A review on high temperature thermochemical heat energy storage

P. Pardo
a
, A. Deydier
a
, Z. Anxionnaz-Minvielle
a,n
, S. Roug
a
, M. Cabassud
b,c
, P. Cognet
b,c
a
CEA, LITEN, LETH, 17 rue des Martyrs, 38054 Grenoble, France
b
Universit de Toulouse; INPT, UPS, Laboratoire de Gnie Chimique, 4, Alle Emile Monso, F-31432 Toulouse, France
c
CNRS, Laboratoire de Gnie Chimique, F-31432 Toulouse, France
a r t i c l e i n f o
Article history:
Received 9 December 2011
Received in revised form
18 October 2013
Accepted 19 December 2013
Available online 5 February 2014
Keywords:
Thermal Energy Storage (TES)
Thermochemical
Reversible reactions
Concentrated solar plant (CSP)
a b s t r a c t
Solar thermal energy represents an increasingly attractive renewable source. However, to provide continuous
availability of this energy, it must be stored. This paper presents the state of the art on high temperature (573
1273 K) solar thermal energy storage based on chemical reactions, which seems to be the most advantageous
one for long-term storage. The paper summarizes the numerical, experimental and technological studies done
so far. Each system is described and the advantages and drawbacks of each reaction couple are considered.
& 2014 Elsevier Ltd. All rights reserved.
Contents
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
2. Thermal energy storage: denitions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
2.1. Energy density. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 593
2.2. Comparison of different TES systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
3. State-of-the-art on solar thermal energy storage based on chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
3.1. Technical disciplines and skills for developing a thermochemical TES system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
3.2. Hydrogen systems: metallic hydrides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
3.3. Carbonate systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
3.3.1. Calcite calcination/carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
3.3.2. Cerrusite calcination/carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
3.4. Hydroxide systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
3.4.1. Hydration/dehydration of magnesium oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
3.4.2. Hydration/dehydration of calcium oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
3.5. The REDOX system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.5.1. Oxidation/decomposition of barium peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.5.2. Other oxidation/decomposition peroxide couples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
3.6. Ammonia system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.6.1. The ammonium hydrogen sulfate system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
3.6.2. Dissociation/synthesis of NH
3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
3.7. Organic systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
3.7.1. Methane reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
3.7.2. Cyclohexane dehydrogenation benzene hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
3.7.3. Thermal dissociation of sulfur trioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
3.8. Summary of case studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/rser
Renewable and Sustainable Energy Reviews
1364-0321/$ - see front matter & 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.rser.2013.12.014
n
Corresponding author.
E-mail address: [email protected] (Z. Anxionnaz-Minvielle).
Renewable and Sustainable Energy Reviews 32 (2014) 591610
1. Introduction
The use of renewable energy is essential today to decrease
the consumption of fossil resources and to decrease the pro-
duction of carbon dioxide partly responsible for the greenhouse
effect [1]. Solar energy constitutes an attractive source of
energy because it is both free and endless. It can be converted
into electricity by means of a concentrated solar plant (CSP)
composed of four elements: a concentrator, a receiver, a trans-
port media system and a power conversion machine. However,
the major drawback of this energy is its intermittence. One
solution is to develop thermal energy storage (TES) systems,
which will store heat during the sunshine periods and release it
during the periods of weak or no solar irradiation. A CSP
equipped with a TES system would continuously supply elec-
tricity. Thus, the development of an efcient and cost-effective
TES system is crucial for the future of this technology.
At the moment, three kinds of TES systems are known: the
sensible heat storage, the latent heat storage and the thermo-
chemical heat storage [1,2]. Sensible heat storage systems are the
most mature technologies. They have been and are still being used
in industrial plants, most notably in Spain, with the PS10 and PS20
projects (2007 and 2009) or the Andasol 1 and 2 plants (2008), but
also in the USA, e.g. with Solar One (1982) [2]. Among the other
techniques, thermochemical heat storage seems to be a valid
option to be used as a TES system [3,4]. However, in order to be
efcient and cost-effective, the appropriate reversible chemical
reactions have to be identied [5]. Recently, two reviews focusing
on low temperature (273573 K) TES systems based on chemical
reactions have been published. They respectively concern long-
term sorption solar energy storage [6] and chemical heat pump
technologies and their applications [7]. Cot-Gores et al. [8] also
published a state-of-the-art on sorption and chemical reaction
processes for TES application and some of the high temperature
reactions are listed in the Felderhoff et al. article [9].
The purpose of this work is to provide a state-of-the-art of
the thermochemical heat storage solutions, focusing on tem-
peratures comprised between 573 K and 1273 K. General deni-
tions as well as the disciplines involved in the development of a
TES system are detailed. The experimental facilities at pilot or
laboratory scales and their applications are reviewed and
described. The systems have been classied according to their
reaction family (carbonation, hydration, oxidation) since they
often share the same advantages and drawbacks. The main data
have been compiled in 2 graphs (densities versus temperature)
and a general table which summarizes the literature data about
reversible reactions studied for thermochemical storage appli-
cations is given.
2. Thermal energy storage: denitions
Thermal storage systems have to be used to correct the existing
mismatch between the discontinuous solar energy supply and the
continuous electricity consumption [1]. They involve at least three
steps: heat charging, storage and discharging. Three mechanisms
of storing thermal energy exist. They are described below.
In sensible heat storage systems, during the charging step, solar
energy is used to heat a uid or a solid medium, thus, increasing
its energy content. Then, the medium is stored at the charging
step temperature. When this energy is released (discharging step),
the medium temperature decreases. The sensible heat stored
is associated with this increase or decrease of temperature.
The thermal energy stored by sensible heat can be expressed as
Q mCpT
Where m is the mass of the material (kg), Cp is the specic heat
over the temperature range operation (kJ kg
1
K
1
) and T is the
temperature difference (K). Two reviews list the materials and the
works done for high temperature thermal energy storage based on
sensible heat [1,2].
In latent heat storage, during the charging step, solar energy
can be used as the heat source that initiates a phase change. Then,
the medium is stored at the charging step temperature into its
new phase. When this energy is released (discharging step), the
medium phase changes into the rst state. The latent heat stored is
associated with this phase change. The thermal energy stored in
phase change material can be expressed as:
Q mL
Where m is the mass of the material (kg) and L is the latent heat of
the material (kJ kg
1
).Many publications deal with latent TES
systems. For instance, a review lists the materials, the heat transfer
analysis and the applications [10]; another one lists both the
materials and the works done for high temperature thermal
energy storage based on phase change material (PCM) [11].
The reactions involved in the thermochemical heat storage
system are reversible ones:
AH
r
3BC
Heat is stored during the endothermic reaction step and
released during the exothermic one. The thermochemical heat
stored is linked to the reaction enthalpy. During the charging step,
thermal energy is used to dissociate a chemical reactant (A), into
products (B) and (C). This reaction is endothermic. During the
releasing step, the products of the endothermic reaction (B and C)
are mixed together and react to form the initial reactant (A). This
reaction is exothermic and releases heat. The products of both
Nomenclature
A product A [dimensionless]
B Product B [dimensionless]
C product C [dimensionless]
Cp specic heat of the media, kWh kg
1
K
1
or kJ kg
1
K
1
D
m
gravimetric energy density, kWh kg
1
D
v
volumetric energy density, kWh m
3
K thermodynamic equilibrium constant [dimensionless]
L latent enthalpy, kWh kg
1
M mass of media, kg
n
A
mol number of product A, mol
P
u
useful power, kW
Q thermal energy stored, kWh
T temperature of the system, K
T
n
turning temperature, K
V volume of media, m
3
H
r
reaction enthalpy, kWh mol
1
or kJ mol
1
t time difference, s
T temperature difference, K
S
r
reaction entropy kJ K
1
thermal efciency [dimensionless]
advantages level of importance (high,
medium, low) [dimensionless]
drawbacks level of importance ( high,
medium, low) [dimensionless]
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 592
reactions can be stored either at ambient temperature or at
working temperature. The thermal energy stored in thermoche-
mical material can be expressed as:
Q n
A
H
r
Where n
A
is the mol number of the reactant A (mol) and H
r
is the
reaction enthalpy (kWh mol
A
1
). The simplied scheme of a TES
system based on chemical reactions is presented on Fig. 1.
2.1. Energy density
In this paper, the energy density is assessed from the endother-
mic reactant (A) mass or volume. The energy density can be
dened in two ways. The rst one and also the most used is the
volumetric energy density, expressed as:
D
v
Q=V
Where D
v
is the volumetric energy density (kWh m
3
), Q is
the stored thermal energy (kWh) and V is the storage material
volume (m
3
).
In case of G/S reactions, if the A product is a gas, the
temperature and pressure conditions have to be specied. If the
A product is a solid, it is important to know which property among
the true density, the apparent density or the bulk density is being
used. True density is dened as the material density without
porosity. Apparent density is dened as the average density of the
material and includes the volume of pores within the particle
boundary. Bulk density is dened as the density of the packed bed
of particles. Once this property is known, the volume can be
assessed. To be rigorous, the volumetric energy density should be
calculated with the biggest volume or the installation volume.
The second denition is that of gravimetric energy density,
expressed as
D
m
Q=m
Where D
m
is the mass energy density (kWh kg
1
), Q is the stored
thermal energy (kWh) and m is the storage material mass (kg).
Both energy densities are important in order to estimate the
size and the cost of the TES system.
Table 1
Characteristics and comparison of the thermal energy storage systems [1].
Sensible heat storage system Latent heat storage system Thermochemical storage system
Energy density
Volumetric density Small 50 kWh m
3
of material Medium 100 kWh m
3
of material High500 kWh m
3
of reactant
Gravimetric density Small 0.020.03 kWh kg
1
of material Medium 0.050.1 kWh kg
1
of material High 0.51 kWh kg
1
of reactant
Storage temperature Charging step temperature Charging step temperature Ambient temperature
Storage period Limited (thermal losses) Limited (thermal losses) Theoretically unlimited
Transport Small distance Small distance Distance theoretically unlimited [12]
Maturity Industrial scale Pilot scale Laboratory scale
Technology Simple Medium Complex
Fig. 1. Simplied scheme of a TES system based on chemical reactions.
Thermochemical
TES system
Fig. 2. Technical disciplines necessary to the development of a TES system based on chemical reactions [4].
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 593
2.2. Comparison of different TES systems
To compare the three different TES systems, six parameters
are considered: the energy density, the storage temperature,
the storage period, the material transportation possibility, the
maturity of the TES system and the complexity of associated
technologies.
The characteristic data of each storage system are given in
Table 1.
Thermochemical storage systems have several advantages.
Their energy densities are 5 to 10 times higher than latent
heat storage system and sensible heat storage system respec-
tively. Both storage period and transport are theoretically un-
limited because there is no thermal loss during storage, as
products can be stored at ambient temperature. Thus, these
systems are promising to store solar thermal energy during a
long-term period. Nevertheless, unlike sensible and latent heat
storage systems there is only little experience feedback on
thermochemical storage.
3. State-of-the-art on solar thermal energy storage based on
chemical reactions
3.1. Technical disciplines and skills for developing a thermochemical
TES system
Thermochemical TES systems are still at a very early stage of
development. Most of the studies are done at laboratory scale.
Considerable amount of time, money and efforts are required
before a commercially viable system becomes operational. The
technical disciplines identied by Garg et al. [4] to develop a
thermochemical TES system are updated and presented on Fig. 2.
Usually, the rst step to develop a thermochemical TES system
is the selection of the reaction and the study of its chemical
characteristics such as the reversibility, the rate of reaction, the
operating conditions (P and T) and the kinetic properties. Went-
worth and Chen [5] reported that the following criteria ought to be
respected for choosing the most suitable chemical reaction in the
thermochemical TES system:

The endothermic reaction used for heat storage should occur at

a temperature lower than 1273 K.

The exothermic reaction used to recover heat should occur at a

temperature higher than 773 K.
Large enthalpies of reaction and a product of small molar
volume are required to maximize the storage capacity
(500 kWh m
3
).

Both reactions should be completely reversible, with no side

reactions, and have high yields in order to use the materials
over a long period of time.

Both reactions should be fast enough so that the absorption of

solar energy and heat release can be carried out rapidly.

The chemical compounds of both reactions should be easily

handleable.

When stored, the chemical compounds should not react with

their environment.

Experiment feedback on the reaction is required to use a well-

known chemical process.

Low costs should be required.

Some papers list reversible reactions which can be used for a
TES system [35,13]. Usually, their characteristics are reactant
family, reaction enthalpy and turning temperature. For a reversible
reaction of the type aA3bBcC and a given pressure, the turning
temperature T
n
is dened as the temperature at which the reaction
rate constant K is equal to 1, and is approximated as T
n
H
r
/Sr.
As Ko1 when T4T
n
and K41 for ToT
n
[4,5]. The turning
temperature T
n
may help knowing the required temperature
conditions to carry out both endothermic and exothermic reac-
tions [4,5]. The study of chemistry properties allows the determi-
nation of the required operating conditions. Then, the chemical
engineering work can start with the choice of the reactor technol-
ogy, the material, the operating process plant design and the
system analysis.
The following state-of-the-art underlines the different reactions
which were or are studied for a thermochemical TES plant. These
reactions are classied in six systems which are illustrated in Fig. 3.
3.2. Hydrogen systems: metallic hydrides
The general form of a reaction using a metal M, is
MH
n
H
r
3Mn=2H
2
Usually, the reversible metallic hydride reactions are used to store
hydrogen. In fact, one of the rst research works were performed in
the automotive industry for the hydrogen motor [14]. They led to
the design of reactor before being used for heat pumps [15] and,
in the beginning of the 90s, for the thermal energy storage [14].
Fig. 3
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 594
Three metallic hydrides have been studied for the thermal energy
storage in concentrated solar plants: lithiumhydride (LiH) for the TES
using its energy of phase change, calcium hydride (CaH
2
) for heat
storage at high temperature between 1223 and 1373 K and magne-
sium hydride (MgH
2
) for both applications [16].
We only focus on the reaction involving magnesium hydride
studied for a thermochemical TES application [17]. The reaction is
written as
MgH
2s
H
r
3Mg
s
H
2g
with H
r
75 kJ mol
1
:
The working temperatures range between 523 and 773 K with
a hydrogen partial pressure between 1 and 100 bar. The knowl-
edge of the H
2
dissociation (equilibrium) pressure as a function of
temperature is of fundamental importance for the use of MgH
2
/Mg
couple as storage system (Fig. 4).
In the beginning of the 90s, the rst research works start with the
magnesium hydride [17] because of its high capacity of hydrogen
storage (7.7 wt%) [16]. Nevertheless, using magnesium hydride
involves major problems like slow kinetics and transfer limitations
for large quantities of products. A paper reviews the works done for
TES application [18]. In order to improve the rate of chemical
reactions, the Mg powder was doped with a commercial Ni powder
(410 wt%) and a Fe-powder (50 mol%). More than 1000 cycles were
achieved with the MgNi mixed powder, but a sintering phenomenon
occurred. With the Mg
2
FeH
6
powder, this phenomenon did not occur.
600 cycles were achieved without any drop in hydrogen capacity and
the working pressure was lower than the working pressure for the
pure material.
The Max-Planck institute designed and built three prototypes [18]:
a steam generator (Fig. 5), a thermochemical solar plant (Fig. 6) and a
solar cooking and cooling device.
The steamgenerator involves a MgH
2
/Mg heat storage. The volume
of the pressure vessel, closed to 20 L, is lled with a magnesium
powder doped with a Ni powder (14.5 kg). A H
2
permeable tube set in
the centre of the pressure vessel allows the hydrogen supply and the
hydrogen recovery. Pressurized water owing in a helical tube is set
into the metallic hydride for the heat recovery and the vapour
generation. The endothermic reaction can be implemented with a
ribbon heater sealed around the pressure vessel. The hydrogen
produced during the endothermic reaction is stored in six commercial
vessels. The operating conditions are at a maximal pressure of 50 bar, a
maximal temperature of 723 K and a maximal power of 4 kW.
The thermochemical solar plant is composed of a solar radiation
concentrator, a cavity radiation receiver, a Stirling engine, a hydrogen
tank pressure, a heat exchanger and a MgH
2
/Mg storage device. The
operating temperatures range between 623 K and 723 K. During the
sunshine periods, electricity is produced and heat is stored by
dissociating MgH
2
. During the periods of weak or no solar irradiation,
the hydrogen stored is supplied to the reactor to produce heat. Then,
the heat is converted into electricity by the Stirling engine.
Table 2 presents the advantages and the drawbacks of the
MgH
2
/Mg system as a thermochemical TES system.
3.3. Carbonate systems
The general reaction form is
MCO
3s
H
r
3MO
s
CO
2g
Usually, these reactions occur at high temperature (T4723 K).
The calcination/carbonation reactions are driven by the CO
2
partial
pressure and the temperature of the system. Two reversible
reactions, the calcite and the cerrusite calcination/carbonation,
were studied for a TES application. Today, most studies focus on
the CO
2
sequestration with calcium carbonate [19].
3.3.1. Calcite calcination/carbonation
The reaction is
CaCO
3s
H
r
3CaO
s
CO
2g
with H
r
178 kJ mol
1
:
The reversibility of the reaction can be used for a TES system
application, for CO
2
sequestration or for limestone production.
The working temperatures range between 973 and 1273 K with
CO
2
partial pressure between 0 and 10 bar.
Fig. 5. Steam generator process based on MgH
2
[13].
Fig. 4. Dissociation pressure curve of MgH
2
[13].
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 595
In the mid 70s, Barker [20] suggests to use this reaction for
energy storage. His work focuses on the reversibility of the
reaction. Many problems are observed with a 10 mm particle size
powder due to the loss of specic surface. Indeed, a passivation
layer is created during the carbonation and leads to a reaction
limitation by decrease of the CO
2
diffusion in the particles. In order
to solve this limitation, submicron particles have been used to
avoid diffusion problems and nally to improve the reaction
reversibility. While the material conversion reaches 93%, another
problem arises. The volumetric energetic density of the product
does not exceed 10% of the theoretical value of 35.3 kWh m
3
[21].
This huge decrease comes from the diminution of the density of
the product in bulk.
At the beginning of the 80s, the calcination reaction is operated
in two technologies of reactor: a uidized bed in a batch mode
(Fig. 7) and a continuous rotary kiln (Fig. 8) [22]. The uidized bed
works at a temperature between 873 and 1573 K with a solar
furnace useful power of 1,4 kW.
A total conversion of CaCO
3
is reached. The thermal efciency,
dened as the ratio between the sum of the sensible energy and
the reaction energy over the useful power given to the material
during t, is between 20 and 40%. It is expressed as
mCpT nH
r
=tP
u

Where is the thermal efciency ([-]), m is the initial mass of the

reactant A (kg), Cp is the specic heat over the temperature range
operation (kJ kg
1
K
1
), T is the temperature difference (K), n is
the mol number of reactant A (mol), Hr is the reaction enthalpy
(kJ mol
1
), t is the time difference (s) and P
u
is the useful
power (kW).
The rotary kiln (see Fig. 8) works at a temperature between 873
and 1573 K with a solar furnace useful power of 1.4 kW and is
inclined 51 to the horizontal. A maximal conversion of 60% of
CaCO
3
is experimentally reached with thermal efciencies ranging
from 10% to 30% [22,23]. Here, the residence times reached in the
reactor are included between 20 and 120 s for rotary speed from
4 to 25 tr min
1
.
In order to improve the energetic efciency of the reactors,
Flamant [22] identies the main causes of thermal losses and
suggests some technological improvements on both the uidization
distributor and the cooling system of the rotary kiln. According to
these proposals, Foro [25] develops an annular continuous uidized
reactor with an electrical power of 3 kW and 1 kW of useful power.
He also demonstrates the thermal decomposition feasibility in the
uidized bed.
After many years without surveys, Kyaw et al. [26] realise
a thermogravimetric study and suggest some new concepts for
the storage system [13]. A conceptual ow diagram of CaOCO
2
Fig. 6. Thermochemical solar plant [13].
Table 2
Advantages and drawbacks of the MgH
2
/Mg system.
Reaction Advantages Drawbacks
MgH
2
H
r
3MgH
2
Reversibility of the reaction (600 cycles)
No by-product
Product separation (Gas-solid)
Experiment feedback
H
2
storage
Slow reaction kinetics
Need of Fe- or Ni-doping
Sintering
Operating pressure (50100 bar)
Heat transfer (solid/wall)
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 596
energy storing system is evaluated [26]. Three ways are used to
store CO
2
:

a compressor and a tank;

a carbonation reaction with MgO; and

an adsorption reaction with zeolite.

The CaOCO
2
MgO system was the best system to convert heat
energy at 773 K to temperatures around 1273 K. The CaOCO
2
compressor system was the most suitable for storing and deliver-
ing thermal energy at the same temperature. The efciency of
CaOCO
2
-zeolite systems was strongly governed by the adsorption
power of the zeolite.
Aihara et al. [27] improved the reversibility of the reaction by
doping the material with titanium oxide (CaTiO
3
). A thermogravi-
metric study was done and showed a stabilisation of the reversi-
bility and no sintering. 10 cycles have been reached without loss of
reversibility and with a global conversion rate of 65%. The operat-
ing conditions for the carbonation and the calcination were
respectively 1023 K in nitrogen atmosphere and 1023 K with a
gas mixture of N
2
CO
2
containing 20% of CO
2
.
Meier et al. [24] developed a new solar reactor based on the
technology of the rotary kiln (Fig. 8). The objective was to produce
calcium oxide from limestone with an available power of 10 kW.
The experiments have been done with 1 to 5 mm particles size and
a conversion rate of 9098% has been reached with a thermal
efciency of 20%.
Table 3 presents the advantages and the drawbacks of the CaO/
CaCO
3
system as the thermochemical TES system.
3.3.2. Cerrusite calcination/carbonation
The reaction scheme is
PbCO
3s
H
r
3PbO
s
CO
2g
with H
r
88 kJ mol
1
:
This reaction was studied for chemical heat pump applications
[2830] in order to be combined with the CaCO
3
/CaO system. The
authors give operating temperatures from 573 to 1730 K with
partial pressure of CO
2
included between 0 and 1 bar. A thermo-
gravimetric analysis of the PbCO
3
/PbO/CO
2
system was done
to study the equilibrium relationship, the reaction reversibility
(7 cycles of carbonation without loss of reactivity were achieved)
and the kinetics of the reaction system [29]. The following
mechanism of the decomposition reaction has been proposed:
Step A: 2PbCO
3
Pb PbCO
3
CO
2
Step B: 3(PbO PbCO
3
)2(2PbO PbCO
3
)CO
2
Step C: 2PbO PbCO
3
3PbOCO
2
A packed bed reactor which combined PbO and CaO was built
to study the thermal storage performance of the chemical heat
pump [30]. The authors showed that the heat released by
carbonation of CaO was measured experimentally up to 1143 K
under a reaction pressure up to 1 atm.
Table 4 presents the advantages and the drawbacks of the PbO/
PbCO
3
system as thermochemical TES system.
3.4. Hydroxide systems
The general reaction scheme is
M OH
2s
H
r
3MO
s
H
2
O
g
These reactions occur at medium temperature, usually
523oTo723 K. The H
2
O partial pressure and the temperature
drive the hydration/dehydration reactions. Fig. 9 shows some of
couples which could be used for a thermochemical TES application.
Two reversible reactions were studied for a TES application [3,4].
These reactions are MgO/Mg(OH)
2
and CaO/Ca(OH)
2
hydration/
dehydration.
3.4.1. Hydration/dehydration of magnesium oxide
The reaction is
MgOH
2s
H
r
3MgO
s
H
2
O
g
with H
r
81 kJ mol
1
:
The preliminary studies showed that the reaction rate (forward
and backward reactions) is sufcient to be used for a TES applica-
tion [3,4]. This reaction couple is proposed for chemical heat pump
application to store and convert heat at temperatures of 370
440 K [32].
Ervin [3] made a cycling study over 500 cycles. He observed a
conversion decrease from 95% to 60% within the fortieth cycle. It
then stabilized for the next 460 cycles.
Table 3
Advantages and drawbacks of the CaO/CaCO
3
system.
Reaction Advantages Drawbacks
CaCO
3
H
r
3CaOCO
2
No catalyst
Industrial technology known for the limestone production
Material energy density (Theoretical: 692 KWh m
3
)
No by-product
Easy product separation (gas-solid)
Availability and price of the product
Agglomeration and sintering
Poor reactivity
Change of volume (105%)
CO
2
storage
Doping with Ti
Table 4
Advantages and drawbacks of the PbO/PbCO
3
system.
Reaction Advantages Drawbacks
PbCO
3
H
r
3PbOCO
2
No catalyst
Material energy density (Theoretical: 300 KWh m
3
)
No by-product
Product separation (gas-solid)
Poor reversibility
Few experiment feedback
CO
2
storage
Toxicity of the products
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 597
The following studies have been done in a Japanese laboratory
of the institute of Tokyo, the nuclear reactors laboratory. These
researches aimed at developing chemical heat pumps. The rst
kinetic study of the hydration reaction was led by Kato et al. [33]
for 10 m particles. A 4 steps mechanism between MgO
(s)
and
H
2
O
(g)
has been proposed: (i) containment of water as xed
structural, (ii) physical adsorption of water, (iii) chemical reaction
with water producing Mg(OH)
2(s)
and (iv) inert portion of water.
The kinetic parameters have been assessed and the model shows a
good accuracy with the experimental results.
Kato et al. [13] led a reversibility study in a thermobalance with a
10 nm Mg(OH)
2
powder [32]. In order to get a durable reversibility of
the reaction, the authors concluded that the system temperature had
to be between 363 and 383 K and the water partial pressure between
47.4 and 57.8 kPa. They observed a constant reversibility with a
conversion rate of 50%.
Kato et al. [34,35] have also developed a packed bed reactor
used as a chemical heat pump (Fig. 10).
The packed bed (1.8 kg Mg(OH)
2
) was suspended to a balance
in order to measure the mass change of the bed during the
reaction. An evaporator and a vacuum pump controlled the water
partial pressure in the system. A heating tube controlled the
temperature in the system. The operating conditions of dehydra-
tion reaction were a temperature of 703 K and a water partial
pressure of 14.7 kPa. Regarding the hydration reaction, several
water pressures were tested: 31.2, 47.4 and 70.1 kPa. The results
showed the possibility to use the chemical heat pump to produce
heat at 383 K.
In 2005, Kato et al. [36] developed a new heat pump which is
able to operate with partial steam pressure from 30 to 203 kPa.
Higher pressures increase the return temperature during the
hydration reaction. Here, 52 kg of Mg(OH)
2
are introduced in
Fig. 9. Equilibrium relationship for metal oxide/water reactions systems [26]. Fig. 7. Solar uidized bed reactor [19].
Fig. 8. Solar rotary kiln (a) [19] and (b) [21].
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 598
the reactor which is heated by an electrical resistor during the
dehydration reaction. For the hydration reaction, the study of the
inuence of steam partial pressure underlines that for a steam
pressure of 203 kPa, the temperatures in the reactor were close to
473 K. Later, the works [31,3739] dealt with the shaping and the
doping of the material in order to diminish the costs and the
minimum temperature for dehydration. To reduce the price of Mg
(OH)
2
, the authors used magnesium hydroxide of sea water
which they have puried and obtained a cost divided by 10.
Concerning the doping, the authors used Ni and LiCl and a
decrease of the dehydration temperature of Mg(OH)
2
(around
100 K) was observed.
Table 5 presents the advantages and the drawbacks of the MgO/
Mg(OH)
2
system as thermochemical TES system.
3.4.2. Hydration/dehydration of calcium oxide
The reaction is [40]:
Ca OH
2s
H
r
3CaO
s
H
2
O
g
with H
r
104 kJ mol
1
The operating temperatures range from 623 to 1173 K with
steam partial pressures from 0 to 2 bar. Many authors studied this
reaction for many applications: heat pump, heat storage of con-
centrated solar plants, motors preheating or electrical generation
on the moon. In the following sub-sections, these works are
classied into two categories: the heat pumps and the thermal
energy storage.
3.4.2.1. The heat pumps. Matsuda et al. [41] studied the kinetics of
both the Ca(OH)
2
dehydration and the CaO hydration in a
thermogravimetric apparatus for heat pump applications. The
study have been done with 5 m Ca(OH)
2
particles and 10 mg of
product. The following table lists the range of temperature and
steam partial pressure for both hydration and dehydration
reactions. Table 6
From the end of the 90s to the beginning of the 2000s, most of
the studies have been carried out in a Japanese institute, the
Kyushu Institute of Technology (KIT) ([4147]). These works
allowed developing and simulating the chemical heat pumps
using the couple CaO/Ca(OH)
2
. These heat pumps work in closed
Fig. 10. (a) Laboratory-scale chemical heat pump; (b) reactor bed design [30].
Table 5
Advantages and drawbacks of the MgO/Mg(OH)
2
system.
Reaction Advantages Drawbacks
Mg(OH)
2
H
r
3MgOH
2
0 No catalyst
Material energy density (Theoretical: 380 KWh m
3
)
Operating pressure (1 bar)
Good reversibility of the reaction
No by-product
Product separation (gas-solid)
No toxicity
Experimental feedback (10 years)
Availability and price of the product
Change of volume
No industrial feedback
Product reactivity (50%)
Doping
Low thermal conductivity
Table 6
Range of temperature and steam partial pressure for both hydration and dehydra-
tion reactions for the kinetic study of Mastuda et al. [41].
Reaction Temperatures (K) Steam concentration (vol%)
Dehydration 693723 1.56%
Hydration 356611 2.015.7%
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 599
system and Fig. 11 presents the principle and the operating
schemes.
3.4.2.2. The thermal heat storage. Ervin [3] was the rst to suggest
using this reaction in a thermal energy storage plant. He achieved
290 cycles with an average conversion rate of 95%. Kanzawa and
Arai [48] developed a xed bed reactor. To increase the heat
transfer during the Ca(OH)
2
dehydration, they proposed to use a
reactor with copper ns. They made a 2D unsteady state model for
the xed bed and determined the optimal distance between the
copper ns. Darkwa [49] aimed at developing an energy storage
system for the preheating of motors. Experimental and numerical
studies have been carried out and he underlined the fact that the
heat transfer into the installation limits the reaction. Azpiazu et al.
[50] studied the reversibility in a xed bed reactor with copper
ns and 20 cycles were achieved. They observed that using an air
atmosphere causes the apparition of a side reaction: the calcium
oxide carbonation.
The following studies focus on the development of a thermo-
chemical storage system for applications in solar plants.
Wereko-Brobby [51] worked on the feasibility of the storage
system applied to a 1 MWh concentrated solar plant. He suggested
using a uidized bed reactor and he obtained a storage system
yield of 45% with reactant storage temperature of 298 K. Brown
et al. [52] carried out a technical-economic survey on the devel-
opment of a thermochemical storage process. The results demon-
strate the feasibility of the process for a solar plant with an energy
efciency of 80% and an initial price for the installation of
45 $ kWh
1
th
. Fujii et al. [53] achieved a study on the kinetics of
the particles of calcium hydroxide and calcium oxide as pellets and
spheres. The work has been realized with pure products (spheres
and pellets) and doped products (pellet) with copper, zinc and
aluminum. The best results, for the reaction kinetics are obtained
with aluminum doping for an optimal concentration of 15% in
weight. Between 2010 and 2013, Schaube et al. [54,55] carried out
a survey on the feasibility of the storage process in a thermo-
dynamical solar plant. They used a xed bed reactor and simulated
a one dimensional chemical reactor in unsteady state. They
concluded that the heat transfer between the bed and the wall
was not a viable solution because the heat conductivity of the
material is too low. To improve the heat transfer, they suggested
using the circulating gas into the reactor as the heat transfer uid.
In 2012, Schaube et al. [56] worked on the physic-chemical
characterization of the products. The authors determined the
particles diameter, the specic heat, the reaction enthalpy and
the kinetics of both hydration and dehydration with a thermo-
gravimetric analysis. They achieved 100 cycles without reversi-
bility loss. Later, Schaube et al. [57,58] led experimental and
numerical studies on the technology of the xed bed reactor. They
used the reactor presented on Fig. 12 for the experimental part and
achieved 25 cycles without reversibility loss. The numerical model
in two dimensions and in unsteady state has been developed with
the COMSOL software. The authors obtained a good accuracy
between the simulated and the experimental results.
Table 7 presents the advantages and the drawbacks of the CaO/
Ca(OH)
2
system as a thermochemical TES system.
3.5. The REDOX system
The general reaction form is
M
x
O
ys
H
r
3xM
s
y=2O
2
These reactions occur at temperatures between 623 and 1373 K.
Only few studies have been made on these materials. The rst
studied couple was BaO
2
/BaO in 1978 [59] and after 30 years without
survey, DLR is interested again in these systems for storage applica-
tion in tower centrals.
3.5.1. Oxidation/decomposition of barium peroxide
The reaction is
2BaO
2s
H
r
32BaO
s
O
2g
with H
r
77 kJ mol
1
:
This reaction occurs at temperatures between 673 and 1300 K
for partial oxygen pressure between 0 and 10 bar. Preliminary
thermogravimetric studies showed the potential of BaO/BaO
2
system for a thermochemical TES application [59,60]. Some
difculties arose when trying to achieve the complete conversion
of reaction, because of mass transfer limitations and a crusting of
the material surface [60]. The kinetic equations of both forward
and reverse reactions were determined and the reaction reversi-
bility had shown a decrease after the rst cycle [59]. Recently,
Wong et al. [60] studied this couple and compared it with other
redox couples for a feasibility study in tower centrals
Fig. 12. Experimental setup of a laboratory scale of the DLR system [34].
Fig. 11. Standard type chemical heat pump [39].
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 600
Table 8 presents the advantages and the drawbacks of the BaO/
BaO
2
system as thermochemical TES system.
3.5.2. Other oxidation/decomposition peroxide couples
More recently, a study about the potential of six oxide/peroxide
couples for a thermochemical TES application has been investi-
gated by Wong et al. [61]. To assess the relevance of various
couples, a thermodynamic analysis, an engineering feasibility
study and thermogravimetric measurements have been done.
The relevant couples are: Co
3
O
4
/CoO, MnO
2
/Mn
2
O
3
, CuO/Cu
2
O,
Fe
2
O
3
/FeO, Mn
3
O
4
/MnO and V
2
O
5
/VO
2
. Nevertheless, for their
application, the most promising reaction is:
2Co
3
O
4s
H
r
36CoO
s
O
2g
with H
r
205 kJ mol
1
:
The decomposition occurs at 1123 K in a nitrogen atmosphere and
the oxidation occurs at 973 K in an air atmosphere with partial oxygen
pressure between 0 and 1 bar. This reaction has been implemented
both in a thermogravimetric balance and in a xed bed [62]. 500
cycles have been achieved and the morphologic study of the product
showed a progressive magnication of the particles progressively
during the cycles. Buckingham et al. [63] have done a numerical
analysis of packed bed parameters and operating conditions. They
Table 8
Advantages and drawbacks of the BaO/BaO
2
system.
Reaction Advantages Drawbacks
2BaO
2
H
r
32BaOO
2
Operating temperature (4001300 K)
O
2
reactant
No catalyst
No side reaction
Products separation (gas-solid)
Operating pressure (010 bar)
Incomplete conversion of both forward and reverse reactions
No experiment feedback
Table 9
Advantages and drawbacks of the Co
3
O
4
/CoO system.
Reaction Advantages Drawbacks
2Co
3
O
4
H
r
36CoOO
2
High reaction enthalpy (205 kJ mol
1
)
O
2
as a reactant
No catalyst
No by product
Reversibility (500 cycles)
Products separation (gas-solid)
Few experiment feedback
Storage of O
2
Toxicity of the products
Cost of the products
Table 7
Advantages and drawbacks of the CaO/Ca(OH)
2
system.
Reaction Advantages Drawbacks
Ca(OH)
2
H
r
3CaOH
2
0 No catalyst
Material energy density (Experimental: 300 KWh m
3
)
Reversibility of the reaction (100 cycles)
No by-product
Product separation (gas-solid)
Operating pressure (1 bar)
Availability and price of the product
Nontoxic product
Experimental feedback (10 years)
Agglomeration and sintering
Change of volume (95%)
Low conductivity
Table 10
Advantages and drawbacks of the NH
4
HSO
4
/NH
3
/H
2
O/SO
3
system.
Reaction Advantages Drawbacks
NH
4
HSO
4
Hr3NH
3
H
2
OSO
3
Material energy density (Theoretical: 860 KWh m
3
)
No catalyst
Product separation (gas-liquid)
Corrosive products
Toxic products
No experiment feedback
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 601
concluded that a packed bed design for metal oxide TES couple will
not be economically competitive and recommended to study a
moving bed design, as a rotary kiln, to improve the TES process.
Neises et al. [64] used a rotary kiln based on the work of Buckingham
et al. [63] to implement the reaction which is heated through a solar
furnace of 22 kW. They carried out a reversibility study on three
samples: pure Co
3
O
4
and two mixtures of doped Co
3
O
4
with alumina
oxide. They achieved 30 cycles and demonstrated the feasibility of the
process with an energetic density in the reactor of 95 kWh m
3
.
Table 9 presents the advantages and the drawbacks of the
Co
3
O
4
/CoO system as the thermochemical TES system.
3.6. Ammonia system
Historically, two reactions using the Ammonia system have
been studied. The rst one, studied by Wenthworth et Chen [5] is
the decomposition of NH
4
HSO
4
but only few surveys have been
carried out. The second one, studied by the Australian National
University (ANU) since 40 years, is the decomposition/synthesis of
the ammonia for thermal energy storage.
Fig. 14. Solar ammonia dissociation reactor (a) design of the cavity receiver with 15 kW
sol
and its assembly on ANU
0
s 20 m
2
dish without insulation tted; and (b) reactor in
operation on the ANU
0
s 20 m
2
dish [49].
Fig. 13. Installation of a parabolic through power plant with chemical energy
storage [49].
Fig. 15. Design of the 10 kW
th
ammonia synthesis heat recovery [49].
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 602
3.6.1. The ammonium hydrogen sulfate system
The reaction is
NH
4
HSO
4l
H
r
3NH
3g
H
2
O
g
SO
3g
with H
r
336 kJ mol
1
:
A preliminary study showed the potential of this system for
TES application [5]. The reaction occurs at 690 K and 1.46 atm.
No catalysts are required for both forward and reverse reactions.
A process owsheet was designed to carry out a thermochemical
TES process based on ammonium hydrogen sulfur cycle [5].
Prengle et al. [5] dened the thermal efciency as the ratio
between the released heat energy and the required solar energy.
The preliminary energy analysis of the cycle conrmed the
engineering feasibility of the process with a thermal efciency of
62% and a theoretical energetic density of 860 kWh m
3
.
Table 10 presents the advantages and the drawbacks of the
NH
4
HSO
4
/NH
3
/H
2
O/SO
3
system as the thermochemical TES system.
3.6.2. Dissociation/synthesis of NH
3
The reaction is
2NH
3g
H
r
3N
2g
3H
2g
with H
r
66:9 kJ mol
1
:
This reaction occurs at temperatures between 673 and 973 K and
pressures between 10 and 30 bar. The HaberBosch process is based
on this reaction for the NH
3
production since 100 years. A lot of
Fig. 16. ANU
0
s 500 m
2
paraboloidal dish concentrator [57].
Fig. 17. Schematic diagram of the EVA-ADAM process cycle for heat conversion and transportation of nuclear energy [58].
Table 11
Advantages and drawbacks of the NH
3
/N
2
/H
2
system.
Reaction Advantages Drawbacks
2NH
3(g)
H
r
3N
2(g)
3H
2(g)
Ammoniac synthesis known since 100 years (Haber-Bosch process)
Ammoniac: liquid at ambient conditions
ANU
0
s important experiment feedback (40 years)
No side reaction
H
2
and N
2
storage (gases)
Use of catalyst (Fe/Co)
Operating pressure (80200 bar)
Incomplete conversion of both forward and
reverse reactions
Fig. 18. Schematic diagram of reforming methane process cycle using carbon dioxide for heat conversion and transportation of concentrated solar energy [58].
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 603
studies (e.g.: kinetic studies by Temkin et al. [65]) have already been
done for this application (NH
3
production). Fig. 13 shows the scheme
of the installation developed and used by the Australian National
University (ANU) for a thermochemical TES application.
Both forward and reverse reactions are catalysed. The catalyst
materials used in the endothermic reactor and in the exothermic
reactor are respectively the Haldor-Topse DNK-2R [66] and
Haldor-Topse KM1 [67].
The works on a thermochemical TES system using the ammo-
nia system began with Carden [68] and Williams and Carden [69].
They assessed a theoretical energetic efciency of 90% if the
conversion rate of the ammonia into the reactor was higher than
60%. Later, the thermodynamic limitations associated with the use
of the reversible reaction of the ammonia have been studied by
Lovegrove et al. [70,71] thanks to a pseudo-homogeneous two
dimensions model of reactor. The rst solar driven high pressure
ammonia reactor of 1 kW has been successfully tested in a closed
loop system [67]. This reactor allowed the validation of a numer-
ical model to predict the temperatures in the catalyst, on the wall
and in the gas, and also the conversion rate and the product
owrates. A detailed study of a 10 MW
e
base load power plant in
Australia, has indicated that levelled electricity costs lower than
AUS $ 0.15/kWh were potentially achievable [72]. A scale-up
(Fig. 14) of the rst solar driven ammonia reactor has been done
in order to accept the full (15 kW) input from the ANU
0
s 20 m
2
dish system [66].
Fig. 15 shows the design of the ammonia synthesis heat
recovery reactor of 10 kW
th
[66].
A new 500 m
2
parabolic dish solar concentrator has been built
by the ANU in 2009 (Fig. 16). The receiver geometry was numeri-
cally optimized to improve the dissociation reaction [73]. This
numerical model can then be applied to develop an ammonia
receiver for the 500 m
2
SG4 dish concentrator.
ANU has done the most advanced works in this sector, by
working for over 40 years on the thermochemical energy storage
using the dissociation and synthesis of ammonia. ANU is also the
rst laboratory which continuously store and release energy
during 24 h thanks to its closed loop system composed of a solar
reactor of 15 kW for the dissociation reaction and a synthesis
reactor of 10 kW [75].
Table 11 presents the advantages and the drawbacks of the
NH
3
/N
2
/H
2
system as the thermochemical TES system.
3.7. Organic systems
3.7.1. Methane reforming
Reforming of methane using steam or carbon dioxide is
industrially used for the H
2
production. These reactions have also
been studied for heat transportation. There is no study about the
TES system based on the methane reforming, but this could be an
application. Both reactions are catalysed by Ni-based or Ru-based
catalysts [76].
3.7.1.1. Methane steam reforming. The reaction is
CH
4g
H
2
O
l
H
r
3CO
g
3H
2g
with H
r
250 kJ mol
1
CH
4
:
The side reaction is
CO
g
H
2
O
l
3CO
2g
H
2g
H
r
with H
r
41:2kJ mol
1
CO
:
This reaction occurs at temperatures between 873 and 1223 K
and pressures between 20 and 150 bar. In 1975, Kugelers et al. [77]
suggested to use the reaction of methane steam reforming for the
transport of the thermal energy coming from the nuclear plants. The
authors made a feasibility survey and proposed a process owsheet
(Fig. 17) with energetic efciencies between 60% and 73%. In order to
study and understand the phenomena involved during the reaction,
a rst pilot plant, EVA I, was built by Fedders et al. [78]. An
industrial-scale pilot plant EVA I/ADAM I of 300 kW was developed
in 1979 at the Intitut fr Reaktorbauelemente in Germany. 850
operating hours have been investigated. They showed the feasibility
of the energy transport system by means of the reversible reaction
[79]. More recently, a new design process (ICAR: immediate catalytic
accumulation of ionizing radiation energy) was developed by
Aristov et al [80]. The endothermic reactor is directly combined
with the nuclear reactor to improve the process efciency.
3.7.1.2. Methane reforming using carbon dioxide. Methane refor-
ming using carbon dioxide presents an advantage for a TES
Fig. 19. Schematic of the solar chemical receiverreactor [64].
Table 12
Advantages and drawbacks of the CH
4
/CO
2
and the CH
4
/H
2
O systems.
Reaction Advantages Drawbacks
CH
4
H
2
OH
r
33H
2
CO Industrial feedback
High reaction enthalpy (250 kJ mol
1
)
Gas phase
H
2
storage
Cost of CH
4
Side reactions
Use of catalyst
Low reversibility
CH
4
CO
2
H
r
32H
2
2CO
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 604
application compared to the steam reforming process. It does not
involve water evaporation [76].
The carried out reaction is
CH
4g
CO
2g
H
r
32CO
g
2H
2g
with H
r
247 kJ mol
1
CH
4 :
The side reaction is:
CO
2g
H
2g
H
r
3CO
g
H
2
O
g
with H
r
41:2 kJ mol
CO
1
:
Fig. 18 shows the process owsheet. During the endothermic
reaction, methane and carbon dioxide are decomposed at a
temperature between 973 and 1133 K and absolute pressure of
3.5 bar to form hydrogen and carbon monoxide. Edwards and
Maitra [81] outlined the potential of this reforming for TES
application. Edwards et al. [82] achieved a technical-economic
survey in order to evaluate the energetic efciencies of two
different processes for a production of 100 MWe. The rst one
works in closed loop (Solar/Rankine cycle plant) and the second
one in open loop (Solar/Gas turbine combined cycle). Both cases
have energetic efciencies of 33.6% and 44.6%.
Later, the DLR [83] developed a solar reactor of 300 kW to
implement the reforming reaction (Fig. 19). This solar reactor has
been used in a global test loop at the WIS (Weizmann Institute of
Science) in Rehovot, Israel. Nevertheless, in spite of good conver-
sion rate of methane, many problems of catalyst deactivation
appeared due to a deposit of sodium.
Table 12 presents the advantages and the drawbacks of the
CH
4
/CO
2
and the CH
4
/H
2
O systems as thermochemical TES system.
3.7.2. Cyclohexane dehydrogenation benzene hydrogenation
The carried out reaction is
C
6
H
12g
H
r
3C
6
H
6g
3H
2g
with H
r
206 kJ mol
1
:
This reaction is well known in the chemical industry and the
reactor technologies to carry out both forward and reverse reactions
are known. During the charging step, the cyclohexane is heated up to
566 K at 1 bar at which the endothermic reaction occurs. The
decomposition reaction products are hydrogen (gas) and benzene
(gas). During the storing step, benzene can be stored as a liquid at
atmospheric pressure and hydrogen has to be compressed and stored.
During the discharging step, benzene and hydrogen are mixed at
610 K and 70 bar to generate heat and the initial cyclohexane. Both
forward and reverse reactions are catalysed [4]. Process simulations of
chemical heat pumps were investigated to improve the coefcient of
performance (COP) [80,84].
Table 13 presents the advantages and the drawbacks of the
C
6
H
12
/C
6
H
6
system as the thermochemical TES system.
Table 13
Advantages and drawbacks of the C
6
H
12
/C
6
H
6
system.
Reaction Advantages Drawbacks
C
6
H
12
H
r
3C
6
H
6
3H
2
Industrial feedback
Operating temperature (580 K)
H
2
storage
Use of Catalyst
Secondary reaction
Toxic products
Reversibility
Table 14
Advantages and drawbacks of the SO
3
/SO
2
/O
2
system.
Reaction Advantages Drawbacks
2SO
3
H
r
32SO
2
O
2
Industrial feedback with the H
2
SO
4
production
Operating temperature (7731223 K)
O
2
as a reactant
Corrosive product
Toxic product
Need of catalyst
Storage of H
2
Fig. 20. Energy density versus turning temperature for the reversible reactions
studied as a TES system in the literature: (a) volumetric energy density; and
(b) mass energy density.
P. Pardo et al. / Renewable and Sustainable Energy Reviews 32 (2014) 591610 605
Table 15
Literature data about reversible reactions studied for thermochemical storage systems (temperature range of 5731273 K).
Reaction Phase Reaction enthalpy (kJ/
mol
A
)
Operating temperature
conditions
Energetic density Related works Technology References
Hydride system
MgH
2
H
r
3MgH
2
Solid-gas Hr75 kJ/mol Heat Charge: 653 K
Heat release: 503 K
580 kWh/m
3
MgH2
0.80 kWh/kg
MgH2
Kinetic study
Reversibility study
Reactor design
heat exchanger design
Review
Steam generator (3.6 kWh)
Packed bed reactor
Solar power station
Solar cooking and cooling device
Heat exchanger
[17,18]
Carbonate system
PbCO
3
H
r
3PbOCO
2
Solid-gas Hr88 kJ/mol Heat charge: 723 K
Heat Release: 573 K
303 kWh/m
3
PbCO3
0.09 kWh/kg
Equilibrium relationship
Kinetics study
TGA (thermogravimetric analysis) [2830]
CaCO
3
H
r
3CaOCO
2
Solid-gas Hr178 kJ/mol Heat charge: 1133 K
Heat release: 1153
692 kWh/m
3
CaCO3
0.49 kWh/kg
CaCO3
Reversibility
Reactivity
Reactor design
Decarbonation reactor
CO
2
capture
Review
TGA
Fluidised bed reactor
Packed bed reactor
Chemical heat pump
Horizontal rotary reactor
[13,1927]
Hydroxide system
Mg(OH)
2
H
r
3MgOH
2
O Solid-gas Hr81 kJ/mol Heat charge: 423 K
Heat release: 373 K
388 kWh/m
3
Mg(OH)
2
0.39 kWh/kg
Mg
(OH)2
Equilibrium relationship
Kinetic study
Reversibility
Reactor design
TGA
Packed bed reactor
Chemical heat pump
[3,4,3136]
Ca(OH)
2
H
r
3CaOH
2
O Solid-gas Hr104 kJ/mol Heat charge: 723 K
Heat release: 298673 K
437 kWh/m
3
Ca(OH)2
0.39 kWh/kg
Ca
(OH)2
Equilibrium relationship
Kinetic study
Reversibility
Reactor design
Simulation
Heat transfer enhancement
Cost analysis
TGA
Packed bed reactor
Chemical heat pump
[3,4,4058]
Ammonium system
NH
4
HSO
4
H
r
3NH
3
H
2
OSO
3
Liquid-
gas
Hr336 kJ/mol Heat charge: 1200 K
Heat release: 700 K
860 kWh/
m
3
NH4HSO4
0.81 kWh/
kg
NH4HSO4
Theoretical analysis
Thermodynamics analysis
Process simulation
[] [4,5]
2NH
3(g)
H
r
3N
2(g)
2H
2(g)
Gas Hr
Heat Charge
66.9 kJ/
mol
Hr
Heat Release
53 kJ/mol
Heat charge: 723 K;
P9150 bar
Heat release: 723 K;
P10300 bar
745 kWh/m
3
NH3(l)
1.09 kWh/kg
NH3(l)
Kinetic study
Process simulation
Technical and economical
feasibility study
Reactor design study
Ammonia receiver design
1 kW
chem.
Laboratory-scale
ammonia
dissociation and synthesis reactor
10 kW
chem.
Laboratory-scale
ammonia
dissociation and synthesis reactor
Ammonia receiver design for
a 500 m dish
[4,6574,87
89]
P
.
P
a
r
d
o
e
t
a
l
.
/
R
e
n
e
w
a
b
l
e
a
n
d
S
u
s
t
a
i
n
a
b
l
e
E
n
e
r
g
y
R
e
v
i
e
w
s
3
2
(
2
0
1
4
)
5
9
1

6
1
0
6
0
6
REDOX system
2Co
3
O
4
H
r
36CoOO
2
Solid-gas Hr205 kJ/mol T11431173 K 295 kWh/m
3
Co3O4
0.24 kWh/kg
Co3O4
Equilibrium analysis
Kinetic study
Mixed oxide reaction
Thermodynamic analysis
TGA
Packed bed reactor
[61,63]
2BaO
2
H
r
32BaOO
2
Solid-gas Hr77 kJ/mol T9631053 K 328 kWh/m
3
BaO2
0.13 kWh/kg
BaO2
Equilibrium analysis
Kinetic study
TGA [59,60]
Organic system
CH
4
H
2
OH
r
33H
2
CO Gas 250 kJ/mol Heat charge: 1223 K
Heat release: 803 K
7.8 kWh/m
3
CH4(g)
4.34 kg/kg
CH4(g)
Process simulation
Reactor design
Kinetic study
Energy transport
Laboratory pilot plant
Industrial size pilot plant
300 kW
transported
(EVA I/ADAM I)
[7680]
CH
4
CO
2
H
r
32H
2
2CO Gas 247 kJ/mol Heat charge: 1223 K
Heat release: 803 K
7.7 kWh/m
3
CH4(g)
4.28 kg/kg
CH4(g)
Technical and economical
feasibility study
Reactor design
Energy transport
Design of the receiver reactor
200300 kW (DLR)
[76,79,8183]
C
6
H
12
H
r
3C
6
H
6
3H
2
Liquid-
gas
Hr206.7 kJ/mol Heat charge: T590 K
Heat release: T670 K
530 kWh/m
3
C6H12(l)
0.68 kWh/kg
C6H12(l)
Process simulation analysis
in chemical heat pump
[] [4,80,84]
SO
3
system
2SO
3
H
r
32SO
2
O
2
Liquid-
Gas
Hr98 kJ/mol Heat charge: 10731273 K
Heat release: 773873 K
646 kWh/m
3
SO3(l)
0.34 kWh/kg
SO3(l)
Process analysis to produce
a continuous 100 MW
electric
power output
[] [4,85]
P
.
P
a
r
d
o
e
t
a
l
.
/
R
e
n
e
w
a
b
l
e
a
n
d
S
u
s
t
a
i
n
a
b
l
e
E
n
e
r
g
y
R
e
v
i
e
w
s
3
2
(
2
0
1
4
)
5
9
1

6
1
0
6
0
7
3.7.3. Thermal dissociation of sulfur trioxide
The reaction is
2SO
3g
H
r
32SO
2g
O
2g
with H
r
98 kJ mol
1
so
3G
:
This reaction occurs at temperatures between 773 and 1373 K
for pressures between 0.1 and 0.5 MPa. During the charging step,
the liquid sulfur trioxide is heated up to vaporization. This phase
change requires 43 kJ mol
1
SO
3 l
. The gas product is heated up to
the decomposition temperature (10731373 K), at which the
endothermic reaction occurs. The endothermic reaction has to be
catalysed, generally with V
2
O
5
[4,85]. The decomposition reaction
products are sulfur dioxide (gas) and oxygen (gas). During the
discharging step, the oxygen is added to the sulfur dioxide to
regenerate the heat (773973 K) and the initial sulfur trioxide. A
process analysis has been done by Chubb [85] to use this reaction
in a Solchem system to produce a continuous 24 h electricity
output of 100 MW with a 72 h storage. A process simulation
assessed the thermal efciency to 58% [4].
Table 14 presents the advantages and the drawbacks of the SO
3
/
SO
2
/O
2
system as the thermochemical TES system.
3.8. Summary of case studies
Several numerical, experimental and technological studies
concerning thermochemical energy storage have been found in
the literature. Fig. 20a and b plot the volumetric energy density
and the gravimetric energy density versus the turning tempera-
ture of the studied reactions. To assess the volumetric energy
density of the solid reactant, the bulk density with a packed bed
porosity of 0.5 has been chosen. Usually, a packed bed porosity of
spherical particle is between 0.4 and 0.5 [86]. The volume of pores
inside a particle is considered to be equal to zero.
Fig. 20 is extremely useful to quickly screen the candidate
reactions in the desired temperature and the energy density
ranges. Each reaction system is detailed in Table 15. Table 15 lists
the reversible reaction, the phase of the A reactant, the reaction
enthalpy by mol of reactant A, the operating temperatures, the
energy density and the related works and technologies.
4. Conclusion
This paper presents a state of the art of the current numerical
and experimental researches on chemical reactions for high
temperature thermochemical heat energy storage. Most of the
described systems were only tested on laboratory scale until now.
This paper has also offered an updated review of the high
temperature (5731273 K) thermochemical TES system which
have the potential to become an important part of sustainable
handling of energy in a close future. The following conclusions
that can be drawn are

The energy density of a thermochemical TES system

(500 kWh m
3
) is 5 to 10 times higher than latent heat
storage systems and sensible heat storage systems respectively.

Thermochemical TES systems appear to be the most promising

way to store solar thermal energy during a long-term period.
Indeed, both storage period and transport distance are theoreti-
cally unlimited because there is no loss of thermal energy during
storage as products can be stored at ambient temperature.

Laboratory-scale experiments, numerical and technological

studies have demonstrated the feasibility of several reaction
systems for a TES application.

The system involving the ammonia dissociation and synthesis

is the most mature technology for a high temperature
TES application with 40 years of researches and pilot-scale
equipment.

The dehydration/hydration of the Ca(OH)

2
/CaO couple shows a
high potential for TES application but future works need to
focus on the intensication of heat and mass transfers inside
the reactor.

For a high temperature thermochemical heat storage (CSP

application), the following chemical reactions seem to be the
most interesting ones in terms of actual development, cost and
temperature range:
MgH
2
3MgH
2
PbCO
3
3PbOCO
2
CaOH
2
3CaOH
2
O
NH
3
3N
2
H
2
Nowadays, the storage system with the reaction couple
NH
3
3N
2
H
2
is the most mature one especially with the ANU
works and their 40 years feedback. Nevertheless, recently the
reaction couple Ca(OH)
2
3CaOH
2
O appears to be promising for
thermochemical heat storage and many studies and projects
contribute to develop this system. The main barriers to remove
are linked to the reactor heat and mass transfers. As a consequence
the development of intensied heat exchanger/reactor could be
interesting to study. Mass transfer issues have also to be
addressed, especially if fast hydration and dehydration kinetics
are expected. A compromise between particle diameter and mass
transfer limitation will have to be found and future works could
focus on the functionalization of the particles, supported particles
or doping. Moreover, for G/S reactions in general, an effort should
be done on the optimization of the particle size and the reaction
bed structure to guarantee a constant heat output during the
discharging step. This optimization must be done without com-
promising, as far as possible, the system compactness.
Another area of research is the optimization of the temperature
level during charging/discharging steps. The objective is to dimin-
ish the difference of temperature between both steps to improve
the efciency and the ease to control the process and the down-
stream turbine for instance.
At present, only laboratory and pilot experiments have been
done and scale-up is an important point to address. Large-scale
experiments are necessary to prove the feasibility of the thermo-
chemical TES system for both short and long-term storage. The
process must be reversible with a constant conversion rate and
without degradation after a large number of cycles. To support the
scale-up procedure, numerical models of the storage process have
to be developed. The objective is to insert them in the whole
power plant scheme to assess the performances according to the
application case (seasonal storage, 24 h electricity production,
peak load,).
The future works should also allow the denition of a meth-
odology to choose suitable materials for a given TES application.
Technical-economic studies will be required to assess the prot-
ability of the whole TES process. Thus, storage materials, storage
equipment, control strategies of the system and applications cases
are important points to address.
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