under investigation by Canada, the U.S. and
France.
Solar-based thermochemical cycles constitute an attrac-
tive option for large-scale hydrogen production, since they
permit a reduction or elimination of greenhouse gas emis-
sions. Such cycles allow complete recycling of chemicals,
internally within the cycle. The production of hydrogen from
a two-step thermochemical cycle based on a SnO2/SnO redox
reaction was presented by Abanades et al. [5]. The cycle
consists of a solar endothermic reduction of SnO2 into SnO(g)
and O2, followed by a non-solar exothermic hydrolysis of SnO
(s) to form H2 and SnO2(s). A thermochemical cycle based on

* Corresponding author.
E-mail address: greg.naterer@uoit.ca (G.F. Naterer).
0360-3199/$ e see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.05.028

Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
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Nomenclature S energy storage, J

s solid
aq aqueous solution
V electrical energy
cp specific heat at constant pressure, kJ/kg K
t time, h
DNI direct normal irradiation, kWh/m2 year
Wel electrical energy, kJ
g gas
l liquid Greek
Q heat 3 emissivity
Qnuc heat supplied by nuclear plant per unit mol of F solar power, W
hydrogen produced, kJ/mol H2 h heat-to-electricity efficiency
Qsol heat supplied by the solar plant per unit mol of J power output, W
hydrogen produced, kJ/molH2 r density, kg/m3

a Zn/ZnO redox reaction was studied by Steinfeld [6]. The first

endothermic step is the thermal dissociation of ZnO(s) into Zn 2. Process description of the
(g) and O2 at 2030
C, using concentrated solar energy as the copperechlorine cycle
source of process heat. The second non-solar exothermic step
is the hydrolysis of Zn(l) at 430
C to form H2 and ZnO(s). The The chemical reaction steps in the CueCl cycle are shown in
sulfureiodine (SeI) thermochemical cycle, as described by Table 1. The total heat requirement of the cycle is between 554.7
Huang and Raissi [7], consists of four processes: acid produc- kJ/mol H2 and 1363.7 kJ/mol H2, depending on the extent and
tion and separation with oxygen purification, sulfuric acid nature of the drying process [11]. A significant portion of heat
concentration and decomposition, hydro-iodic acid concen- can be recycled internally from exothermic to endothermic
tration, and hydro-iodic acid decomposition with hydrogen processes. About 116 kJ of heat is released internally within the
purification. In this process, solar energy is used for the cycle (by exothermic reactions, solidification and cooling) and
decomposition of sulfuric acid at about 1000
C [7]. Galvez 277.4 of heat is required (for endothermic reactions, drying and
et al. [8] investigated a two-step solar thermochemical cycle heating) for each gram of hydrogen produced [11] in the CueCl
based on the MgO/Mg redox reaction. The carbothermal and cycle. The heat requirement of the oxygen reactor (a key
methanothermal reductions of MgO proceeds endothermi-
cally at above 1700 and 1900
C, respectively. The second step
is steam-hydrolysis of Mg for the production of H2 and MgO. Table 1 e Chemical reaction steps in the CueCl cycle.
The feasibility of a solar thermochemical cycle based on CeO2/ Step Reaction Temperature Feed and output
Ce2O3 was experimentally demonstrated at a lab scale by (
C)
Abanades and Flamant [9]. The solar activation of Ce(IV) oxide 1 Hydrogen 450 Feed: Electrolyte Cu(s)
was performed under concentrated solar irradiation over 2000 production step þ dry HCl(g) þ Q


C, with thermal reduction by releasing O2 at reduced pres- 2Cu(s) þ 2HCl(g) / Output: H2(g) þ
sure. Then the activated Ce(III) oxide reacts completely with 2CuCl(l) þ H2(g) molten CuCl(l)
water to produce hydrogen. 2 Electrolysis step Ambient Feed: Granular CuCl(s)
4CuCl(aq) / and HCl(aq) þ V
Most thermochemical cycles require process heat at high
2CuCl2(aq) þ 2Cu(s) Output:Cu(s)slurry þ
temperatures, which restrict the availability and flexibility of
(in HCl solution) HCl(aq),CuCl2(aq) þ
existing solar thermal technologies. Recently, alternative HCl(aq)
lower temperature cycles have been developed to accommo- 3 Drying step 70 Feed: CuCl2(aq)
date solar heat sources. Such cycles can be more readily 2CuCl2(aq) / solution containing
integrated with existing solar technologies to produce 2CuCl2(s) HCl(aq) þ Q
hydrogen. The copperechlorine (CueCl) cycle in particular is 2.2H2O(l) / 2.2H2O Output: Granular
(g) CuCl2(s) þ H2O(g) þ
especially promising [10]. This thermochemical cycle consists
0.1HCl(aq) / 0.1HCl HCl(g)
of a series of chemical reactions, in which water is decom-
(g)
posed into hydrogen and oxygen via reactions involving 4 Hydrolysis step 375 Feed: Granular
intermediate copper and chlorine compounds, which are 2CuCl2(s) þ H2O(g) CuCl2(s) þ H2O(g) þ Q
recycled. / CuO*CuCl2(s) þ Output: Granular
In this article, an energy and cost analysis is conducted for 2HCl(g) CuO*CuCl2(s) þ 2HCl
hydrogen generation from the copperechlorine water-split- (g)
5 Oxygen production 530 Feed: Granular
ting cycle, using solar energy. An analysis of heat balances
step CuO*CuCl2(s) þ Q
and solar field sizes will be performed for plants with different CuO*CuCl2(s) / Output: O2(g) þ Molten
hydrogen production capacities in three cities across Canada. 2CuCl(l) þ 1/2
2(g) CuCl(l)
It will be shown that solar hydrogen production with the
Q, heat; V, electrical energy; g, gas; l, liquid; s, solid; aq, aqueous
CueCl cycle is a potentially advantageous technology that
solution.
warrants further development towards industrialization.

Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
 ARTICLE IN PRESS
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Fig. 1 e Schematic of a solar power plant with two-tank
molten salt storage.
process to split water) can be separated into two parts: (1)
heating CuO*CuCl2(s) from 375
C to 530
C (20.2 kJ/mol H2) and
(2) heat of reaction at 530
C (129.2 kJ/mol H2) [11]. Such heat
cannot be provided by current nuclear plants. Therefore, solar
energy is used to provide the heat requirement of the endo-
thermic oxygen reactor.
The heat supply for the oxygen reactor can be achieved by
a solar plant consisting of a linear parabolic collector system
developed by ENEA (Italian National Agency for New Tech-
nologies, Energy and the Environment) [12]. This has an
adequate thermal storage capability to overcome the solar
input variability. A mixture of molten salts is used as the heat
transfer fluid and storage media. Such molten salts have been
successfully used for solar power plants and they are
currently being studied at the ENEA Research Centre [12,13].
A schematic of a solar plant is illustrated in Fig. 1. It
consists of a solar parabolic concentrator, storage tanks,
circulation pumps and a heat exchanger reactor. The linear
parabolic mirrors concentrate direct solar radiation onto
a receiver pipe, absorbing radiant energy and converting it to
high temperature sensible energy of molten salts, which are
collected and sent to a hot tank for heat storage. On demand,
the hot salts are delivered to the chemical process and cooled
to lower temperature levels. After cooling, the molten salts are
sent to the cold tank and pumped to the parabolic troughs to
restart the heat collection loop. The heat exchanger reactor is
a counter-current type with molten salts on the shell side. The
molten salts from the hot storage tank of the solar plant have
an inlet temperature of about 550
C and they cool to about
500
C by heat transfer to the reacting CuO*CuCl2 that is
flowing in the inner tube.
3. Utilization of concentrated solar energy
Solar thermal technology has made significant advances in
the past few decades, especially for solar electric generating
systems (SEGS). Current solar thermal power technologies are
distinguished by the way they concentrate solar radiation, i.e.,
(1) solar tower systems, (2) solar dish systems and (3) parabolic
trough systems (see Fig. 2). Tower systems, which are also
Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
3
called central receiver systems, use a field of heliostats (two-
axis tracking parabolic mirrors) that focus the sun’s rays onto
a solar receiver mounted on top of a centrally located tower.
Dish systems use paraboloidal mirrors to focus sunlight on
a solar receiver positioned at their focus. Trough systems use
linear, two-dimensional parabolic mirrors to focus sunlight
onto a solar tubular receiver positioned along their focal line.
Parabolic solar troughs are usually aligned with their long
axes from north to south. They are mounted on supports that
allow them to track the sun from east to west across the sky.
Among current technologies, parabolic trough solar tech-
nology is a proven and low cost large-scale technology. For
example, plants with total capacity of 354 MWel are in oper-
ation in the southwestern United States (nine commercial-
scale plants, with the first built in 1984) [15]. The receiver pipe,
located on the focal line of the mirrors, is composed of two
concentric cylinders separated by a vacuum gap for thermal
insulation. The external glass cylinder represents a protective
casing, while the internal steel cylinder absorbs solar energy
by means of the heat transfer fluid. A spectrally selective
coating compound for a receiver tube, developed by ENEA to
maximize the efficiency at higher temperatures (550
C),
covers the steel pipe and guarantees maximum absorption for
solar radiation, and reduction of infra-red emissions from the
hot tubes [16]. The overall thermal efficiency, namely the
fraction of incoming solar energy delivered at the end of each
collection tube, is about 78%. This evaluation is based on an
optical efficiency of 0.835, due to a tracking error of 0.1
(0.985),
reflectance of the parabolic mirrors (0.94), transmittance of
the protecting glass (0.97) and absorptance of the ENEA
coating (0.93) [12].
4. Heat storage in the molten salt
The heat storage unit performs an important function of
transforming the intrinsically variable solar energy resource
into a fully dispatchable continuous energy source. Disconti-
nuities may be divided into four broad classes: (1) accidental,
unpredictable, generally short term, interruptions of direct
solar intensity, due to cloud movements and other factors,
during an otherwise productive day; (2) night-time idling
period; (3) poor weather days, due to adverse weather condi-
tions; and (4) seasonal variations, related to the yearly cycle
[12].
Consider the conversion of the natural distribution of solar
power, F(t)  0, into a required (uninterrupted) delivery
pattern of power, J(t)  0, based on energy storage contained
at time t (in hour) with energy S(t). Energy conservation
implies dS/dt ¼ F(t)  J(t), which after integration gives [12]
Zt1
Sðt1 Þ ¼ ½fðtÞ  jðtÞdt þ Sðt0 Þ (1)
t0
The integral of a periodic function is also a periodic func-
tion. This ensures that S(t) is also daily periodic. A minimum S
(tmin) ¼ Smin and maximum S(tmax)¼(Smax) of the function S(t)
will characterize the maximum capacity of heat storage, Q ¼
Smax  Smin. The minimum and maximum of the function S(t)
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Fig. 2 e Solar collectors: (a) tower system, (b) dish system, (c) parabolic trough system (adapted from Ref. [14]).

Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
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Table 2 e Predicted costs of different storage media [19].
Composition Commercial Cost DT Cost of storage
name ($/kg) (
C) energy at DT
($/kWh)
60/40, Na/K Solar salt 0.49 270 4.29
nitrate
7/53, Na/K Hitec 0.93 200 10.7
nitrate, 40 Na
nitrite
42/15/43, Ca/Na/ Hitec XL 3.49 200 44.4
K nitrate
are characterized by zeros of its derivative, dS/dt ¼ F(t) e J(t) ¼
0, namely for both cases, F(t) ¼ J(t). Neglecting the short time
differences between tmin, tmax and the neighbouring points at
which F(t) ¼ 0, the maximum capacity of the heat storage
becomes [12]
Z þ24
tmin
Q ¼ Smax  Smin ¼ jðtÞdt
tmax
where F(t) ¼ 0 for tmax < t < tmin þ 24. This confirms that
energy storage must supply the total energy delivered during
the period in which the sun is absent. This is a specified
fraction of the time of integrated energy, supplied by the sun.
If the required delivery pattern power is constant, J(t) ¼ W0,
then
Q ¼ W0 ½1  ðtmax  tmin Þ=24  24
During the night, F(t) ¼ 0 and J(t) > 0, so S(t) decreases until
it reaches a minimum Smin at time tmin. The point of minimum
storage occurs at the moment in which the rising sun is
capable of a delivery of a peak power equal to the required
deliverable power. The maximum of energy storage is reached
when the declining solar power again crosses the condition of
F(t) ¼ J(t) [12].
Recently, molten nitrate mixtures have demonstrated
a viable large-scale thermal storage capability, reaching
storage efficiencies higher than 99% and the ability to provide
solar heat at a constant rate, due to their high heat capacity per
unit volume [17]. Unlike organic oils, molten nitrate mixtures
are stable at high temperatures (up to 600
C), relatively inex-
pensive, widely available, not flammable, and they have minor
environmental impact. Moreover, these molten salts have
a very low vapor pressure and low corrosion rates with
common-piping materials. Inorganic nitrate salt mixtures are
the preferred storage media because the salts offer a favorable
combination of density, specific heat, chemical reactivity,
vapor pressure and cost. The three principal candidate salts
include Hitec, a ternary mixture of NaNO2, NaNO3 and KNO3
with a freezing point of 120
C; Hitec XL, a ternary mixture of
Ca(NO3)2, NaNO3 and KNO3, with a freezing point of 130
C; and
solar salt, a binary salt mixture of NaNO3 and KNO3, with
a freezing point of 220
C [18]. The prospective costs of these
three salts are presented in Table 2 [19].
The most promising molten salt for solar applications
appears to be the NaNO3/KNO3 (60/40) mixture, which has
been long tested as a solar heat carrier and heat storage
Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
5
medium up to 565
C in a Solar-Two pilot tower plant in Bar-
stow, CA, USA [15]. The properties of the mixture are as
follows: specific heat capacity cp ¼ 1529 J/kg K, density r ¼ 1739
kg/m3, and thermal storage capacity per unit volume dE/dV ¼
0.69 GJ/m3. In the next section, sample results will be pre-
sented for this molten salt in a solar CueCl thermochemical
plant.
5. Solar thermochemical plant costs
The total capital investment is the sum of the fixed-capital
investment (capital needed for manufacturing and plant
facilities) and the working capital (capital needed for the
ongoing operation). Expenses for piping, instruments, insu-
lation, foundations and site preparation are included in the
manufacturing fixed-capital investment. Fixed capital
required for chemical plant components that are not directly
related to the process is known as the non-manufacturing
fixed-capital investment. These components may include the
land, building, laboratory, transportation, shipping and
(2)
receiving facilities, machine shops and other parts of the
plant.
The working capital for an industrial plant consists of raw
materials carried in stock, finished products, accounts
receivable, cash kept on hand for monthly payment of oper-
ating expenses such as salaries and raw material purchases,
accounts payable, and taxes payable. The ratio of the working
capital to total capital investment varies with companies, but
most chemical plants use an initial working capital of 10e20%
(3)
of the total capital investment [20].
Because of the lack of data for a commercial CueCl plant,
a logarithmic relationship known as the six-tenths-factor rule
gives a preliminary reasonable approximation, for a new unit
of equipment that is similar to one of another capacity, for
which cost data is available [20]. This paper uses a ratio esti-
mate and approximates the equipment cost by scaling down
the cost that was reported previously by Giaconia et al. [21] for
the sulfureiodine cycle.
In addition to the capital investment, other important costs
are related to operating the plant and selling the products.
These costs are grouped under a general category of the total
product cost. This total product cost involves the
manufacturing costs and general expenses. Manufacturing
costs are divided into: (1) direct production costs including
expenses directly connected with the manufacturing opera-
tion; (2) fixed charges that remain nearly constant from year to
year such as taxes and insurance; and (3) plant overhead
costs, including the various services, general plant mainte-
nance, social security and life insurance, warehouse and
special facilities.
General expenses are classified into: (1) administrative
expenses including costs for executive and clerical wages,
office supplies, engineering and legal expenses; (2) distribu-
tion and marketing expenses incurred in the process of selling
and distributing the various products; (3) research and
development expenses incurred for technological advance-
ment with facilities in the plant; and (4) financing expenses
including the extra costs involved in procuring the funds
needed for capital investment [20]. Table 3 shows a summary
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dimension has been defined based on the average thermal

Table 3 e Estimated total product cost and its breakdown
[20]. power of the plant supply, as a function of the solar energy
collected. As collectors are mounted in parallel rows, it is
I Manufacturing cost Production cost þ fixed charges þ plant
necessary to consider the effect of shadows between the
overhead costs
A. Direct production About 60% of total product cost collectors during their movement with respect to the sun. As
cost a result, the irradiation available on the collector aperture for
1. Raw materials 10e50% of total product cost Toronto, Sarnia, and Calgary is respectively about 1195, 1188,
2. Operating labor 10e20% of total product cost and 1144 kWh/(m2 year) [12].
3. Direct supervisory 10e25% of operating labor For 6000 kg/day of hydrogen production, the heat
and clerical labor
requirement of the oxygen reactor is about 6.5 MW [11].
4. Utilities 10e20% of total product cost
5. Maintenance and 2e10% of fixed capital investment
Based on the solar irradiation mentioned earlier, the total
repairs surface of the solar collectors is about 68,000 m2 for Toronto.
6. Operating supplies 0.5e1% of fixed capital investment In Table 4, the main parameters of the solar plant in Toronto
7. Laboratory charges 10e20% of operating labor are reported. Figs. 4e7 illustrate daily variations of the
8. Patents and 0e6% of total product cost collected, delivered and stored power for four different days
royalties
in the year, based on irradiation data of nearby American
B. Fixed charges 10e20% of total product cost
cities in 1990 [22]. Negative values of stored energy in the
1. Depreciation 10% of fixed capital investment þ 2e3%
of building cost winter indicate that the energy stored during the day is not
2. Local taxes 1e4% of fixed capital investment enough for the thermochemical plant, and stored energy
3. Insurance 0.4e1% of fixed capital investment from the summer must be used. The energy delivered is
4. Rent 8e10% of value of rented land and constant during the day. When the energy collected is more
buildings than the delivered energy, the remaining energy is stored in
C. Plant overhead costs 5e15% of total product cost
the storage tank. Fig. 4 shows that on January 15, the
II General expenses Administrative costs þ distribution and
maximum energy stored in the storage tank is about 80 MWh
selling costs þ research and
development costs at around 4 p.m. After 4 p.m., since the collected energy is
A. Administrative costs 2e5% of total product cost less than the required energy, the stored energy is used and
B. Distribution and 2e20% of total product cost the energy stored in the tank is reduced. At midnight, the
selling costs energy stored in the tank is about 40 MWh, which will be
C. Research and 5% of total product cost used in the next day.
development costs
Fig. 5 shows that in April, unlike January, the energy
D. Financing 0e7% of total capital investment
III Total product cost Manufacturing cost þ general expenses
collected is more than the required energy for more than 10 h in
a day. The energy stored in the storage tank is much more than
a similar day in January. On April 15, more than 240 MWh is
of how costs are typically subdivided amongst various cate- stored in the tank by 7 p.m. The energy stored in the storage
gories, with reference to a solar thermochemical CueCl plant. tank is increased in the summer and on July 15, about 350 MWh
energy is stored in the tank by 8 p.m., as shown in Fig. 6. Almost
100 MWh of this stored energy is used until 7 a.m. of the next
6. Results and discussion day when the sun rises and the remaining energy can be kept
for the cold days of winter. Based on the information obtained
In this section, the dimensions and characteristics of the main from the graphs, the storage tank volume can be calculated.
components of the solar hydrogen plant will be described. The Table 5 shows the main parameters of the storage tanks
solar field characteristics, number of collectors, and the operated with the binary mixture 60% NaNO3 and 40% KNO3.
thermal storage dimensions affect the power output, level of A cost analysis has been performed for a plant with
solar irradiation and thermal performance of collectors. The a hydrogen capacity of 6000 kg/day, coupled with a solar plant
following analysis considers plants in three Canadian loca- of 6.5 MW. The working capital investment is about 15% of the
tions: Toronto, Sarnia, and Calgary. The values of direct normal total capital investment, and the fixed-capital investment is
irradiation (DNI) for these locations are about 1453, 1445, and 85%. Also, 70% of the fixed-capital investment is direct costs,
1391 kWh/(m2 year), respectively. These values are obtained
from NASA based on nearby American cities. Fig. 3 shows the
typical mean daily irradiation values for these cities. Since the
Table 4 e General parameters of a solar plant in Toronto,
plant uses parabolic trough collectors, with the sun following ON.
a system on the NeS axis, the incident radiation on the col-
Number of collectors 110
lecting plane will be lower (88% of the DNI) [12].
Total collector area (m2) 6.8  104
The plant is analyzed based on collector characteristics Collector spacing (m) 11.5
studied at ENEA: length of 100 m and aperture of 5.76 m. The Solar field area (m2) 12  104
peak thermal efficiency is 0.79, while the mean annual Solar field peak power output (MW) 44
thermal efficiency is 0.667 [12]. The space between two rows of Molten salt flow rate at peak power output (kg/s) 260
collectors (collector spacing) is two times the collector aper- Solar energy on the collector plane (GWh/year) 60.5
Solar energy transferred to molten salt (GWh/year) 40.5
ture, in order to optimize the available area minimizing the
Storage capacity (MWh) 700
shadow effect between the collectors. The solar field

Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
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7
Daily Solar Irradiation (kW h/m2day)

240
6

5 180

Power (MW )
4 120 Power collected
Power delivered
3 Toronto, ON
60 Power stored

2 Sarnia, ON
0
1 Calgary, AB 0 4 8 12 16 20 24

0 Hour of the day

1 2 3 4 5 6 7 8 9 10 11 12 Fig. 5 e Power collected, delivered, and stored on April 15,
Month 1990, in Toronto.

Fig. 3 e Daily solar irradiation distribution for three cities

in Canada.
is the heat-to-electricity power transduction efficiency
(assumed to be 0.4) [19].
including the equipment, installation, instrumentation, Fig. 8 illustrates the total area of collectors versus the
piping, electrical, service facilities and land. The remaining hydrogen production rate for the three locations. The results
30% is indirect costs, engineering and supervision, and of Sarnia are very close to those for Toronto because of similar
construction expenses. solar conditions, but quite different than for Calgary. It is
As mentioned earlier, the heat requirement of the oxygen reasonable that the total area of collectors increases with
reactor is 149.4 kJ/mol H2, which is supplied by the solar plant. a higher rate of hydrogen production, as the energy require-
The work needed for pumping the molten salt is about 40 kJ/ ment of the oxygen reactor and therefore the collected energy
mol H2 [19]. The electrical energy required for the electrolysis increases. Since the irradiation in Calgary is less than in the
step is 62.6 kJ/mol H2 (see Table 2; Ref. [11]). The thermal two other cities, the total area of collectors should be more
efficiency is defined as the ratio between energy output, in than that of Toronto and Sarnia to provide the same amount
terms of the higher heat value (HHV) of H2 (285.9 kJ/mol), and of energy for the thermochemical plant. Fig. 9 shows the
total energy consumption: energy in storage at the end of each day. Negative values show
that energy storage is not possible. The collected energy
HHVH2
h¼ ¼ 0:49 (4) during the day is not enough for the hydrogen plant, so the
Qsol þ Qnuc þ Wel =hr
stored energy is required. The maximum energy shortage for
where Qsol is the energy supplied by the solar plant, Qnuc is the Calgary is about 30 MWh more than for Toronto and Sarnia.
nuclear energy required per mol of hydrogen produced and hr Therefore, the energy storage in the summer in Calgary must
be more than that of the two other cities to compensate for the
shortage of energy in the winter.
100

80 350
Power collected 300
60
Power (MW )

Power delivered
250
Power stored
Power (MW )

40 200

150
20 Power collected
100 Power delivered
0 Power stored
50

-20 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24

Hour of the day Hour of the day

Fig. 4 e Power collected, delivered, and stored on January Fig. 6 e Power collected, delivered, and stored on July 15,
15, 1990, in Toronto. 1990, in Toronto.

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copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
 ARTICLE IN PRESS
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 0

200 300
Power collected

Energy Stored (MW h)

Power delivered 240
150
Power (MW )

Power stored 180

100 120

60 Toronto, ON
50
Sarnia, ON
0
Calgary, AB
0 -60
0 4 8 12 16 20 24 0 50 100 150 200 250 300 350
Hour of the day
Day of the Year
Fig. 7 e Power collected, delivered, and stored on October
Fig. 9 e Variation of energy in the storage tank over the
15, 1990, in Toronto.
year for three cities in Canada.

Table 5 e Parameters of the storage tanks. Hydrogen Production Rate (kg/day)

20,000
Hot Cold
tank tank
Toronto, ON
Volume (m3) 2900 2650
Salt mass (tonnes) 4528 4528 15,000 Sarnia, ON
Diameter (m) 17.5 17 Calgary, AB
Height (m) 12 11.7
Nominal salt temperature in the storage tank 550 480
(
C) 10,000

The hot tank volume versus hydrogen production rate is

plotted in Fig. 10. As the solar incoming radiation in Calgary is
5,000
much less than the two other cities in the winter, a larger
5,000 10,000 15,000 20,000 25,000
storage tank is required. The hot tank volume is increased
with a higher hydrogen production rate, because the energy Hot Tank Volume (m3)
requirement of the CueCl plant increases, so a larger tank is
Fig. 10 e Hot tank volume versus hydrogen production rate
needed to store the required energy for the winter. Fig. 11
for three plant locations in Canada.
compares the salt flow rate of the three plants in different

300
20,000 Toronto, ON
Hydrogen Production Rate (kg/day)

Toronto, ON
250 Sarnia, ON
Sarnia, ON
Salt Flow Rate (kg/s)

Calgary, AB Calgary, AB
200
15,000
150

100
10,000
50

0
5,000 0 4 8 12 16 20 24
50,000 100,000 150,000 200,000 250,000
Total Area of Collectors (m2) Hour of the Day

Fig. 8 e Variation of total area of collectors with hydrogen Fig. 11 e Variation of salt flow rate throughout the day on
production rate. February 15, 1990, for the three cities in Canada.

Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 0
550
Cold Tank Temperature (C)
500
450
400
350
0 10
Days
Fig. 12 e Cooling curve of cold storage tank.
locations. The flow rate of molten salt is varied according to
the intensity of the solar irradiation, in order to keep the
temperature at the inlet of the hot tank constant. In the
winter, solar irradiation in Calgary is much less than that in
the two other cities, so the collected energy is lower. There-
fore, to keep the molten salt temperature at a constant value,
the mass flow rate in the collectors must be less than that for
Toronto and Sarnia.
Heat loss measurements of the salt storage tanks were
performed at Solar Two project [15]. A regression analysis was
performed to develop an empirical heat loss equation from
measured values as follows:
qloss ¼ 0:00017 Tsalt þ 0:012 kW=m2

thermochemical production of hydrogen is feasible on a large-
where Tsalt is the temperature (in C) of the salt in the storage
tank. The heat loss calculation is used to determine if and
when freeze protection operation is required. The freezing
point of the molten salt is about 220
C. It has to be guaranteed
that during bad weather periods or plant outages, the salt
temperature stays well above this point. Fig. 12 shows the
result for cooling of the cold storage tank, if it is out of oper-
ation for several weeks. After 30 days without charging and
discharging the storage, the temperature will be above the
freezing point. Such a long standstill period of the system is
not expected during normal operation.
Assuming a piping insulation (with rock wool or calcium
silicate) thickness of 150 mm, with a thermal conductivity of
0.075 W/m
C, the thermal network total losses are about 800
kW, corresponding to about 120 W/m [12]. During night
conditions, it is necessary to have a flow of molten salt in the
piping equal to about 100 kg/s, to compensate for heat losses
of radiation in the receiver piping of about 50 W/m, and
radiation of the collector network, equal to about 80 W/m [12].
For the night flow circulation, the molten salt temperature is
about 480
C and the temperature difference between the fluid
leaving the tank and the fluid flowing back to the tank is 40
C
[12]. There should be a cover a highly reflective screen which is
located inside the vacuum tube and deployed during the
night-time idling period. In the daytime, the screen covers
only an unexposed angular range of the collecting tube.
A screen of 9.25 cm diameter, with an emissivity of 3 ¼ 0.02,
Please cite this article in press as: Ghandehariun S, et al., Solar thermochemical plant analysis for hydrogen production with the
copperechlorine cycle, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.05.028
ARTICLE IN PRESS
9
thermally floating between the inner tube at 290
C and the
outer glass (e ¼ 0.84) at 27
C will have a temperature of 89
C
[12]. The corresponding heat loss will be about a factor of 10
times smaller than without the screen so the radiative heat
losses of the heat collecting unit become much smaller.
7. Conclusions
This article has analyzed a solar plant coupled with a CueCl
thermochemical plant to produce hydrogen at three locations
in Canada. Several hydrogen production rates have been
20 30 considered. Since the heat requirement of the oxygen reactor
needs a higher temperature source (530
C) than currently
available with nuclear plants, the solar concentrators are used
for this endothermic oxygen reactor. Some characteristic
parameters of the solar field, have been presented. A binary
mixture of 60% NaNO3 and 40% KNO3 is considered, which
appears to be the most promising molten salt for solar appli-
cations. Based on the energy requirement of the oxygen
reactor and the energy collected by the solar plant, the
dimensions of the storage unit were predicted. Since the solar
irradiation in Calgary is much less than in Toronto and Sarnia
in the winter, a larger storage tank is required. The storage
tank size will be increased with larger hydrogen production
rates. Night flow circulation is necessary to compensate for
heat losses of radiation in the collectors. In addition, a screen
is required to bring the level of radiation heat loss down to
a much smaller level. The cost and efficiency of the plant were
also estimated. A logarithmic relationship was used for a new
unit of equipment that is similar to one of another capacity
(5) with available cost data. The results indicate that solar-based
scale and that, based on such factors as efficiency and envi-
ronmental impact, it has significant future promise.
Acknowledgements
Support of this research from the Natural Sciences and Engi-
neering Research Council of Canada (NSERC) is gratefully
acknowledged.
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