Development of a Moving Bed Pilot Plant for

Thermochemical Energy Storage with CaO/Ca(OH)2

Matthias Schmidt1, a, Marie Gollsch1, Franz Giger 2, Manfred Grün2, Marc Linder1
1
German Aerospace Center – DLR e.V., Institute of Engineering Thermodynamics, Germany
2
Bühler AG, Gupfenstraße 5, 9240 Uzwil, Switzerland
a)
Corresponding author: Matthias.Schmidt@dlr.de

Abstract

Thermochemical energy storage, for instance with Ca(OH)2, offers high energy densities at low material costs and could
therefore be a promising storage alternative for CSP-plants. Yet, due to the low thermal conductivity of the Ca(OH)2
material large storage capacities operated in an indirectly heated fixed bed also require large heat exchangers. In other
words the fixed bed concept somehow opposes one of the main advantages of Ca(OH)2, its low material costs. One
approach to overcome this issue is to detach the costly reactor with the heat exchanger (power) from the storage material
(capacity). This can be accomplished by a moving bed concept where the material moves through the reactor. Therefore a
novel moving bed pilot plant was developed within the consortium of the European project TCS Power. The pilot plant
was set into operation and revealed important information about the material flow through the reactor and the operation
strategy of a moving bed concept.

INTRODUCTION

Efficient thermal energy storage systems for high temperature are one of the key components for dispatchable
renewable power at reasonable costs. Due to the good availability at low cost and its favorable temperature range
current work at DLR focused on hydrated quick lime as thermochemical storage material (calcium hydroxide):

CaO(s) + H2O(g) ↔ Ca(OH)2(s)+ ∆Hreaction (1)

The reaction has already been investigated in the early 80´s [1, 2] and complete reversibility and cycle stability
of the reaction has been demonstrated [3]. Additionally, due to its fast effective reaction kinetics, the high reaction
enthalpy of 100 kJ/mol and the temperature range between 400 °C and 600 °C, the system is a promising candidate
for a thermal energy storage system in CSP-plants.
In order to investigate the reaction system, a multifunctional test bench as well as an indirectly operated fixed
bed reactor for 25 kg Ca(OH)2 was developed and set into operation at DLR. With the experimental set up the
feasibility to store energy thermo-chemically on a technically relevant scale (10 kW – 25 kg material) was
demonstrated [4]. The applied design simulation model was validated [5] and possible operation modes of the
systems were identified experimentally. Pardo et al. recently investigated the reaction system in a fluidized bed
reactor [6].
However, regarding the development of thermochemical storage systems for large capacities, a moving bed
concept was identified as one possibility to decouple the costly reactor from the inexpensive storage capacity. To
realize such a concept it is necessary to move the material through the reactor. Ca(OH)2 is a fine, cohesive powder
(d50 = 5 µm), hence its flowability is in general very poor. Additionally, the thermal conductivity of the material is
low, therefore only a short distance between the particles and the heat exchanger surface can be allowed in order to
reach sufficient heat flux into the reaction bed. Even though a coating of the Ca(OH)2 material with nano additives
has been recently identified as a possible way to improve the material properties of the bulk [7]the design of a heat
exchanger for moving Ca(OH)2 particles under reaction condition is challenging and has not yet been addressed.

DESIGN CONSTRAINTS FOR THE PILOT PLANT

Regarding the intended application as a storage system for parabolic through or molten salt tower CSP-plants the
following design constraints have been defined for the development of the pilot plant:

 Demonstration of a storage capacity of 100 kWh (270 kg of storage material)

 Theoretical possibility of an “unlimited” enlargement of the storage capacity
 10 kW thermal power of the reactor
 Operating temperature 300 – 550°C
 Operating pressure 0,1-2 bar

In parabolic through as well as molten salt tower plants the heat transfer medium is liquid. This implies that in the
heat exchanger the heat transfer fluid must be physically separated from the storage material. As a consequence an
indirectly heated reactor concept is considered.

MATERIAL DEVELOPMENT

Enhancement of Flowability Through Nano-Additives

A recent study [7] investigated the influence of coating calcium hydroxide with SiO2 nanoparticles on the bulk
properties. It was shown that coating with nanoparticles prevents agglomeration of the material due to reduction of
cohesive forces between the particles. But besides this positive effect also unfavourable side reactions between the
SiO2 particles and the Ca(OH)2 did occur during cycling. The formed side product is Ca5(SiO4) and does not react in
the desired operating range of the Ca(OH)2 storage system [7]. As a result the rate of conversion of the modified
material is clearly reduced.
To overcome this issue mixtures of Ca(OH)2 with different nano-additives have been investigated regarding their
influence on the flowability of the bulk and on the reaction. In summary all of the tested nano-additives could
improve the flowability but also formed reactive or inertial side products during cycling. The determination of the
side products and their influence on the reaction is still ongoing. Out of the first results a Al2O3 nano particle product
was chosen as an additive for operation of the moving bed pilot plant. The mixture with Al2O3 seems to be stable
during cycling and shows a higher rate of conversion compared to a mixture of Ca(OH)2 and SiO2 nano particles
even though the amount of additive needed to improve the flowability is significantly higher. FIGURE 1 shows the
level of conversion achieved over 10 cycles of two mixtures consisting of Ca(OH)2 with 6 w% SiO2 respectively 12
w% Al2O3 compared to pure Ca(OH)2. It can clearly bee seen that the level of conversion of the mixture with Al2O3
is significantly higher as well as more stable over 10 cycles compared to the mixture with SiO2. Therefore, for the
investigations with the pilot plant approximately 450 kg of Ca(OH)2 were prepared using 12 w% Al2O3 as nano-
additive.
 FIGURE 1. Level of conversion for pure Ca(OH)2 and two mixtures with nano particles

Material Flow Tests

In order to assess possible designs of the heat exchanger in the reactor the flow behavior of the storage material
through two different geometries was tested. One approach was to have the material flow through a rectangular gap
between two plates. The heat transfer fluid would run inside the plates delivering the thermal energy to the storage
material. A second approach was to have the material flow inside the tubes of a tube bundle heat exchanger whilst
the heat transfer fluid would run on the shell side. The material flow of both concepts was tested in two cold
geometry models.
FIGURE 2 (a) shows the material flow through the rectangular gap with a width of 20 mm. As it can be seen the
material flow in the rectangular gap was distributed inhomogeneously. This inhomogeneity is directly related to the
inhomogeneous material transport of the screw conveyers at the outlet of the gap. Thus a homogenous flow through
the rectangular gap could only be reached by applying an additional rotating spline at the outlet of the gap.

(a)
(b)
FIGURE 2. Material flow of nano coated Ca(OH)2 through a rectangular geometry (a) and a tube (b)

FIGURE 2 (b) shows the material flow through a tube with an inner diameter of 28 mm. In this case a
homogenous flow through the tube could be reached without any additional distribution devices. Therefore a tube
geometry was considered for the development of the moving bed reactor.
 Reaction Gas Distribution
For the design of the reactor it is important to ensure that the reaction gas, water vapour, is able to flow through
the material bulk without a significant pressure drop. A loss in pressure over the material bulk directly results in a
reduced reaction temperature. As a consequence the power of the reactor decreases. To identify a length of the tube
with reasonable pressure drop, simlations using Comsol Multiphysics have been performed.
For these simulations a tube with an inner diameter of 28 mm and a length of 400 mm filled with a bulk of the
storage material with a permeability of 1*10-11 m² was assumed. The pressure at the inlet is constant and the material
“consumes” water vapour due to the hydration reaction. Consequently, the mass flow of reaction gas is induced by
the material itself. Two cases were analyzed where in the first case the reaction gas inlet of 1 bar water vapor was
only at the bottom of the tube and in the second case the reaction gas inlet was placed at the top and the bottom of
the tube.
FIGURE 3 (a) shows the pressure distribution wihtin the tube when the reaction gas can enter only at the bottom
of the tube. It can be seen that along the length of the tube (from the bottom to the top) a significant pressure loss
occurs. Whereas at the reaction gas inlet the gas pressure is 1 bar (red area) the pressure at the top of the tube is
reduced to 0,27 bar (blue area). According to the equilibrium line of the reaction such a pressure drop would result
in a decrease of the reaction temperature from 500°C to 400°C and is therefore unaccaptable.

(a) (b)
FIGURE 3. Simulation of pressure loss of reaction gas in the tube (a) reaction gas inlet only at the bottom of the tube (b)
reaction gas inlet at bottom and top of the tube

FIGURE 3 (b) shows the pressure distribution in the tube where the reaction gas enters at the top and the bottom
of the tube. It can bee seen that at both gas inlets the reaction gas pressure is assumed as 1 bar (red area). The
pressure reduces on the way into the tube reaching a minimum pressure of 0,91 bar in the center of the tube.
Accordingly the maximum pressure loss for case (b) is only ~ 0,1 bar compared to ~ 0,7 bar for case (a). As a
consequence the reaction gas in the pilot reactor will be feed in at the top and the bottom of the tube bundle.

PILOT PLANT DEVELOPMENT

Reactor Design
Due to the performed material flow tests through different geometries it was decided to design a tube bundle heat
exchanger as core of the moving bed reactor. FIGURE 4 (a) shows the basic design of the heat exchanger. The
storage material flows in 158 tubes with an inner diamter of 28 mm. On the shell side of the heat exchnager the heat
transfer fluid air flows in conuter-current direction. It enters the reactor at the connection at the right side and flows
around the tubes directed by six baffle plates. The outlet of the heat transfer fluid leaves the reactor at the opposite
side. With an overall heat transfer area of 5 m² the heat exchanger is designed to transfer a power of 10 kW at a
nominal airflow of 160 Nm³/h and a temperature difference between air in- and outlet of 200 K.

(a) (b)

FIGURE 4. Heat exchanger for moving particles and air (a); moving bed reactor (b)

FIGURE 4 (b) shows the complete reactor consisting of three attachable parts. First part is the top of the reactor
where the material inlet is located. In the top is also an additional flange connection where the reaction gas can enter
the reactor above the tube bundle. A 2 µm filter sieve prevents the material from flowing into the reaction gas unit.
Two sensors, one optical and one mechanical, measure the bulk height above the tubes. The sensors give a signal
when the material level in the reactor reaches a certain height. Based on this signal the mass flow through the reactor
will be adjusted. An arm is rotating over the tube bundle in order to distribute the material homogeneously from the
eccentric material inlet.
The middle part of the reactor is the heat exchanger shown in detail in FIGURE 4 (a). To drive the
thermochemical reaction, thermal energy will be exchanged between the heat transfer fluid on the shell side and the
material moving downwards inside the tubes.
In the bottom of the heat exchanger the outlet area of the reactor is attached. In this part an additional connection
is foreseen to supply or remove reaction gas from below the tube bundle. In the flat bottom area a rotating scraper is
installed to move material from the outer tubes to the outlet cross section located in the center. The outlet cross
section has a diameter of DN 100 and a rotary valve is attached there. Through the speed of the rotary valve the
mass flow through the reactor can be controlled.

Pilot Plant Design and Control Strategy

FIGURE 5 shows the design of the moving bed pilot plant including transport and storage facilities for the
material. In the first storage container approximately 270 kg of Ca(OH)2 material can be stored. The container is
placed on a load cell to measure the mass flow feed into the plant. With a rotary valve under the container this mass
flow can be adjusted. The material is then transported via a screw feeder into the gas lock situated above the reactor
inlet. In the gas lock the atmosphere between the storage container and the reactor atmosphere can be exchanged.
The particles then fall out of the gas lock into the reactor. While the particles move through the tube bundle, thermal
energy is delivered by the heat transfer fluid (air) driving the reaction of the material. The reaction gas is supplied
into the reactor at the connections at the top and the bottom of the reactor. Once the material has reacted it leaves the
reactor and is transported to the outlet gas lock where again the atmosphere of the reactor is changed to ambient
atmosphere. The material is then transported into the product container. The two containers can then be exchanged
to conduct the reverse reaction.
 FIGURE 5. Pilot plant for moving bed reactor

FIGURE 6 shows the integration of the pilot plant (yellow) into the existing test facility for thermochemical
storage systems at DLR. The moving bed reactor is connected to the heat supply unit (green) which is able to deliver
an air flow of 160 Nm3/h at temperatures up to 1000 °C. Additionally the two reaction gas inlets of the reactor are
connected to the condenser/ evaporator unit (blue). With the condenser it is possible to adjust a water vapor
atmosphere between 0.1 and 2 bar in the reactor. The change of the water level in the condenser is measured giving
the level of conversion in the reactor.

Moving bed pilot Heat supply

plant (FIGURE 5) unit

Evaporator/ condenser

FIGURE 6. Integration scheme of the pilot plant into existing thermochemical test bench at DLR
 CONCLUSION
For the scale-up of thermochemical storage systems to large capacities required e.g. in CSP-plants it is important
to detach the costly reactor with the heat exchanger (power) from the storage material (capacity). In this work an
indirectly heated moving bed concept realized in 10 kW / 100 kWh scale is presented.
Ca(OH)2 is a very cohesive powder and shows poor ability to flow gravity assisted. Coating Ca(OH)2 with nano-
additives proved to be a possibility to facilitate free flow of the bulk material. Nevertheless all of the additives
investigated so far also formed inertial or reacting side products during cycling. In summary the admixture of 12 w%
Al2O3 showed the highest heat development of still 88 % as well as 78 % conversion compared to pure Ca(OH)2 and
was therefore chosen as additive for the storage material for the pilot plant. 450 kg of Ca(OH)2 mixed with 12 w%
Al2O3 were produced for the operation of the pilot plant.
Cold flow test with the modified material revealed that a homogenous flow through a tube with an inner diameter
of 28 mm can be achieved. A simulation analysis showed that if the reaction gas is supplied above and below the
tube bundle an acceptable pressure drop can be realized.
Based on these preliminary studies a moving bed reactor with a tube bundle heat exchanger with a thermal power
of 10kW was developed. Besides the reactor also the necessary infrastructure to store and transport up to 270 kg
Ca(OH)2 was designed and set into operation. Future work will address the experimental analysis of the material
flow in the moving bed reactor during ongoing reaction. The operation of the pilot plant will reveal important
information about possible operation strategies of moving bed thermochemical storage systems.

ACKNOWLEDGMENTS

This work has been partially funded by the European Commission under the 7th Framework Programme in the
frame of the TCS-Power project under contract 282889.

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