Energy Conversion and Management 86 (2014) 93–98

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Energy Conversion and Management

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

Improving powder bed properties for thermochemical storage by adding

nanoparticles
C. Roßkopf ⇑, M. Haas, A. Faik, M. Linder, A. Wörner
Institute of Technical Thermodynamics, German Aerospace Center, Pfaffenwaldring 38-40, 70569 Stuttgart, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Thermochemical storage offers interesting potential to store thermal energy, especially in the field of
Received 20 February 2014 industrial waste heat utilization or for concentrated solar power (CSP) plants.
Accepted 2 May 2014 However, at present the development of thermochemical storage technology is in its initial stage with
investigations mainly on material aspects or small lab-scale systems. With regard to its thermodynamics
and kinetics, it has been shown that the CaO/Ca(OH)2 reaction system is suitable for thermochemical heat
Keywords: storage at a temperature range of 400–600 °C. However, the behaviour in a small lab-scale system was
Ca(OH)2
mainly dominated by heat and mass transfer limitations originating from the small particle size and
Nano particles
Flowability
changes in the bulk properties. It is shown that by the addition of small amounts of additives like nano-
Ò

Moving bed particles of SiO2 (Aerosil ), the bulk properties can be stabilized and consequently the cycling stability
Thermochemical storage ensured. In addition, channelling effects can be minimized resulting in a more homogeneous flow
through the reaction bed improving the overall reaction behaviour of the thermochemical storage.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction The following equation shows the equilibrium reaction where

Constantly rising energy prices and increasing emissions of car-
bon dioxide necessitate a rethinking of how energy is used.
Thermal energy storage is one important cornerstone on the
CaðOHÞ2ðsÞ þ DHR
way to higher efficiency in industrial processes as well as for the
implementation of dispatchable regenerative energy especially in
concentrated solar power (CSP) plants [1,2]. Heat storage can be
divided into three different technologies: sensible, latent and
thermochemical.
Sensible heat storage has been most researched and is already
employed e.g. in solar power plants as two-tank molten salt stor-
age systems [3].
Latent storage makes use of the phase change of the storage
material. The operation of a 700 kW h storage generating steam
for 3000-h has been successfully demonstrated [4,5].
In comparison to sensible and latent heat storage systems,
thermochemical technologies are only in the initial phase of devel-
opment but show great potential with regard to energy density and
long-term storage behaviour [6–9].
The CaO/Ca(OH)2 reaction system has been investigated
extensively and is appropriate for thermal energy storage in a
temperature range of 400–600 °C [6,10,11].
⇑ Corresponding author. Tel.: +49 (0)711 6862 8045.
E-mail address: Christian.Rosskopf@dlr.de (C. Roßkopf).
DHR correspondents to the reaction enthalpy used to chemically
store the thermal energy.
CaOðsÞ þ H2 OðgÞ
During the charging process heat is supplied to the storage sys-
tem while water vapour is drawn out. During the discharging pro-
cess calcium oxide powder reacts with water vapour to calcium
hydroxide thereby releasing heat. In case of a directly operated
reactor, the heat is directly decoupled by a heat transfer fluid
(HTF). This means that the HTF flows through the bed and is in
direct contact with the powder. An advantage of this system is
the large heat exchange area between the particle surface and
the HTF. However, fast discharging demands a high HTF velocity
leading to a high pressure drop in the reaction bed due to the
low permeability of the powder bed. To avoid this problem either
the particle diameter has to be increased which is difficult due to
the volume change of the particles during the reaction or the
porosity of the reaction bed has to be increased. The main problem
occurring especially during the cycling of the thermochemical stor-
age is the worsening of the reaction material [12,13]. After two
cycles, small agglomeration lumps begin to form, growing in size
from cycle to cycle and therefore constant thermophysical bed
properties cannot be guaranteed. Fig. 1 shows an agglomerate of
calcium hydroxide after 4 cycles in the lab-scale reactor. Due to
the mechanical stability of this agglomerate, it grows continuously
at each cycling step.

http://dx.doi.org/10.1016/j.enconman.2014.05.017
0196-8904/Ó 2014 Elsevier Ltd. All rights reserved.
94 C. Roßkopf et al. / Energy Conversion and Management 86 (2014) 93–98
Fig. 1. Calcium hydroxide agglomerate after 4 cycles in the laboratory reactor.
Accordingly, a homogeneous flow of the reaction and HTF gases
through the fixed reaction bed is not possible. A large fraction of
the HTF passes the reaction bed through wide channels within
the bed. Therefore an optimum mass and mainly heat transfer is
not ensured. Transfer of the HTF into the agglomerates is insuffi-
cient due to their low permeability. Fig. 2 shows a powder bed of
Ca(OH)2 at ambient temperature while N2 flows through it from
bottom to top within a glass tube. Even though the material has
not reacted yet, the channels demonstrate the cohesiveness of this
powder.
In order to solve the problem of agglomeration one option is to
reduce the attractive forces between the particles. This can be
achieved on one hand by pelletizing the fine powder which is dif-
ficult due to the volume change of the single particles during the
reaction of the material. Another possibility to minimize these
forces is to increase the surface roughness by coating the surface
of the particles with additives. In bulk industries nanoparticles
are used in order to increase these roughness and consequently
Fig. 2. Channeling effects within the powder bed of Ca(OH)2 at ambient
temperature.
minimize the contact area between particles to improve the flow
behaviour of powder beds [14]. For thermochemical heat storage,
a usage of nanoparticles in order to improve reaction behaviour
is not known in literature. Nevertheless, Valverde et al. inserted
nanoparticles to Ca(OH)2 bulk powder in order to increase the
fluidization behaviour and reactivity for CO2 absorption [15–19].
Contrary to Valverde et al. who add a ratio of guest particles up
to 30% and coat these nanoparticle agglomerates with Ca(OH)2, this
contribution shows the coating of Ca(OH)2 with nanoparticles to
preserve the high storage capacity. To this end much less material
is added. This paper therefore reports on the experimental results
in a reactor with direct heat transfer and analyses the effects of the
addition of SiO2 nanoparticles on agglomeration and channelling.
Wang also investigated the enhancement of reactivity for CO2 cap-
ture with Li4SiO4-based sorbents by adding SiO2 nanoparticles [20].
2. Material and methods
2.1. Lab-scale reactor
A directly heated lab-scale reactor is used for cycling experi-
ments and analysing the reaction behaviour. The flow chart of
the test bench is presented in Fig. 3 with additional details given
in [12].
A nitrogen flow (0–75 Nl/min) is heated up to the required
temperature of 600 °C. Distilled water (0–1000 g/h) can be evapo-
rated, overheated and added to the nitrogen flow in a mixing
chamber. This mixture flows either through the thermochemical
reactor from bottom to top or through a bypass. A dew point meter
after the reactor outlet measures the steam content in the gas mix-
ture whereby the conversion during the reaction process can be
determined. The H2O pressure can be calculated by the equation
of Sonntag which is described in detail in [12]. A maximum theo-
retical error of 0.1 K can be assumed with this measurement proce-
dure and is taken into account in the standard deviation of the
conversion. By means of a back pressure regulator the absolute
pressure within the reactor can be controlled. Fig. 4 shows a pic-
ture of the thermochemical reactor and the positions of the Typ
K thermocouples with a diameter of 1 mm and a maximum mea-
suring inaccuracy of 0.1 °C inside.
The diameter of the reaction zone within the reactor is 54.5 mm
and its height measures 158 mm.
The reactor is equipped with thermocouples which are placed
at the central axis and close to the reactor wall within the reaction
bed.
The reactor is filled with 60 g of Ca(OH)2 which correspondents
to a chemically stored capacity of about 21 W h [13].
In order to investigate the influence of the additives on the
powder, the discharging process is considered. Here, the reactor
is preheated to the starting temperature of 300 °C. By means of
the back-pressure regulator the absolute pressure in the reactor
is set in advance. The valve in front of the reactor is closed and
the gas flow is directed through the bypass. Then, the desired
water vapour/nitrogen mixture of nH2O = 0.4 is adjusted. As soon
as the dew point meter outputs a constant signal, the valve in front
of the reactor is opened and the gas mixture flows through the
reactor defining the starting point t = 0 for the experiment.
2.2. CaO/Ca(OH)2
For the investigation of the influence of the additives white
hydrated lime Ca(OH)2 by HeidelbergCement, Germany is used.
White hydrated lime is a fine powder whose main commercial
application is in the production of mortar. The most important
key data are the true density of 2200 kg/m3, the bulk density of
 C. Roßkopf et al. / Energy Conversion and Management 86 (2014) 93–98 95

Fig. 3. Set-up of the test bench.

Fig. 4. Lab-scale reactor, photographic image (left) and position of powder bed and thermocouple (right).

450 kg/m3, the mean diameter d50 of 5 lm and the purity of
97.8%. The hydroxide form of the material Ca(OH)2 was chosen
as starting material due to the less harmful handling compared
to CaO and to start the cycling with a shrinking reaction bed
instead of an expanding reaction bed.
2.3. Additive
As outlined above, the attractive forces of the reacting particles
are decreased by increasing the roughness of their surface [21,22].
In order to resist the high thermal stresses and to avoid side reac-
tions as well as transformations, fumed silica SiO2 that is thermally
stable up to 1000 °C and moderately reactive is used.
In bulk material technology and pharmaceutical industries, sil-
ica nanoparticles are commonly used to reduce adhesive forces in
Ò
bulks of fine particles. In this work the hydrophilic Aerosil 300 is
used for experiments in the thermochemical storage reactor. The
mean size of the primary particles is about 7 nm. The surface of
Ò
Aerosil 300 is smooth and nonporous and the solid density is
similar to the one of calcium hydroxide [23]. The nanoparticles
are deposited on the surface of calcium hydroxide by means of a
magnetic stirrer with agitator in a dry process. The standard mix-
ing time is 30 min.
3. Results and discussion
In order to assess the flow-through characteristics, the reaction
bed is first investigated in a glass tube at ambient temperature
(Fig. 5). The velocity of the nitrogen flowing through the bed from
bottom to top corresponds to the velocity in the lab-scale reactor
and is assumed not leading to a fluidization of the bed.
The strong channelling effects observed in Fig. 2 already disap-
pear by the addition of 2 wt% of nanoparticles. However, the poros-
Ò
ity of the powder bed rises with increasing amount of Aerosil as
highlighted in [18]. In the unmodified powder bed, most part of
the nitrogen flow passes the bed through these wide channels
which present less resistance to the flow. With the minimization
of the channels the flow is forced to pass the whole reaction bed
96 C. Roßkopf et al. / Energy Conversion and Management 86 (2014) 93–98
Fig. 5. Powder bed with addition of two percent of Aerosil nanoparticles at ambient
temperature.
through very narrow passages leading to a rising pressure drop
compared to the unmodified bed. In order to investigate the
influence on the storage the effects on the bulk material are
investigated within the lab-scale reactor.
In the following experiments the discharging process of the
lab-scale reactor is considered. The procedure is carried out as
mentioned above. Fig. 6(left) shows the temperature development
at T7 within the powder bed of the hydration process in the
lab-scale reactor.
The reactor is heated up uniformly to a temperature of 300 °C
and the pressure within the reaction chamber is adjusted to
2 bar g. After switching the mixed flow from the bypass to the
reactor, the hydration process starts (at t = 0). The temperature of
the whole reaction bed jumps instantaneously to the equilibrium
temperature of 500 °C. The duration of the complete reaction
process can be approximated by the temperature development
within the reaction bed (T7 in Fig. 6(left)). The process seems to
be completed when T7 equals the starting temperature. However,
Fig. 6. Temperature development (left) and reaction rate (right) during hydration of the unmodified material with T0 = in = 300 °C, P0 = out = 2 bar g and fH2O = 0.4.
by taking the reaction rate (Fig. 6(right)) measured via the dew
point meter into account, it can be seen that most of the conversion
is already completed after 2700 s.
At the beginning the reaction takes place in the whole bed until
the equilibrium temperature is reached. At this point, the conver-
sion rate reaches its maximum of 125 g H2O/h. Afterwards, the
reaction continues only at the section of the reaction bed where
the heat is dissipated. After 2700 s the rate of reaction is almost
negligible as only sensible heat is still stored within the reaction
bed. The decline of the temperature therefore correspondents to
the cooling of the bulk without chemical reaction. By integrating
this curve the overall conversion of the reaction can be determined
(compare [12]). The absorbed mass of H2O is 13.32 g where the
standard deviation was found to be 0.37 g. Taking the standard
deviation and the impurity of the material into consideration, full
conversion of the material can be assumed [12].
After investigating the reference case, the reaction of Ca(OH)2
Ò
with addition of Aerosil is analysed. The conditions are exactly
Ò
the same, except that 0.5 wt% of Aerosil is added to the calcium
hydroxide powder by means of a dry coating process. Fig. 7(left)
and (right) shows corresponding to Fig. 6(left) and (right) the
temperature development and the reaction rate of the discharging
process for the modified calcium hydroxide.
The immediate rise of the bulk temperature to the equilibrium
temperature can also be observed in the modified bed. However,
the reaction is faster since the initial temperature is reached in
about half the time. The development of the reaction rate also con-
firms the faster reaction behaviour since after 100 s 11.06 g have
reacted compared to 9.44 g H2O for the unmodified material. The
absorbed mass of water at the end of reaction equals 13.28 g with
a standard deviation of 0.37 g confirming a full conversion. Com-
paring the reference material with the modified one, the consider-
ably faster reaction behaviour as well as the faster cooling of the
bulk is notable since only the material has been changed. It can
be concluded that a reduction of channelling was also possible in
the lab-scale reactor leading to a more homogeneous distribution
of the HTF inside the bulk.
Therefore, with the addition of nanoparticles the heat transfer
into the gas is clearly increased resulting in faster cooling of the
reaction bed and overall faster dynamics of the reactor.
In addition to the promising results of the thermochemical stor-
age behaviour of the modified material, the cycling stability of this
effect is analysed. Fig. 8 shows the temperature developments of
the hydration processes of eight consecutive cycles.
These cycling processes are carried out using the same proce-
dure as in the previous experiments. For the dehydration of the
material the reactor is heated up to 500 °C and the reactor is
purged by nitrogen. After 10 cycles, the reaction material is taken
 C. Roßkopf et al. / Energy Conversion and Management 86 (2014) 93–98 97

Fig. 7. Temperature development (left) and reaction rate (right) during hydration with T0 = in = 300 °C, P0 = out = 2 bar g and fH2O = 0.4 with addition of 0.5 wt% Aerosil.

out of the reactor in its hydrated state. The mass loss after treat-
ment in an oven (nitrogen atmosphere) at 600 °C amounts to
13.1 g with a measure uncertainty of the scales of 0.01 g which
means that the whole material has been fully converted. The tem-
perature developments of the single cycles remain almost
unchanged leading to the assumption that the nanoparticles are
stable on the particle surface.
To confirm this observation a SEM picture of the surface after
this cycling is taken (Fig. 9).
In the SEM view the nanoparticles can be clearly seen on the
surface (branched structures). No change of structure or coating
behaviour can be noticed. Based on the cycling stability in the reac-
Ò
tor and the visual confirmation by the SEM, the Aerosil is assumed
to be stable. Nevertheless this stability has to be proven by other
material characterization methods at significantly more cycles.
Summarizing, it can be noted that agglomeration effects within
fine powder bulks can be minimized by addition of small amounts
of nano scaled additives (Fig. 10) and cycling stability during ther-
mochemical operations has been demonstrated for 10 cycles.
Additionally, due to reduced adhesive forces between the parti- Fig. 9. SEM picture of Ca(OH)2 particle mixed with 5 wt% of Aerosil after three
cycles in the lab scale-reactor.
cles cohesiveness within the powder bed is reduced leading to
improved flow-through characteristics. Consequently, the mass
and heat transfer in the reaction bed as well as the applicability
for thermochemical storage are enhanced. Nevertheless, further
extensive investigations of processes during chemical reaction
and influences for thermochemical storage behaviour have to be
performed.

Fig. 10. Calcium hydroxide powder with 0.5 wt% Aerosil after 4 cycles in the lab-
scale reactor.

4. Conclusions

Fig. 8. Temperature developments during eight hydration cycles with addition of Thermochemical systems offer high energy densities and long-
0.5% Aerosil. term storage possibilities due to the chemically stored thermal
98 C. Roßkopf et al. / Energy Conversion and Management 86 (2014) 93–98
energy. However, due to the generally fine powdered material and
its potentially cohesive character, an application is hindered due to
an easy formation of bulk inhomogeneity like e.g. agglomeration. It
has been shown that the addition of a small amount of hydrophilic
Ò
Aerosil prevents agglomeration during the cycling of CaO/Ca(OH)2
without having a negative influence on the reaction dynamics.
Thus, the cycling stability of the powder bed within 8 cycles is
demonstrated and confirmed by SEM pictures. This leads to a sig-
nificantly improved heat and mass transfer within the experimen-
tal reactor and the charging and discharging times of the storage
are considerably reduced. Therefore, the possibility to improve
the cycling stability of bulk properties during thermochemical
cycles could be transferred to different applications dealing with
fine-powdered material. However, due to the chemical reactions
and the changing atmosphere investigations of cycling stability
have to be extended.
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